BRPI0919323B1 - POLYOL METHODS AND COMPOSITIONS POLYCARBONATE - Google Patents

Abstract

POLYCARBONATE POLYOL METHODS AND COMPOSITIONS In one aspect, the present disclosure includes polymerization systems for the copolymerization of CO2 and epoxides comprising 1) a catalyst including a metal coordination compound having a permanent linker set and at least one linker that is a polymerization initiator, and 2) a chain transfer agent with two or more sites that can initiate polymerization. In a second aspect, the present disclosure encompasses methods for the synthesis of polycarbonate polyols using the polymerization systems of the invention. In a third aspect, the present disclosure encompasses polycarbonate polyol compositions, characterized in that the polymer chains have a high percentage of terminal -OH groups and a high percentage of carbonate linkages. The compositions are further characterized in that they contain polymer chains having a polyfunctional moiety embedded in a plurality of individual polycarbonate chains.

Description

Priority Claim

This application claims priority from U.S. Provisional Patent Application Serial No. 61/095,178, filed on September 8, 2008, the entire contents of which are incorporated herein by reference.

Background

Aliphatic polycarbonates (APCs) are useful as polyol building blocks for the construction of copolymers, such as flexible polyurethane foams, urethane coatings, rigid urethane foams, urethane/urea elastomers and plastics, adhesives, polymer coatings and surfactants, among others.

Examples of such APCs include (poly)propylene carbonate (PPC), (poly)ethylene carbonate (PEC), (poly)butylene carbonate (PBC); and (poly)cyclohexene carbonate (PCHC), as well as copolymers of two or more of these.

For usefulness in these applications, it is preferable that all ends of the polycarbonate polymer chains terminate with hydroxyl groups. Such hydroxyl groups serve as reactive portions for crosslinking reactions or act as sites where other blocks of a copolymer can be built. This is problematic if a portion of the chain ends in the APC are not hydroxyl groups, as this results in incomplete crosslinking or block copolymer termination. A typical specification for aliphatic polycarbonate polyol resins for use in such applications is that at least 98%, or in some cases more than 99%, of the chain ends terminate in hydroxyl groups. Furthermore, these applications typically require relatively low molecular weight oligomers (e.g., polymers with average molecular weight numbers (Mn) between about 500 and about 15,000 g/mol). It is also desirable that the 5 polyols have a finely defined molecular weight distribution – for example, a polydispersity index of less than about 2 is desirable, but much narrower distributions (i.e., PDI <1.2) may be advantageous. Furthermore, for certain 10 applications, polycarbonate polyols with little or no contamination with ether linkages are desirable.

Aliphatic polycarbonates can be conveniently synthesized by copolymerization of carbon dioxide and epoxides, as shown in Scheme 1.

Currently, there are several catalytic systems used for such syntheses, namely: heterogeneous catalyst systems based on aluminum or zinc salts; double metal cyanide (DMC) catalysts; and homogeneous catalysts based on coordination complexes of transition metals or aluminum.

Catalytic systems using heterogeneous aluminum or zinc salts are typified by those first described by Inoue in the 1960s (e.g., in U.S. Patents Nos. 3,900,424 and 3,953,383). Further improvements to these catalysts have been made over the years (e.g., as described in W. Kuran, et al. Chem. Macromol. Chem. Phys. 1976, 177, pp. 11-20 and Gorecki, et al. J. Polym. Sci. Part C 1985, 23, pp. 299-304). However, these catalyst systems are generally not suitable for the production of polyol resins with the low molecular weights and limited polydispersity required by many applications. The catalysts are of relatively low activity and produce high molecular weight polymers with broad polydispersity. Furthermore, the polycarbonates produced by These catalysts have a significant proportion of ether linkages in the chain, which may be undesirable in certain applications.

A second class of catalysts for the polymerization of epox and CO2 are double metal cyanide (DMC) catalysts. Such catalysts are exemplified by those reported by Kruper and Smart in U.S. Patent No. 4,500,704. Compared to Inoue-type catalysts, DMC systems are more suitable for the formation of low molecular weight polymers and produce a predominance of chains with hydroxyl terminal groups. However, these catalysts produce polymers having a high proportion of ether linkages, and the materials they produce are more accurately considered as polycarbonate-polyester copolymers rather than aliphatic polycarbonates per se.

A more recently developed class of catalysts is based on aluminum coordination complexes or a variety of transition metals, particularly cobalt, chromium, and manganese complexes. 30 Examples of such catalysts are disclosed in the Patents.

American Patents Nos. 6,870,004 and 7,304,172. In some cases, these catalytic systems are highly active and are capable of providing aliphatic polycarbonate with limited polydispersity, a high percentage of carbonate linkages, and good regional selectivity (e.g., high head-to-tail ratios for the incorporation of monosubstituted epoxides). However, at high conversions under standard conditions, these catalysts produce high molecular weight polymers, which are not suitable for many polyol applications. Furthermore, the use of these systems has not been practical for synthesizing polycarbonate polyols with a high percentage of hydroxyl terminal groups.

The lack of hydroxyl terminal groups is due to the fact that the anion(s) associated with the metal center of the catalyst complex become covalently linked to the polymer chain during the initial growth of the polymer chain. This is also true for the anions associated with any optionally present cationic co-catalysts used in these reactions. Without wishing to dwell on the theory, or to limit the scope of the present invention, the sequence shown in Scheme 2 shows a likely reaction sequence showing why the anions X) associated with the catalyst complex (denoted They become covalently bonded to the polycarbonate chain.

The counter ions typically used for these catalysts include halides, sulfonates, phenolates, carboxylates, and azides. Since polymerization is initiated when one of these anions opens an epoxide ring, one end of each polymer chain (the initiation end) is necessarily capped with a non-hydroxyl moiety such as a halogen, an alkyl sulfonate, a phenyl ether, an acyl group, or an azide, respectively.

The other factor that discourages the use of these catalytic systems for the production of polyol resins is the fact that they produce high molecular weight polymers when driven to high conversions. Typical molecular weights are in the range of 20,000 to 400,000 g/mol – values well above the desired molecular weight range for most polyol resin applications. Potential strategies for producing low molecular weight materials include: stopping the polymerization at low conversion; using high catalyst concentrations; degrading the high molecular weight polymer into shorter chains; or using chain transfer agents (CTAs), such as alcohols, during polymerization. Stopping the reaction at low conversion or increasing the catalyst concentration are undesirable due to the added costs and difficulties in purification caused by the higher concentration of catalyst-derived contaminants in the crude polymer. The degradation of higher molecular weight polymers to produce low molecular weight resins leads to increased polydispersity, adds additional steps to the production process, and leads to contamination with cyclic byproducts. Chain transfer agents can be successfully employed to decrease the molecular weight of the polymer without a significant increase in cost or contamination. However, this strategy does not alleviate the problem of non-hydroxyl terminal groups, since polymer chains initiated by the chain transfer agent still have an end capped with a non-hydroxyl moiety (i.e., an ether corresponding to the alcohol used as CTA).

Therefore, there continues to be a need for catalysts and methods that are capable of efficiently producing high-carbonate polycarbonate polyols.

Summary of the Invention

In one aspect, the present disclosure includes polymerization systems for the copolymerization of CO2 and epoxides comprising 1) a metal complex including a metal coordination compound having a permanent linker set 25 and at least one linker that is a polymerization initiator, and 2) a chain transfer agent with two or more sites that can initiate polymerization.

In some embodiments, a linker that is a polymerization initiator has two or more sites capable of initiating polymerization; this variation leads to polycarbonate polyols with an extremely high proportion of -OH end groups. In certain embodiments, the chain transfer agent and the linker that is a polymerization initiator are the same molecule (or ionic forms of the same molecule).

In certain embodiments, a polymerization system also includes a co-catalyst. In some embodiments, the co-catalyst is an organic cationic molecule. In certain embodiments, an anion present to balance the charge of a cationic co-catalyst is also a polymerization initiator having two or more sites that can initiate polymerization. In certain embodiments, the ligand that is a polymerization initiator, and the counter ion of the co-catalyst are the same molecule. In certain embodiments, the chain transfer agent, the ligand—which is a polymerization initiator—and an anion associated with a co-catalyst are the same molecule (or ionic forms of the same molecule).

In some embodiments, the present disclosure 20 includes methods for the synthesis of polycarbonate polyols.

In some embodiments, a method includes the steps of: 1) providing a reaction mixture that includes one or more epoxides and at least one chain transfer agent having two or more sites capable of initiating polymerization, 2) contacting the reaction mixture with a metal complex comprising a metal coordination compound having a permanent linker set and at least one linker that is a polymerization initiator, and 3) allowing the polymerization reaction to continue for a period of time sufficient for the average molecular weight of the polycarbonate polyol formed to reach a desired value. In some embodiments, the method further includes contacting the reaction mixture with a co-catalyst.

In some embodiments, the present disclosure covers polycarbonate polyol compositions characterized by the fact that the polymer chains have a high percentage of -OH terminal groups and a high percentage of carbonate linkages. These compositions are further characterized by the fact that the polymer chains contain within them a polyfunctional moiety linked to a plurality of individual polycarbonate chains. In certain embodiments, the polycarbonate polyol compositions are further characterized by having one or more of the following features: a carbonate-ether linkage ratio of at least 10:1, a head-to-tail ratio of less than 5:1, or a polydispersity index of less than 2. In certain embodiments of this aspect, a polymer composition is further characterized by the fact that a polymer contains a plurality of types of polymer chains differentiated by the presence of different polyfunctional polymerization initiators incorporated into the chain, or by differences in the terminal groups present in the polymer chains.

In certain embodiments, polycarbonate polyol compositions of the present disclosure are further characterized by the fact that they contain a mixture of two or more chain types, wherein the different chain types are distinguished from each other by differences in the identity of the incorporated polyfunctional polymerization initiators, the absence of incorporated polyfunctional polymerization initiators, or the presence of non-hydroxyl terminal groups in certain chains.

Definitions

The definitions of specific functional groups and chemical terms are described in more detail below. For the purposes of this invention, chemical elements are identified according to the Periodic Table of Elements, CAS version, Handbook of Chemistry and Physics, Ed. 75, back cover, and specific functional groups are generally defined as described herein. Furthermore, the general principles of organic chemistry, as well as specific functional groups and reactivity, are described in Organic Chemistry, Thomas Sorrell, University Science Books, Sausalito, 1999; Smith and March's Advanced Organic Chemistry, 5th Edition, John Wiley & Sons, Inc., New York, 2001; Larock, Comprehensive Organic Chemistry.

Transformations, VCH Publishers, Inc., New York, 1989; Carruthers, Some Modern Methods of Organic Synthesis, 3rd Edition, Cambridge University Press, Cambridge, 1987; the entire content of each of these is incorporated by reference in this document.

Certain compounds of the present invention may comprise one or more asymmetric centers, and thus may exist in various stereoisomeric forms, for example, enantiomers and/or diastereomers. Thus, the inventive compounds and compositions thereof may be in the form of an individual enantiomer, diastereomer or geometric isomer, or may be in the form of a mixture of stereoisomers. In certain embodiments, the compounds of the invention are enantiopure compounds. In certain other embodiments, mixtures of enantiomers or diastereomers are provided.

Furthermore, certain compounds, as described herein, may have one or more double bonds that may exist as the Z or E isomer, unless otherwise indicated. The invention further encompasses the compounds as individual isomers substantially free of other isomers and, alternatively, as mixtures of several isomers, for example, racemic mixtures of enantiomers. In addition to the compounds mentioned above by themselves, this invention also encompasses compositions comprising one or more compounds.

As used herein, the term "isomers" includes any and all geometric isomers and stereoisomers. For example, "isomers" include cis and trans isomers, E and Z isomers, R and S enantiomers, diastereomers, (D)-isomers, 15 (L)-isomers, racemic mixtures of the same and other mixtures of the same, as being within the scope of the invention. For example, a stereoisomer may, in some embodiments, be provided substantially free of one or more corresponding stereoisomers, and may also be referred to as "stereochemically enriched".

Where a particular enantiomer is preferred, it may, in some embodiments, be provided substantially free of the opposite enantiomer, and may also be referred to as "optically enriched". "Optically enriched", as used herein, means that the compound is formed from a significantly higher proportion of one enantiomer. In certain embodiments, the compound consists of at least about 90% by weight of a preferred enantiomer. In other embodiments, the compound consists of at least about 95%, 98% or 99% by weight of a preferred enantiomer. Preferred enantiomers may be isolated from racemic mixtures by any method known to persons skilled in the art, including chiral high-performance liquid chromatography (HPLC) and the formation and crystallization of chiral salts or preparations by asymmetric synthesis. See, for example, Jacques, et al. , Enantiomers, Racemates and Resolutions (Wiley Interscience, New York, 1981); Wilen, S. H., et al., Tetrahedron 33: 2725 (1977); Eliel, E. L. Stereochemistry of Carbon 10 Compounds (McGraw-Hill, NY, 1962); Wilen, S. H. Tables of Resolving Agents and Optical Resolutions p. 268 (E. L. Eliel, Ed., Univ, of Notre Dame Press, Notre Dame, IN 1972).

The terms "halo" and "halogen," as used herein, refer to an atom selected from fluorine (fluorine, -F), chlorine (chlorine, Cl-), bromine (bromine, -Br), and iodine (iodine, -I).

The term "aliphatic" or "aliphatic group," as used herein, denotes a hydrocarbon moiety that may be linear (i.e., unbranched), branched, or cyclic (including fused, bridged, and spiro-fused polycyclic) and may be fully saturated or may contain one or more unsaturation units, but which are not aromatic. Unless otherwise specified, aliphatic groups contain from 1 to 30 carbon atoms. In certain embodiments, aliphatic groups contain from 1 to 12 carbon atoms. In certain embodiments, aliphatic groups contain from 1 to 8 carbon atoms. In certain embodiments, aliphatic groups contain from 1 to 6 carbon atoms. In some embodiments, aliphatic groups contain from 1 to 5 carbon atoms, in some embodiments, aliphatic groups contain from 1 to 4 carbon atoms, in still other embodiments aliphatic groups contain from 1 to 3 carbon atoms, and in still other embodiments aliphatic groups contain 1 or 2 carbon atoms. Suitable aliphatic groups include, but are not limited to, linear or branched alkyl, alkenyl and alkynyl groups, and their hybrids, such as (cycloalkyl)alkyl, (cycloalkenyl)alkyl or (cycloalkyl)alkenyl.

The term "unsaturated," as used here, means that a portion has one or more double or triple bonds.

The terms "cycloaliphatic," "carbocyclic," or "carbocyclic," used alone or as part of a larger molecule, refer to saturated or partially unsaturated cyclic aliphatic monocyclic or polycyclic ring systems, as described herein, having from 3 to 12 members, wherein the aliphatic ring system is optionally substituted as defined above and described herein. Cycloaliphatic groups include, without limitation, cyclopropyl, cyclobutyl, cyclopentyl, cyclopentenyl, cyclohexyl, cyclohexenyl, cycloheptyl, cycloheptenyl, cycloctyl, cycloctenyl, norbornyl, adamantil, and cycloctadienyl. In some embodiments, the cycloalkyl has from 3 to 6 carbons. The terms "cycloaliphatic," "carbocycle," or "carbocyclic" also include aliphatic rings, which are fused to one or more aromatic or non-aromatic rings, such as decahydronaphthyl or tetrahydronaphthyl, where the radical or attachment point is on the aliphatic ring. In certain embodiments, the term "3- to 8-membered carbocycle" refers to a saturated or partially unsaturated 3- to 8-membered monocyclic carbocyclic ring. In certain embodiments, the terms "3- to 14-membered carbocycle" and "C3_i4 carbocycle" refer to a saturated or partially unsaturated 3- to 8-membered monocyclic carbocyclic ring, or a saturated or partially unsaturated 7- to 14-membered polycyclic carbocyclic ring. In certain embodiments, the term "C3_2o carbocycle" refers to a saturated or partially unsaturated monocyclic carbocyclic ring of 3 to 8 members, or a saturated or partially unsaturated polycyclic carbocyclic ring of 7 to 20 members.

The term "alkyl," as used herein, refers to saturated, linear or branched hydrocarbon chain radicals derived from an aliphatic moiety containing one to six carbon atoms by the removal of a single hydrogen atom. Unless otherwise specified, alkyl groups contain from 1 to 12 carbon atoms; in certain embodiments, alkyl groups contain from 1 to 8 carbon atoms; in certain embodiments, alkyl groups contain from 1 to 6 carbon atoms; in some embodiments, alkyl groups contain from 1 to 5 carbon atoms; in some embodiments, alkyl groups contain from 1 to 4 carbon atoms; in still other embodiments, alkyl groups contain from 1 to 3 carbon atoms; and in still other embodiments, alkyl groups contain from 1 to 2 carbon atoms. Examples of alkyl radicals include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, sec-pentyl, isopentyl, tert-butyl, n-pentyl, neopentyl, n-hexyl, sec-hexyl, n-heptyl, n-octyl, n-decyl, n-undecyl, dodecyl, and the like.

The term "alkenyl," as used in this document, denotes a monovalent group derived from an aliphatic portion of a linear or branched chain having at least one carbon-carbon double bond by the removal of a single hydrogen atom. Unless otherwise specified, alkenyl groups contain from 2 to 12 carbon atoms. In certain embodiments, alkenyl groups contain from 2 to 8 carbon atoms. In certain embodiments, alkenyl groups contain from 2 to 6 carbon atoms. In some embodiments, alkenyl groups contain from 2 to 5 carbon atoms, in some embodiments, alkenyl groups contain from 2 to 4 carbon atoms, in still other embodiments alkenyl groups contain from 2 to 3 carbon atoms, and in still other embodiments alkenyl groups contain 2 carbon atoms. Alkenyl groups include, for example, ethenyl, propenyl, butenyl, l-methyl-2-buten-l-yl, and the like.

The term "alkynyl," as used in this document, refers to a monovalent group derived from an aliphatic portion of a linear or branched chain having at least one carbon-carbon triple bond by the removal of a single hydrogen atom. Unless otherwise specified, alkynyl groups contain 2 to 12 carbon atoms. In certain embodiments, alkynyl groups contain 2 to 8 carbon atoms. In certain embodiments, alkynyl groups contain 2 to 6 carbon atoms. In some embodiments, alkynyl groups contain 2 to 5 carbon atoms, in some embodiments, alkynyl groups contain 2 to 4 carbon atoms, in still other embodiments, alkynyl groups contain 2 to 3 carbon atoms, and in still other embodiments, alkynyl groups contain two carbon atoms. Representative alkynyl groups include, but are not limited to, 30-ethynyl, 2-propynyl (propargyl), 1-propynyl, and the like.

The term "aryl" used alone or as part of a larger portion, such as "aralkyl", "aralkoxy" or "aryloxyalkyl" refers to monocyclic and polycyclic ring systems with a total of five to 20 ring members, wherein at least one ring in the system is aromatic and wherein each ring in the system contains from three to twelve ring members. The term "aryl" may be used interchangeably with the term "aryl ring". In certain embodiments of the present invention, "aryl" refers to an aromatic ring system that includes, but is not limited to, phenyl, biphenyl, naphthyl, anthracil and the like, which may contain one or more substituents. Also included within the scope of the term "aryl", as used herein, is a group in which an aromatic ring is fused with one or more additional rings, such as benzofuranil, indanil, phthalimidyl. In certain embodiments, the terms "6- to 10-membered aryl" and "C6-10 aryl" refer to a phenyl or a polycyclic aryl ring of 8 to 10 members. In certain embodiments, the term "6- to 12-membered aryl" refers to a phenyl or a polycyclic aryl ring of 8 to 12 members. In certain embodiments, the term "C6-14 aryl" refers to a phenyl or a polycyclic aryl ring of 8 to 14 members.

The terms "heteroaryl" and "heteroar-", used alone or as part of a larger group, for example, "heteroaralkyl" or "heteroaralkoxy", refer to groups having from 5 to 14 ring atoms, preferably 5, 6, or 9 ring atoms; with 6, 10, or 14 shared π electrons in a cyclic arrangement; and having, in addition to carbon atoms, from one to five heteroatoms. The term "heteroatom" refers to nitrogen, oxygen, or sulfur, and includes any oxidized form of nitrogen or sulfur, and any quaternized form of a basic nitrogen. Heteroaryl groups include, without limitation, tienyl, furanyl, pyrrolyl, imidazoles, pyrazolyl, triazolyl, tetrazolyl, oxazolyl, isoxazolyl, oxadiazolyl, thiazolyl, isothiazolyl, thiadiazolyl, pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, indolizinyl, purinyl, naphthyridinyl, benzofuranyl, and pteridinyl. The terms "heteroaryl" and "heteroar-", as used herein, also include groups in which a heteroaromatic ring is fused to one or more aryl, cycloaliphatic, or heterocyclyl rings, where the radical or point of attachment is on the heteroaromatic ring. Non-limiting examples include indolyl, isoindolyl, benzothienyl, benzofuranyl, dibenzofuranyl, indazolyl, benzimi-da-zo-l-i-1, benzothiazolyl, quinolyl, isoquinolyl, cinolinyl, phthalazinyl, quinazolinyl, quinoxalinyl, 4H-quinolizinyl, carbazolyl, acridinyl, phenazinyl, phenothiazinyl, phenoxazinyl, tetrahydroquinolinyl, tetrahydroisoquinolinyl, and pyrido[2,3-b]-1,4-oxazin-3(4H)-one. A heteroaryl group may be mono- or bicyclic. The term "heteroaryl" may be used interchangeably with the terms "heteroaryl ring," "heteroaryl group," or "heteroaromatic," any of which terms include rings that are optionally substituted. The term "heteroaryl alkyl" refers to an alkyl group substituted by a heteroaryl, wherein the alkyl and heteroaryl moieties are independently and optionally substituted. In certain embodiments, the term "5- to 10-membered heteroaryl" refers to a 5- to 6-membered heteroaryl ring with 1 to 3 heteroatoms independently selected from nitrogen, oxygen, or sulfur, or an 8- to 10-membered bicyclic heteroaryl ring having 1 to 4 heteroatoms independently selected from nitrogen, oxygen, or sulfur. In certain embodiments, the term "5- to 12-membered heteroaryl" refers to a 5- to 6-membered heteroaryl ring having 1 to 3 heteroatoms independently selected from nitrogen, oxygen, or sulfur, or an 8- to 12-membered bicyclic heteroaryl ring having 1 to 4 heteroatoms independently selected from nitrogen, oxygen, or sulfur.

As used herein, the terms "heterocycle," "heterocyclyl," "heterocyclic radical," and "heterocyclic ring" are used interchangeably and refer to a stable 7- to 14-membered polycyclic heterocyclic or 5- to 7-membered monocyclic heterocyclic moiety that is saturated—or partially unsaturated—and having, in addition to carbon atoms, one or more, preferably one to four, heteroatoms, as defined above. When used in reference to a ring atom of a heterocycle, the term "nitrogen" includes a substituted nitrogen. As an example, in a saturated or partially unsaturated ring having 0 to 3 heteroatoms selected from oxygen, sulfur, or nitrogen, the nitrogen may be N (as in 3,4-dihydro-2H-pyrrolyl), NH (as in pyrrolidinyl), or +NR (as in N-substituted pyrrolidinyl). In some embodiments, the term "3- to 7-membered heterocyclic" refers to a saturated or partially unsaturated monocyclic heterocyclic ring of 3 to 7 members with 1 to 2 heteroatoms independently selected from nitrogen, oxygen, or sulfur. In some embodiments, the term "3- to 8-membered heterocyclic" refers to a saturated or partially unsaturated monocyclic heterocyclic ring of 3 to 8 members having 1 to 2 heteroatoms independently selected from nitrogen, oxygen, or sulfur. In some embodiments, the term "3- to 12-membered heterocyclic" refers to a saturated or partially unsaturated monocyclic heterocyclic ring of 3 to 8 members with 1 to 2 heteroatoms independently selected from nitrogen, oxygen, sulfur, or a saturated or partially unsaturated polycyclic heterocyclic ring of 7 to 12 members having 1 to 3 heteroatoms independently selected from nitrogen, oxygen, or sulfur. In some embodiments, the term "3 to 14 membered heterocycle" refers to a saturated or partially unsaturated monocyclic heterocyclic ring of 3 to 8 members with 1 to 2 heteroatoms selected independently from nitrogen, oxygen, sulfur or a saturated or partially unsaturated polycyclic heterocyclic ring of 7 to 14 members having 1 to 3 heteroatoms selected independently from nitrogen, oxygen or sulfur.

A heterocyclic ring can be attached to its pendant group on any heteroatom or carbon atom, resulting in a stable structure, and any of the ring atoms can optionally be substituted. Examples of such saturated or partially unsaturated heterocyclic radicals include, without limitation, tetrahydrofuranil, tetrahydrothienyl, pyrrolidinyl, pyrrolidonyl, piperidinyl, pyrrolinyl, tetrahydroquinolinyl, tetrahydroisoquinolinyl, decahydroquinolinyl, oxazolidinyl, piperazinyl, dioxanil, dioxolanil, diazepinyl, oxazepinyl, thiazepinyl, morpholinyl, and quinuclidinyl. The terms "heterocycle," "heterocyclyl," "heterocyclyl ring," "heterocyclic group," "heterocyclic moiety," and "heterocyclic radical" are used interchangeably in this document, and also include groups where a heterocyclyl ring is fused to one or more aryl, heteroaryl, or cycloaliphatic rings, such as indolinyl, 3H-indolyl, chromanyl, phenantridinyl, or tetrahydroquinolinyl, where the radical or attachment point is on the heterocyclyl ring. A heterocyclyl group can be mono- or bicyclic. The term "heterocyclylalkyl" refers to an alkyl group substituted by a heterocyclyl, where the alkyl and heterocyclyl moieties are independently and optionally substituted.

As used herein, the term "partially unsaturated" refers to a portion of the ring that includes—at—least—one double or triple bond. The term "partially unsaturated" is intended to include rings with multiple unsaturation sites, but is not intended to include aryl or heteroaryl portions, as defined herein.

A person normally versed in the art will realize that the synthetic compounds and methods, as described herein, can utilize a variety of protecting groups. By the term "protecting group," as used herein, it is intended to mean that a particular functional moiety, for example, O, S, or N, is masked or blocked, allowing, if necessary, a reaction to be carried out selectively at another reactive site in a multifunctional compound. Suitable protecting groups are well known in the art and include those described in detail in Protecting Groups in Organic Synthesis, T. W. Greene and P. G. M. Wuts, 3rd edition, John Wiley & Sons, 1999, the entirety of which is incorporated herein by reference. In certain embodiments, a protecting group reacts selectively in good yield to produce a protected substrate that is stable to the designed reactions: the protecting group is preferably selectively removable by readily available, preferably non-toxic, reagents that do not attack other functional groups; The protecting group forms a separable derivative (more preferably without the generation of new stereogenic centers); and the protecting group will preferably have a minimum of additional functionality to avoid additional reaction sites. As detailed in this document, protecting groups of oxygen, nitrogen, sulfur, and carbon can be used. By way of non-limiting example, hydroxyl protecting groups include—methyl,-methoxymethyl (MOM), methylthiomethyl (MTM), t-butylthioethyl, (phenyldimethylsilyl)methoxymethyl (SMOM), benzyloxymethyl (BOM), p-methoxybenzyloxymethyl (PMBM), (4-methoxyphenoxy)methyl (p-AOM), guaiacolmethyl (GUM), t-butoxymethyl, 4-pentenyloxymethyl (POM), siloxymethyl, 2-methoxyethoxymethyl (MEM), 2,2,2-trichloroethoxymethyl, bis-(2-chloroethoxy)methyl, 2-(trimethylsilyl)ethoxymethyl (SEMOR), tetrahydropyranil (THP), 3-bromotetrahydropyranil, tetrahydrothiopyranil, 1-methoxycyclohexyl, 4-methoxytetrahydropyranil (MTP), 4- 25 methoxytetrahydrothiopyranyl, 4-methoxytetrahydrothiopyranyl S,S-oxide, 1-[(2-chloro-4-methyl)phenyl]-4-methoxypiperidin-4-yl (CTMP), 1,4-dioxan-2-yl, tetrahydrofuranyl, tetrahydrothiofuranyl, 2,3,3a,4,5,6,7,7a- octahydro-7,8,8-trimethyl-4,7-methanobenzofuran-2-yl, 1-ethoxyethyl, 1-(2-chloroethoxy)ethyl, 1-methyl-1-methoxyethyl, 1-methyl-1-benzyloxyethyl, 1-methyl-1-benzyloxy-2-fluoroethyl, 2,2,2-trichloroethyl, 2-trimethylsilylethyl, 2- (phenylselenyl)ethyl, t-butyl, alii, p-chlorophenyl, p-methoxyphenyl, 2,4-dinitrophenyl, benzyl, p-methoxybenzyl, 3,4-5 dimethoxybenzyl, o-nitrobenzyl, p-nitrobenzyl, p-halobenzyl, 2,6-dichlorobenzyl, p-cyanobenzyl, p-phenylbenzyl, 2-picolyl, 4-picolyl, 3-Methyl-2-picolyl N-oxide, diphenylmethyl, p,p'-dinitrobenzhydryl, 5-dibenzosuberyl, triphenylmethyl, α-naphthyldiphenylmethyl, p-methoxyphenyldiphenylmethyl, di (p-methoxyphenyl)phenylmethyl, tri(p-methoxyphenyl)methyl, 4-(4'-bromophenacyloxyphenyl)diphenylmethyl, 4,4',4"-tris(4,5-dichlorophthalimidophenyl)methyl), 4,4',4"- tris(levulinoyloxyphenyl)methyl, 4,4',4"- tris(benzyloxyphenyl)methyl, 3-(imidazol-1-yl)bis(4',4"- dimethoxyphenyl)methyl, 1,1 - bis (4 = methoxyphenylr)—I7-- pyrenylmethyl, 9-antryl, 9-(9-phenyl)xanthenyl, 9-(9-phenyl-10-oxo)anthryl, 1,3-benzodithiolan-2-yl, S,S-benzisothiazolyl dioxide, trimethylsilyl (TMS), triethylsilyl (TES), triisopropylsilyl (TIPS), dimethylisopropylsilyl (IPDMS), diethylisopropylsilyl (DEIPS), dimethyltexylsilyl, t-butyldimethylsilyl (TBDMS), t-butyldiphenylsilyl (TBDPS), tribenzylsilyl, tri-p-xylylsilyl, triphenylsilyl, diphenylmethylsilyl (DPMS), t-butylmethoxyphenylsilyl (TBMPS), formate, benzoylformate, acetate, chloroacetate, dichloroacetate, trichloroacetate, trifluoroacetate, methoxyacetate, triphenylmethoxyacetate, phenoxyacetate, p-chlorophenoxyacetate, 3-phenylpropionate, 4-oxopentanoate (levulinate), 4,4-(ethylenedithio)pentanoate (levulinoyldithioacetal), pivaloate, adamantoate, crotonate, 4-methoxycrotonate, benzoate, p-phenylbenzoate, 2,4,6-trimethylbenzoate (mesitoate), alkylmethylcarbonate, 9-fluorenylmethylcarbonate (Fmoc), alkylethylcarbonate, alkyl 2,2,2-trichloroethylcarbonate (Troc), 2-(trimethylsilyl)ethyl carbonate (TMSEC), 2-(phenylsulfonyl)ethylcarbonate (Psec), 25(triphenylphosphonium)ethylcarbonate (Peoc), alkylisobutylcarbonate, alkylvinylcarbonate alkylalylcarbonate, alkyl p-nitrophenylcarbonate, alkylbenzylcarbonate, alkyl-p-methoxybenzylcarbonate, alkyl 3,4-dimethoxybenzylcarbonate, alkyl-10-nitrobenzyl carbonate, alkyl p-nitrobenzyl carbonate, alkyl S-benzyl thiocarbonate, 4-ethoxy-l-naphthyl carbonate, dithiocarbonate methyl, 2-iodobenzoate, 4- azidobutyrate, 4-nitro-4-methylpentanoate, o-(dibromomethyl)benzoate, 2-formylbenzenesulfonate, 215(methylthiomethoxy)ethyl, 4-(methylthiomethoxy)butyrate, 2—(methylthiomethoxymethyl)benzoate, 2,6-dichloro-4-methylphenoxyacetate, 2,6-dichloro-4-(1,1,3,3-tetramethylbutyl)phenoxyacetate), 2,4-bis(1,1-dimethylpropyl)phenoxyacetate, chlorodiphenylacetate, 20 isobutyrate, monosuccinoate, (E)-2-methyl-2-butenoate, o-(methoxycarbonyl)benzoate, α-naphthoate, nitrate, N,N,N',N'-tetramethylphosphorodiamidate, alkyl N-phenylcarbamate, borate, dimethylphosphinothioyl, alkyl 2,4-dinitrophenylsulfenate, sulfate, methanesulfonate (mesylate), benzylsulfonate and tosylate (Ts). To protect 1,2- or 1,3-diols, protecting groups include methylene acetal, ethylidene acetal, 1-t-butylethylidene acetal, 1-phenylethylidene acetal, (4-methoxyphenyl)ethylidene acetal, 2,2,2-trichloroethylidene acetal, acetonide, cyclopentylidene acetal, cyclohexylidene acetal, cycloheptylidene acetal, benzylidene acetal, p-methoxybenzylidene acetal, 2,4-dimethoxybenzylidene acetal, 3,4-dimethoxybenzylidene acetal, 2-nitrobenzylidene acetal, methoxymethylene acetal, ethoxymethylene acetal, dimethoxymethylene orthoester, 1-methoxyethylidene orthoester, 1-ethoxyethylidyne orthoester. 1,2-dimethoxyethylidene, α-methoxybenzylidene orthoester, 1-(N,N-dimethylamino)ethylidene derivative, α-(N,N'-dimethylamino)benzylidene derivative, 2-oxacyclopentylidene orthoester, di-t-butylsilylene group (DTBS), 10 1,3-(1,1,3,3-tetraisopropyldissiloxanilidene) derivative (TIPDS), tetra-t-butoxydissiloxane-1,3-diylidene derivative (TBDS), cyclic carbonates, cyclic boronates, ethyl boronate and phenyl boronate. Aminoprotective groups include methyl carbamate, 15-ethyl carbamate, 9-fluorenylmethyl carbamate (FmQc), 9-(2-sulfo)fluorenylmethyl carbamate, 9-(2,7-dibromo)fluorenylmethyl carbamate, 2,7-di-t-butyl-[9- (10,10-dioxo-10,10,10,10-tetrahydrothioxantyl)]methyl (DBD-Tmoc), 4-methoxyphenacyl carbamate (Phenoc), 2,2,2-trichloroethyl carbamate (Troc), 2-trimethylsilylethyl carbamate (Teoc), 2-phenylethyl carbamate (Hz), 1-(1-adamantyl)-1-methylethyl (Adpoc), carbamate 1,1-dimethyl-2-haloethyl, 1,1-dimethyl-2,2-dibromoethyl carbamate (DB-t-BOC), 1,1-dimethyl-2,2,2-trichloroethyl carbamate (TCBOC), 1-methyl-1-(4-biphenylyl)ethyl carbamate (Bpoc), l-(3,5-di-t- butylphenyl)-1-methylethyl (t-Bumeoc), 2-(2'- and 4'- pyridyl)ethyl (Pyoc), 2-(N,N-dicyclohexylcarboxamido)ethyl carbamate, t-butyl carbamate (BOC), 30 1-adamantyl carbamate (Adoc), vinyl carbamate (Voc), allyl carbamate (Alloc), carbamate of 1- isopropylallyl (Ipaoc), cinnamyl carbamate (Coc), 4-nitrocinnamyl carbamate (Noc), 8-quinoline carbamate, hydroxypiperidinyl carbamate, 5-alkyldithio carbamate, benzyl carbamate (Cbz), p-methoxybenzyl carbamate (Moz), p-nitrobenzyl carbamate, p-bromobenzyl carbamate, p-chlorobenzyl carbamate, 4-methylsulfinylbenzyl carbamate (Msz), 9-antrylmethyl carbamate, diphenylmethyl carbamate, 2-methylthioethyl carbamate, 2-methylsulfonylethyl carbamate, 2-(p-toluenesulfonyl)ethyl carbamate, [2-(1,3-dithianyl)]methyl carbamate (Dmoc), 4-methylthiophenyl carbamate (Mtpc), 2,4-dimethylthiophenyl carbamate (Bmpc), 2-phosphonioethyl carbamate (Peoc), 2-triphenylphosphonioisopropyl carbamate (Ppoc), carbamate. 1,1^-dimethyl-2-cyanoethyl carbamate, m-chloro-p-acyloxybenzyl carbamate, p-(dihydroxyboryl)benzyl carbamate, 5-benzisoxazolylmethyl carbamate, 2-(trifluoromethyl)-6-chromonylmethyl carbamate (Tcroc), m-nitrophenyl carbamate, 3,5-dimethoxybenzyl carbamate, o-nitrobenzyl carbamate, 3,4-dimethoxy-6-nitrobenzyl carbamate, phenyl(o-nitrophenyl)methyl carbamate, phenothiazinyl-(10)-carbonyl derivative, Nz-p-toluenesulfonylaminocarbonyl derivative, N'-phenylaminothiocarbonyl derivative, t-amyl carbamate, S-benzyl thiocarbamate, p-cyanobenzyl carbamate, carbamate cyclobutyl carbamate, cyclohexyl carbamate, cyclopentyl carbamate, cyclopropylmethyl carbamate, p-decyloxybenzyl carbamate, 2,2-dimethoxycarbonylvinyl carbamate, o-(N,N-dimethylcarboxamido)benzyl, 1,1-dimethyl-3-(N,N-dimethylcarboxamido)propyl, 1,1- dimethylpropynyl, di(2-pyridyl)methyl carbamate, 2-furanylmethyl carbamate, 2-iodoethyl carbamate, isobornyl carbamate, isobutyl carbamate, isonicotinyl carbamate 5, p-(p'-methoxyphenylazo)benzyl carbamate, 1-methylcyclobutyl carbamate, 1-methylcyclohexyl, 1-methyl-1-cyclopropylmethyl carbamate, 1-methyl-l-(3,5-dimethoxyphenyl)ethyl carbamate, 1-methyl-l-(p-phenylazophenyl)ethyl carbamate, 1-methyl-l-phenylethyl carbamate, 1-methyl-l-(4-pyridyl)ethyl carbamate, phenyl carbamate, p-(phenylazo)benzyl carbamate, 2,4,6-tri-t-butylphenyl, 4-(trimethylammonium)benzyl carbamate, 2,4,6-trimethylbenzyl carbamate, formamide, acetamide, chloroacetamide, trifluoroacetamide, trifluoroacetamide, phenylacetamide, 3-phenylpropanamide, picolinamide, 3-pyridylcarboxamide, derivative of N-benzoylphenylalanyl, benzamide, p-phenylbenzamide, o-nitophenylacetamide, o-nitrophenoxyacetamide, acetoacetamide, (N'-dithiobenzyloxycarbonylamino)acetamide, 3-(p-hydroxyphenyl)propanamide, 3-(o-nitrophenyl)propanamide, 2-methyl-2-(o-nitrophenoxy)propanamide, 2-methyl-2-(o-phenylazophenoxy)propanamide, 4-chlorobutanamide, 3-methyl-3-nitrobutanamide, o-nitrocinamide, N-acetylmethionine derivative, o-nitrobenzamide, o-(benzoyloxymethyl)benzamide, 4,5-diphenyl-3-oxazolin-2-one, N-phthalimide, N-dithiasuccinimide (Dts), N-2,3-diphenylmaleimide, N-2,5-dimethylpyrrole, adduct of N-1,1,4,4-tetramethyldisylalazacyclopentane (STABASE), 5-substituted 1,3-dimethyl-1,3,5-triazacyclohexan-2-one, 5-substituted 1,3-dibenzyl-1,3,5-triazacyclohexan-2-one, 1-substituted 3,5-dinitro-4-pyridone, N-methylamine, N-allylamine, N-[2-(trimethylsilyl)ethoxy]methylamine (SEM), N-3-acetoxypropylamine, N-(1-isopropyl-4-nitro-2-oxo-3-pyrolin-3-yl)amine, quaternary ammonium salts, N-benzylamine, N-di(4-methoxyphenyl)methylamine, N-5-dibenzosuberylamine, N-triphenylmethylamine (Tr), N-[(4- methoxyphenyl)diphenylmethyl] amine (MMTr), N-9- phenylfluorenylamine (PhF), N-2,7-dichloro-9-fluorenylmethyleneamine, N-ferrocenylmethylamino (Fem), N'- N-2-picolylamino oxide, N-1,-dimethylthiomethyleneamine, N- benzylideneamine, N-p-methoxybenzylideneamine, N- diphenylmethyleneamine, N-[(2-pyridyl)mesityl]methyleneamine, N-(N', N'-dimethylaminomethylene) amine, N,-N'-isopropylidenediamine, N-p-nitrobenzylideneamine, N-salicylideneamine, N-5-chlorosalicylideneamine, N-(5-chloro-2-hydroxyphenyl)phenylmethyleneamine, N-cyclohexylideneamine, N- (5,5-dimethyl-3-oxo-1-cyclohexenyl)amine, N-borane derivative, N-diphenylborinic acid derivative, N-[phenyl(pentacarbonylchromium or tungsten)carbonyl]amine, N-copper chelate, N-zinc chelate, N-nitroamine, N-nitrosamine, N-amine oxide, diphenylphosphinamide (Dpp), dimethylthiophosphinamide (Mpt), diphenylthiophosphinamide (Ppt), dialkylphosphoramidates, dibenzylphosphoramidate, diphenylphosphoramidate, benzenesulfenamide, o-nitrobenzenesulfenamide (Nps), 2,4-dinitrobenzenesulfenamide, triphenylmethylsulfenamide, 3-nitropyridinesulfenamide (Npys), p-toluenesulfonamide methoxybenzenesulfonamide (Mtr), 2,4,6- trimethoxybenzenesulfonamide (Mtb), 2,6-dimethyl-4- methoxybenzenesulfonamide (Pme), 2,3,5,6-tetramethyl-4- methoxybenzenesulfonamide (Mte), 4- methoxybenzenesulfonamide (Mbs), 2,4,6- trimethylbenzenesulfonamide (Mts), 2,6-dimethoxy-4- methylbenzenesulfonamide (iMDs), 2,2,5,7,8- pentamethylchroman-6-sulfonamide (Pmc), methanesulfonamide (Ms), -trimethylsilylethanesulfonamide (SES), 9- anthracenesulfonamide, 4-(4',8'- dimethoxynaphthylmethyl)benzenesulfonamide (DNMBS), benzylsulfonamide, trifluoromethylsulfonamide and phenacylsulfonamide. Exemplary protecting groups are detailed in this document; however, it will be understood that the invention is not intended to be limited to these protecting groups, but rather to a variety of additional equivalent protecting groups that can be easily identified using the above criteria and used in the method of the present invention. Furthermore, a variety of protecting groups are described by Greene and Wuts (above). As described herein, the compounds of the invention may contain "optionally substituted" moieties. In general, the term "substitute," whether preceded by the term "optionally" or not, means that one or more hydrogens of the designated moiety are replaced by a suitable substituent. Unless otherwise indicated, an "optionally substituted" group may have a suitable substituent at each replaceable position of the group, and when more than one position in any given structure can be substituted with more than one substituent selected from a specific group, the substituent may be the same or different at each position. Combinations of substituents contemplated by this invention are preferably those that result in the formation of stable or chemically viable compounds. The term "stable," as used herein, refers to compounds that are not substantially altered when subjected to conditions that enable the production, detection, and, in certain embodiments, the recovery, purification, and use of one or more of the objectives disclosed herein.

Suitable monovalent substituents on a replaceable carbon atom of an "optionally substituted" group are independently halogen; -(CH2)o-4R°; (CH2) 0-4OR°; -O-(CH2)o-4C(O)OR°; -(CH2) 0-4CH(OR°)2; - (CH2) 0-4SR°/ - (CH2)o-4Ph, which can be substituted with R°; - (CH₂)o40 (CH2)0- iPh, which can be substituted with R°; -CH=CHPh, which can be substituted with R°; -NO2; -CN; -N3; -(CH2) 0-4N(R°) 2; - (CH2) 0- N(R°) C(O)OR°; -N (R°)N(R°) C(O)R°; -N(R°)N(R°) C(O)NR°2; N(R°) N(R°) C (O)OR°; - (CH2)o-4C(O)R°; -C(S)R°; - (CH2) 0- 4C (O)N(R°) 2; - (CH₂) 0-4C(O) SR°; - (CH2) 0-4C(O) OSiR°3; - (CH2) 0- 4OC (O) R°; -OC(O)CH2)0-4SR-; SC(S)SR; -(CH2)o-4SC(O)R°; - (CH2)0- 4C(O)NR°2; -C(S)NR°2; -C(S)SR°; -SC(S)SR°; -(CH2) 0-4O (C) ONR°2; -C(O)N (OR°) R°; -C(O)C(O)R°; -C(O)CH2C(O) R°; -C(NOR°) R°; (CH2)0-4SSR°; - (CH2O-4S(O)2R°; - (CH2)O-4S(O)2OR°; - (CH2)O-4OS(O)2R°; -S(O)2NR°2; - (CH2)O-4S(O)R°; -N(R°)S(O)2NR°2; N(R°)S(O)2R°; -N(OR°)R°; -C(NH)NR°2; -P(O)2R°; -P(O)R°2; OP(O)R°2; -OP(O)(OR°)2; SrI3; - (linear or branched C1-4 alkylene)O-N(R°)2; or - (linear or branched C1-4 alkylene)C(O)O-N(R°)2, wherein each R° may be substituted as defined below and is independently hydrogen, aliphatic C1-8, -CH2Ph, -0 (CH2) 0-iPh, or a saturated, partially saturated or aryl ring of 5 to 6 members, having 0 to 4 heteroatoms independently selected from nitrogen, oxygen or sulfur or, notwithstanding the above definition, two independent occurrences of R°, together with their intervening atom(s), form a saturated, partially unsaturated or aryl ring with 0 to 4 heteroatoms independently selected from nitrogen, oxygen or sulfur, which may be substituted as defined below.

Suitable monovalent substituents on R° (or the ring formed by taking two independent occurrences of R°, along with their intervening atoms), are independently halogen, -(CH2)0-2R., (haloR•), -(CH2)0-2OH, -(CH2)0-2OR•, -(CH₂)0-2CH(OR)2; -O(haloR•),-CN, N3(CH2)0-2C(O)R•, -(CH2)0-2C(O)OH, -(CH2)0-2C(O)OR, -(CH2)0-4C(O)N(R°)2; - (CH2) o-2SR, -(CH2)0-2SH, - (CH2) o-2NH2, - (CH2) o- 2NHR, - (CH2) 0-2NR•2, -NO2, -SiR•3, -OSiR 3,-C(O)SR•,-(linear or branched chain C1-4 alkylene) C (O) OR• or -SSR m wherein each R is unsubstituted or where preceded by "halo", is substituted only with one or more halogens, and is independently selected from aliphatic C1-4, -CH2Ph-, - O(CH2) 0-1Ph, or a saturated, partially unsaturated or aryl ring with 0 to 4 heteroatoms independently selected from nitrogen, oxygen, or sulfur.

Suitable divalent substituents on a saturated carbon atom of R include =O and =S. Suitable divalent substituents on a saturated carbon atom of an "optionally substituted" group include the following: =O, =S, NNR*2, =NNHC(O)R*, NNHC(O)OR*, =NNHS(O)2R*, =NR*, =NOR*, -O (C(R*2))2-3O-, or - S (C (R*2) ) 2-3S-, where each independent occurrence of R* is selected from aliphatic hydrogen C1-6, which may be substituted as defined below, or a saturated 5 to 6 membered, partially unsaturated or aryl ring having 0 to 4 heteroatoms independently selected from nitrogen, oxygen, or sulfur. Suitable divalent substituents that are attached to vicinal replaceable carbons of an "optionally substituted" group include: -O(CR*2) 2.3O-, wherein each independent occurrence of R* is selected from hydrogen, aliphatic C1-6, which may be substituted as defined below, or a saturated 5- to 6-membered, partially unsaturated or aryl ring having 0 to 4 heteroatoms selected independently from nitrogen, oxygen, or sulfur.

Suitable substituents in the aliphatic group of R* include halogen, -R, -(haloR•), -OH, -OR, -O(haloR•), -CN, -C(O)OH, -C(O)OR•, -NH2, -NHR, -NR2 or -NO2, wherein each unsubstituted R or when preceded by "halo" is substituted only with one or more halogens, and is an independent aliphatic C1-4, CH2Ph, -O(CH2)0-1Ph or a 5- to 6-membered saturated, partially unsaturated or aryl ring with 0 to 4 heteroatoms selected independently from nitrogen, oxygen, or sulfur.

Suitable substituents on a replaceable nitrogen of an "optionally substituted" group include -R', -NR'2, C(O)OR, -C(O)C(O)R, -C(O)CH2C(O)R', -s(O)2Rr, -S(O)2NR'2, C(S)NR2, -C(NH)NR¹2 or -N(R¹)S(O)2R¹; wherein each R¹ is independently C1-6 aliphatic hydrogen which may be substituted as defined below, unsubstituted -OPh, or a 5- to 6-membered saturated, partially unsaturated or aryl ring having 0 to 4 heteroatoms independently selected from nitrogen, oxygen or sulfur or, notwithstanding the above definition, two independent occurrences of Rf together with their intervening atom(s) form a saturated 3- to 12-membered mono- or bicyclic ring. Partially unsaturated or aryl having 0 to 4 heteroatoms selected independently of nitrogen, oxygen, or sulfur.

Suitable substituents on the aliphatic group of R' are independently halogen, -R•, -(haloR•),-OH,-OR,-O(haloR•),-CN,-C(O)OH,-C(O)OR•,-NH2,-NHR•, NR2 or NO2, wherein each R• is unsubstituted or where preceded by "halo" is substituted only with one or more halogens, and is independently C₁-4 aliphatic, -CH2Ph, -O(CH2)0-1Ph or a 5- to 6-membered saturated, partially unsaturated or aryl ring having 0 to 4 heteroatoms selected independently from nitrogen, oxygen, or sulfur. As used herein, the term "tautomer" encompasses two or more interconvertible compounds resulting from at least one formal migration of a hydrogen atom and at least one change in valence (e.g., a single bond to a double bond, a triple bond to a single bond, or vice versa). The exact ratio of the 25 tautomers depends on several factors, including temperature, solvent, and pH. Tautomerizations (i.e., the reaction that yields a tautomeric pair) can be acid- or base-catalyzed. Exemplary tautomerizations include keto-α-enol; amide-α-imide; lactam-α-lactim; enamine-α-imine; and enamine-α-enamine tautomerizations (different).

As used in this document, the term "catalyst" refers to a substance whose presence increases the rate and/or extent of a chemical reaction, although it is not consumed or undergoes a permanent chemical change itself.

Detailed Description of Certain Modalities I. Polymerization Systems of the Invention

In one aspect, the present invention provides polymerization systems for the copolymerization of CO2 and epoxides to produce polycarbonate polyol resins with a high proportion of -OH end groups. A polymerization system comprises 1) a metal complex including a set of permanent binders and at least one binder that is a polymerization initiator, and 2) a chain transfer agent with a plurality of sites capable of initiating polymer chains. In some embodiments, a polymerization system further includes a co-catalyst. In certain embodiments, a binder that is a polymerization initiator has a plurality of polymer initiation sites.

I.a Chain Transfer Agents

Suitable chain transfer agents for the present invention include any compound having two or more sites capable of initiating chain growth upon copolymerization of an epoxide and carbon dioxide. Preferably, such compounds do not have other functional groups that interfere with polymerization.

Suitable chain transfer agents have a wide variety of chemical structures. In general, the only requirement is that each chain transfer agent molecule be capable of initiating two or more polycarbonate chains. This can occur through various mechanisms, including: ring opening of an epoxide monomer, reaction with carbon dioxide molecules to produce a molecule capable of sustaining polymer chain growth, or a combination thereof. In some embodiments, a chain transfer agent may have two or more functional groups independently capable of reacting with carbon dioxide or an epoxide; examples of these include, but are not limited to, molecules such as diacids, glycols, diols, triols, hydroxy acids, amino acids, amino alcohols, dithiols, mercaptoalcohols, saccharides, catechols, polyethers, etc. In some embodiments, the chain transfer agent may include a variety of active functional groups—which are capable of reacting multiple times to initiate more than one polymer chain. Examples of the latter include, but are not limited to, single-atom functional groups capable of reacting multiple times, such as ammonia, primary amines, and water, as well as multi-atom functional groups such as amidines, guanidine, urea, boronic acids, etc.

In certain embodiments, the chain transfer agents of the present disclosure have a Y-A-(Y)n structure, where: each -Y group is independently a functional group capable of initiating chain growth of epoxide CO2 copolymers and each Y group may be the same or different, -A- is a covalent bond or a multivalent compound; and n is an integer between 1 and 10 inclusive. In some embodiments, each Y group is independently selected from the group consisting of: -OH, -C(O)OH, -C(OR)OH, -OC(RY)OH, -NHRY, -NHC(O)RY, -NHC=NRY; NRYC=NH; -NRC(NRY2)=NH; -NHC(NR2)=NRY; -NHC (O)ORY, NHC (O) NRY2;-C(O)NHRY, C(S)NHRY, -OC(O)NHRY, -OC(S)NHRY, SH,- C(O)SH, B (ORY)OН, -P(O)a (RY) b (ORY) c(O) аH, OP (O) (RY) b(ORY)c(O)aH, -N(RY) OH, -ON(RY)H; =NOH, =NN(R)H, where each occurrence of RY is independently -H, or an optionally substituted radical selected from the group consisting of aliphatic C1-20, heteroaliphatic C1-20, 3- to 12-membered heterocyclic, 6- to 12-membered aryl, a and b are each independently 0 or 1, c is 0, 1 or 2, p is 0 or 1, and the sum of a, b and c is 1 or 2. In some embodiments, an acidic hydrogen atom bonded to any of the above functional groups may be replaced by a metal atom or an organic cation without departing from the present invention (for example, -C(O)OH may also be -C(O)ON+(R)4, -C(O)O(Ca2+)0.5, -C(O)OPPN+ or -SH may be -S20Na+, etc.) such alternatives are specifically included herein and Alternative methods using such salts are implicitly encompassed by the disclosure and examples in this document.

In some embodiments, one or more Y groups are 25 hydroxyl or hydroxy salts. In certain embodiments, each hydroxyl group is a primary or secondary alcohol. In other embodiments, a hydroxyl group is attached to an aromatic or heteroaromatic ring. In certain embodiments, a hydroxyl group is a phenol. In some embodiments, a 30 hydroxyl group is benzylic, allylic, or propargylic. In other embodiments, the hydroxyl groups are part of a carbohydrate. In other embodiments, a hydroxyl group is part of a polymer or oligomer such as a polyether, a polyester, a polyvinyl alcohol, or a hydroxy-functionalized or hydroxy-terminated polyolefin.

In some embodiments, a chain transfer agent is a polyhydric alcohol. In certain embodiments, a polyhydric alcohol is a diol, while in other embodiments the polyhydric alcohol is a triol, a tetraol, or a higher polyol. In certain embodiments, n is 1 (i.e., two Y groups are present), and both Y groups are hydroxyl groups (i.e., the chain transfer agent is a diol). In some embodiments, two hydroxyl groups are on adjacent carbons (i.e., the chain transfer agent is a glycol).

In some embodiments, two hydroxyl groups are on non-adjacent carbons. In certain embodiments, two hydroxyl groups are at opposite ends of a chain (i.e., the chain transfer agent is an α-diol).

In certain embodiments, such α-o diols include C3 to C2o aliphatic chains (i.e., -A- is an optionally substituted C3-2o aliphatic chain). In certain embodiments, such α-o diols comprise a polyether (i.e., -A- is a polyether chain). In certain embodiments, such α-o diols comprise a hydroxy-terminated polyolefin (i.e., -A- is a polyolefin chain). In certain embodiments, such α-o diols comprise paraformaldehyde (i.e., a polyoxymethylene chain).

In certain forms, -A- is a covalent bond. For example, when Y-A-(Y)n is a covalent bond.

In some embodiments, one -OH group of a diol is phenolic and the other is aliphatic. In other embodiments, each hydroxyl group is phenolic. In certain embodiments, a 5-chain transfer agent is an optionally substituted catechol, resorcinol, or hydroquinone derivative.

In some embodiments, where a Y-group is an -OH group, the -OH group is a tautomer of a carbonyl group. In some embodiments, where the Y-group is an -OH group, the -OH group is a carbonyl hydrate or a hemiacetal.

In other embodiments, where n is 1, only one Y group is -OH, and the other Y group is selected from the group consisting of: -C(O)OH, -C(ORy)OH, -OC(Ry)OH, NHRy, -NHC(O)Ry, -NHC(O)ORy, C(O)NHRy, C-(S)NHRy, -OC(O)NHRy, -OC(S)NHRy, -SH, -C(O)SH, -B- 15(ORy)OH, -P(O)a(Ry)b(ORy)c0H, -OP(O)a(Ry)bJORD^OtU ON(Ry)H; =N0H, =NN(Ry)H. In particular embodiments, n is 1, one Y group is -OH, and the other Y group is selected from the group consisting of -SH, -C(O)OH, -NHRy and -C(O)NHRy. In certain embodiments, n is 1, one Y group is -OH, and the other Y group is -C(O)OH. In other embodiments, where n is 1, one Y group is -OH and the other Y group is -SH. In other embodiments, where n is 1, one Y group is -OH and one Y group is -NHRy. In certain embodiments, n is 2, and each Y group is -OH (i.e., the chain transfer agent is a triol). In particular embodiments, where n is 2, two Y groups are -OH, and the third Y group is selected from the group consisting of -SH, -C(O)OH, -NHRy and -C(O)NHRy. In another embodiment, where n is 2, only one Y group is -OH, while the other two Y groups are independently selected from the group consisting of -SH, -C(O)OH, -NHRy and -C(O)NHRy.

In some embodiments, the polyalcohol chain transfer agents encompass naturally occurring materials such as sugar alcohols, carbohydrates, saccharides, polysaccharides, starch, starch derivatives, lignins, lignans, partially hydrolyzed triglycerides and the like, as well as known derivatives of any of these materials. In certain embodiments, a chain transfer agent is starch. In certain embodiments, a chain transfer agent is isosorbide.

In other embodiments, at least one Y group of a chain transfer agent is an amine. In some embodiments, at least one Y group is a primary amine. In other embodiments, at least one Y group is a secondary amine. In certain embodiments, at least one Y group is a secondary amine.

an aniline or aniline derivative. In some embodiments, at least one Y group is an N-H group that is part of a heterocycle.

In certain embodiments, a chain transfer agent is a polyamine. In some embodiments, a chain transfer agent is a diamine. In other embodiments, a chain transfer agent is a triamine, tetramine, or a higher amine oligomer.

In certain embodiments, at least one Y group is an amine and one or more additional Y groups are independently selected from the group consisting of -OH, -C(O)OH, -C(ORy)OH, -OC(Ry)OH, NHC(O)Ry, -NHC(O)ORy, -C(O)NHRy, -C(S)NHRy, -OC(O)NHRy, -OC(S)NHRy, -SH, -C(O)SH, -B(ORy)OH, -P(O)a(Ry)c(OH), -P-(O)a(Ry)b(ORy), COH, -N-(Ry)OH, -ON(Ry)H, -NOH, -NN(Ry)H. In certain embodiments, at least one Y group is an amine and one or more Y groups are independently selected from the group consisting of -OH, -SH, -C(O)OH and -C(O)NHRy. In some embodiments, a chain transfer agent is an amino alcohol. In some embodiments, a chain transfer agent is an aminothiol. In some embodiments, a chain transfer agent is an aminoamide.

In some embodiments, at least one Y group is a carboxylic acid or a salt thereof. In some embodiments, all Y groups present are salts of carboxylic acids, while in other embodiments, one or more Y carboxylic acid groups are present, along with one or more functional groups that can initiate copolymerization. In certain embodiments, at least one Y group is a benzoic acid derivative.

In certain embodiments, a chain transfer agent is a diacid, a triacid, or a higher polyacid. In some embodiments, a chain transfer agent is a diacid. In certain embodiments, n is 1, and both Y groups present are carboxylic acids. In certain embodiments, a diacid is phthalic acid, isophthalic acid, or terephthalic acid. In certain embodiments, a diacid is maleic acid, succinic acid, malonic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, or azelaic acid. In some embodiments, a chain transfer agent is a triacid. In certain embodiments, a triacid is citric acid, isocitric acid, cis- or trans-aconitic acid, propane-1,2,3-tricarboxylic acid, or trimesic acid. A carboxylic acid or carboxylate and one or more additional Y groups are independently selected from the group consisting of -OH, -C(ORy)OH, -OC(Ry)OH, -NHRy, -NHC(O)Ry, -NHC(O)ORy, -C(O)NHRy, -C(S)NHRy, -OC(O)NHRy, -OC(S)NHRy, -SH, -C(O)SH, -B(ORy)OH, -P(O)a(Ry)b(ORy)COH, -OP(O)a(Ry)b(ORy)COH, -N-(Ry)OH; -ON(Ry)H; =NOH, =NN(Ry)H. In certain embodiments, at least one Y group is a carboxylic acid and one or more additional Y groups are independently selected from the group consisting of -OH, -SH, -NHRy and -C(O)NHRy.

In some embodiments, a chain transfer agent is an amino acid. In certain embodiments, amino acid chain transfer agents include naturally occurring amino acids. In certain embodiments, amino acid transfer chains include peptides. In some embodiments, the peptides contain between 2 and about 20 amino acid residues. In other embodiments, the chain transfer agent is a thiol acid.

In some embodiments, the chain transfer agent is a hydroxy acid. In some embodiments, hydroxy acids are alpha-hydroxy acids. In certain embodiments, an alpha-hydroxy acid is selected from the group consisting of: glycolic acid, DL-lactic acid, D-lactic acid, L-lactic acid, citric acid, and mandelic acid. In some embodiments, a hydroxy acid is a beta-hydroxy acid. In certain embodiments, a beta-hydroxy acid is selected from the group consisting of: 3-hydroxypropionic acid, DL-3-hydroxybutyric acid, D-3-hydroxybutyric acid, L-3-hydroxybutyric acid, DL-3-hydroxyvaleric acid, D-3-hydroxyvaleric acid, salicylic acid, and salicylic acid derivatives. In some embodiments, a hydroxy acid is an α-co-hydroxy acid. In certain embodiments, α-co-hydroxy acids are selected from the group consisting of optionally substituted C3 5 2oaliphatic α-co-hydroxy acids. In certain embodiments, an α-co-hydroxy acid is a polyester ester or oligomeric polyester ester.

In some embodiments, where one or more Y groups is a carboxyl group, a chain transfer agent is provided as a carboxylate salt. In certain embodiments, a carboxylate salt is a group I or II metal salt. In some embodiments, a carboxylate salt is an ammonium salt. In certain embodiments, an ammonium cation is NH4+. In some embodiments, an ammonium cation is a primary, secondary, or tertiary protonated amine. In some embodiments, a salt is a quaternary ammonium salt. In some embodiments, a quaternary ammonium cation of an ammonium salt is tetramethyl, tetrabutyl, or tetrahexylammonium. In certain embodiments, a carboxylate salt is a phosphonium carboxylate.

In other embodiments, at least one Y group of a chain transfer agent is a thiol. In some embodiments, at least one Y group is a primary thiol. In other embodiments, at least one Y group is a secondary or tertiary thiol. In certain embodiments, at least one Y group is a thiophenol or thiophenol derivative.

In certain embodiments, a chain transfer agent is a polythiol. In some embodiments, a chain transfer agent is a dithiol. In some embodiments, a chain transfer agent is a trithiol, a higher thiol oligomer.

In certain embodiments, at least one Y group is a thiol and one or more additional Y groups are independently selected from the group consisting of -OH, -C(0)OH, C(0Ry)0H, -OC(Ry)OH, -NHRy, -NHC(0)Ry, -NHC(0)0Ry, -C(0)NHRy, -C(S)NHRy, -OC(O)NHRy, -OC(S)NHRy, -C(O)SH, -B(0Ry)0H, -P(O)a(Ry)b(0Ry)c0H, -P(O)a(Ry)b(0Ry)c0H, N-(Ry)OH, -ON(Ry)H; =N0H, =NN(Ry)H. In certain embodiments, at least one Y group is a thiol and one or more additional Y groups are independently selected from the group consisting of -OH, -NHRy, -C(O)OH and -C(O)NHRy. In some embodiments, a chain transfer agent is a thio alcohol. In some embodiments, a chain transfer agent is an aminothiol. In some embodiments, a chain transfer agent is a 1-carboxylic acid.

In certain embodiments, a Y group of a chain transfer agent is an active NH-containing functional group. In certain embodiments, a nitrogen atom of the NH-containing functional group is nucleophilic. In certain embodiments, an active NH-containing functional group is selected from the group consisting of C-linked amides, N-linked amides, O-linked carbamates, N-linked carbamates, ureas, guanidines, amidines, hydrazones, and N- or C-linked thioamides. In certain embodiments, one or more Y groups is a primary amide.

In certain embodiments, polymerization systems of the present invention include only one chain transfer agent, whereas in other embodiments, mixtures of two or more chain transfer agents are used.

In certain embodiments, polymerization systems of the present invention include a solvent in which a chain transfer agent dissolves. In certain embodiments, a chain transfer agent is weakly soluble in the epoxide, but is soluble in a mixture of epoxide and another solvent added to the reaction mixture. In certain embodiments, the solvent added to the polymerization system is chosen from the group consisting of esters, nitriles, ketones, aromatic hydrocarbons, ethers, amines, and combinations of two or more of these.

In some embodiments, a polymerization initiator includes a multiply active functional group, which is itself capable of reacting multiple times to initiate more than one polymer chain. A subset of such multiply active functional groups reacts multiple times at the same atom. Examples of these groups include, but are not limited to, ammonia, primary amines, hydrogen sulfide, and water, all of which remain nucleophilic after the first addition and are thus capable of reacting again, initiating additional polymer chains. Another subset of multiply active functional groups can react at different atoms in the functional group to initiate multiple chains. Examples of these groups include, but are not limited to, guanidines, ureas, boronic acids, hydroxylamines, and amidines.

In some embodiments, a chain transfer agent may contain a single multiply active functional group. In some embodiments, the chain transfer agent may contain a single multiply active functional group in addition to one or more of the Y groups described above. In certain embodiments, a chain transfer agent may contain two or more multiply active functional groups. In certain embodiments, a chain transfer agent may contain two or more multiply active functional groups in combination with one or more of the Y groups described above.

I.b. Metal Centralized Catalysts

In certain embodiments, the supplied metal complexes are transition metal catalysts. Thus, in some embodiments, polymerization systems of the present invention incorporate transition metal catalysts capable of catalyzing the copolymerization of carbon dioxide and epoxides. In certain embodiments, the polymerization systems include any of the catalysts disclosed in U.S. Patents Nos. 7,304,172 and 6,787(7,004); in PCT Applications Nos. WO2008136591A1, WO2008150033A1, PCT/US09/042926; and PCT/US09/054773, and in Chinese Patent Applications Nos. CN200710010706 and CN200810229276, the entirety of each of which is incorporated herein by reference.

In certain embodiments, polymerization systems of the present invention include metal complexes denoted LpM-(L1)m, where Lp is a permanent ligand set, M is a metal atom and LI is a ligand that is a polymerization initiator, and e is an integer between 0 and 2 inclusive, representing the number of initiating ligands present.

I.b.l Metal atoms

In some embodiments, a metal atom, M, is selected from groups 3 to 13, inclusive, of the periodic table. In certain embodiments, M is a transition metal selected from groups 5 to 12, inclusive, of the periodic table. In certain embodiments, M is a transition metal selected from groups 5 to 10, inclusive, of the periodic table. In certain embodiments, M is a transition metal selected from groups 5-10, inclusive, of the periodic table.

In certain embodiments, M is a transition metal selected from groups 7-9 of the periodic table inclusive. In some embodiments, M is selected from the group consisting of Cr, Mn, V, Fe, Co, Mo, W, Ru, Al, and Ni. In some embodiments, M is a metal atom selected from the group consisting of: cobalt, chromium, aluminum, titanium, ruthenium, and manganese. In some embodiments, M is cobalt. In some embodiments, M is chromium. In some embodiments, M is aluminum.

In certain embodiments, a metal complex is a complex of zinc, cobalt, chromium, aluminum, titanium, ruthenium, or manganese. In certain embodiments, a metal complex is an aluminum complex. In other embodiments, a metal complex is a chromium complex. In yet another 20 embodiments, a metal complex is a zinc complex.

In certain other embodiments, a metal complex is a titanium complex. In still other embodiments, a metal complex is a ruthenium complex. In certain embodiments, a metal complex is a manganese complex. In certain embodiments, a metal complex is a cobalt complex. In certain embodiments where a metal complex is a cobalt complex, the cobalt metal has an oxidation state of +3 (i.e., Co(III)). In other embodiments, the cobalt metal has an oxidation state of +2 (i.e., Co(II)).

I.b.2 Permanent Bonding Groups

A permanent "Lp" linker group comprises one or more linkers that remain coordinated with a metal center throughout the catalytic cycle. This is in contrast to other linkers, such as polymerization initiators, monomeric molecules, polymer chains, and solvent molecules, which may participate in the catalytic cycle or may be exchanged under polymerization conditions.

In certain embodiments, a permanent linker group 10 comprises a single multidentate ligand that remains associated with the metal center during catalysis. In some embodiments, the permanent linker group includes two or more ligands that remain associated with the methyl center during catalysis. In some embodiments, a metal complex 15 comprises a metal atom -coordinated-to a single tetradentate ligand, while in other embodiments, a metal complex comprises a chelate containing a plurality of individual permanent ligands. In certain embodiments, a metal complex 20 contains two bidentate ligands. In some embodiments, a metal complex contains a tridentate ligand.

In various embodiments, suitable tetradentate ligands for metal complexes of the present invention may include, but are not limited to: 25 salen derivatives 1, salen ligand derivatives 2, bis-2-hydroxybenzamido derivatives 3, Trost ligand derivatives 4, porphyrin derivatives 5, tetrabenzoporphyrin ligand derivatives 6, corroi ligand derivatives 7, phthalocyaninate derivatives 8 and dibenzotetramethyltetraza[14]annulene(tmtaa) derivatives 9 or 9'. where Q, in each occurrence, is independently O or S; R1 and R1' are independently selected from the group consisting of: -H, aliphatic C1 to C3 optionally substituted; optionally substituted 3 to 14 membered carbocycle; optionally substituted 3 to 14 membered heterocycle; and R21; R2 and R2' are independently selected from the group consisting of: -H; optionally substituted aliphatic C1 to C12; optionally substituted 3 to 14 membered carbocycle; optionally substituted 3 to 14 membered heterocycle; R14; R20; and R21; R3 and R3' are independently selected from the group consisting of: -H, optionally substituted aliphatic C1 to C12; optionally substituted 3 to 14 membered carbocycle; optionally substituted 3 to 14 membered heterocycle, and R21; 20 Rc, in each occurrence, is independently selected from the group consisting of: -H, aliphatic Cx to Cx2 optionally substituted; optionally substituted 3 to 14 membered carbocycle; optionally substituted 3 to 14 membered heterocycle, R20; and R21, where two or more Rc groups may be taken together with intervening atoms to form one or more optionally substituted rings and, when two Rc groups are attached to the same carbon atom, they may be taken together with the carbon atom to which they are attached to form a portion selected from the group consisting of: an optionally substituted 3 to 8 membered spirocyclic ring, a carbonyl, an oxime, a hydrazone and an imine; Rd in each occurrence is independently selected from the group consisting of: optionally substituted aliphatic Ci to Ci2; optionally substituted 3 to 14 membered carbocycle; optionally substituted 3 to 14 membered heterocycle; R20 and R21, in which two or more R^ groups may be taken together with intervening atoms to form one or more optionally substituted rings; and represents an optionally substituted portion covalently linking two nitrogen atoms, wherein any of [R2' and R3], [R2 and R3], [R1 and R2], and [R1' and R2] may optionally be taken together with intervening atoms to form one or more rings which may in turn be substituted with one or more groups selected from R14; R20 and R21; and where R14 in each occurrence is independently selected from the group consisting of: halogen; optionally substituted aliphatic C1 to C12; optionally substituted 3 to 14 membered carbocycle; optionally substituted 3 to 14 membered heterocycle; -OR10; -OC(O)R13; -OC(O)OR13; OC(O)NR11R12; -CN; -CNO; -C(R13)zH(3-2); -C(O) R13;-C(O)OR13; - C(O) NR¹R12; -NR11R12; -NR11C (O) R13; -NR1¹C(O)OR13;-NR11SO2R13; N*R11R12R1³x; -p+(R11)3X;-P(R11)3=N*=P(R¹1)3X; -As*R11R12R13XNCO;-N3; -NO2; -S(o)xR13; and-SO2NRR12, R20 in each occurrence is independently selected from the group consisting of: halogen; -OR10; -OC (O) R13; OC(O) OR13; -N+ (R²¹)3X; -P* (R¹1)3X°; -P(R11)3=N*=P (R11)3X; As+R2R12R13x; -OC (O) NR11R12; -CN; -CNO; -C(O) R13; -C(O)OR13; - C(O) NRR12; -C(R13) H(3-z); -NR11R12; -NR¹¹C(O)R13; -NR11C(O) OR13; -NCO; -NR11SO2R13; -S(O)xR13; -S(O)2NR11R12; -NO2; -N3; and 15 Si(R13) (3-2) [(CH2)xR14]z R21 in each occurrence is selected independently of the group consisting of: - (CH2)xR20; - (CH2)kZ"- (CH2)kR20; C(R17) 2H(3-z) ; - (CH2)kC (R17) 2H(3-z); - (CH2)mZ"- (CH2)mC(R17) 2H(3-z); -(CH2)xZ"-R16;X' is any anion, Z" is a divalent ligand selected from the group consisting of -(CH=CH)a-; -(CH=CH)a-; -C(O) -;-C(=NOR11)-; - c(=NNR1¹R12) -; -O-; -OC(O)-; -C(O)0-; -OC(O)0-; N-(R¹1)-; - N(C(O) R13) -;-C(O)NR¹³;-N(C(O) R23) O-;-NR13C(O)R1³N;-S(O)x-; a polyether; and a polyamine, R10 in each occurrence is independently selected from the group consisting of: - -H; optionally substituted aliphatic C1-12; an optionally substituted 3- to 14-membered carbocycle; an optionally substituted 3- to 14-membered heterocycle; - S(O)2R23;-Si(R15)3;-C(O)R13; and a hydroxyl protecting group, R11 and R12 in each occurrence are independently selected from the group consisting of: -H; optionally substituted aliphatic C1 to C12; an optionally substituted 3- to 14-membered carbocycle; an optionally substituted 3- to 14-membered heterocycle; where two or more R1:1 or R12 groups may optionally be taken together with intervening atoms to form a ring of 3 to 10 members optionally substituted, R13 in each occurrence is independently selected from the group consisting of: -H, aliphatic C1 to C12 optionally substituted; a carbocycle of 3 to 14 members optionally substituted; a heterocycle of 3 to 14 members optionally substituted; where two or more R13 groups in the same molecule may optionally be taken together to form a ring. R15 in each occurrence is independently selected from the group consisting of: aliphatic C1 to C12 optionally substituted; a carbocycle of 3 to 14 members optionally substituted; a heterocycle of 3 to 14 members optionally replaced, a is 1, 2, 3 or 4, k is independent in each occurrence an integer from 1 to 8 inclusive, m is 0 or an integer from 1 to 8 inclusive, q is 0, or an integer from 1 to 5 inclusive, x is 0, 1 or 2, and z is 1, 2 or 3.

In certain modalities, from complexes 1 to 4, and selected from the group consisting of a C3.i4 carbocycle, a C6-io aryl group, a 3- to 14-membered heterocycle, and a 5-alO-membered heteroaryl group; a polyether group, or an optionally substituted C2_20 aliphatic group, in which one or more methylene units are optionally and independently substituted by -NRy-,-N(Ry)C(O)-,-C(O)N(Ry)-,-OC(O)N(Ry)-,-N(Ry)C(O)O-,-OC(O)O-,-O-,-C(O)-,-0C(O)-,-C(O)O-,-S-,-SO-,-SO2-,-C(=S)-,-C(=NRy)-,-C(=NORy)- OR-N=N-.

In some embodiments, one or more of the substituents in the metal complexes from 1 to 9' are in an activation moiety. , where represents a covalent ligand containing one or more atoms selected from the group consisting of C, O, N, S, and Si; "Z" is an activating functional group with co-catalytic activity in the copolymerization of the epoxide CO2, ep is an integer from 1 to 4, indicating the number of individual activating functional groups present in a given activating moiety.

In certain forms, the binding portion is 20 as described in co-pending PCT Application number PCT/US09/54773. In some embodiments, one or more Z group(s) present in the activation portion is selected independently from the group consisting of PPN+ (- PR2=N+=PR3) derivatives, ammonium salts; phosphonium salts; or an optionally substituted N-linked imidazolium, thiazolium or oazolium group. In certain embodiments, a Z group is an optionally substituted N-linked piperidine or N-linked pyrrolidine. In some embodiments, a Z group is an optionally substituted guanidine. In other embodiments, a Z group is any of those described in PCT/US09/54773.

In some embodiments, the supplied metal complexes have a structure selected from the group consisting of: where: M, Li, mR1, R1', R2, R2, R3, R3' and R11 are as defined above.

In some embodiments, a permanent linking group is a salen ligand. In certain embodiments, a metal complex is a metalosalenate. In certain embodiments, a metal complex is a cobalt salen complex. In certain embodiments, a metal complex is a chromium salen complex. In other embodiments, a metal complex is an aluminum salen complex.

In certain embodiments, the metal complexes of the present invention have the formula: where: M is the metal atom; Li is a nucleophile capable of opening an epoxide ring; m is an integer from 0 to 2 inclusive; and is the permanent linking group; where as defined previously, and each R' independently represents one or more optionally present substituents on the phenyl rings.

In certain modalities, each R' is independently an Rd group or a group , where two or more adjacent Rz groups can be taken together to form a 3- to 12-membered saturated, partially unsaturated, or optionally substituted aromatic ring containing 0 to 4 heteroatoms.

In certain modalities, the portion and selected from the group consisting of: where Rc and R are as defined previously, Y is a divalent ligand selected from the group consisting of: -N(R1:L)-; -O-; -S(O)X-; -(CH2)k-; -C(O)-; -C(=NOR10)-; -C(Rc)XH2_X-; a polyether; an optionally substituted 3- to 8-membered carbocycle; and an optionally substituted 3- to 8-membered heterocycle. q is 0 or an integer from 1 to 5 inclusive, ex is 0, 1, or 2.

In certain embodiments, the predicted metal complexes have a selected group structure consisting of: where: M, R, R', LI are as defined above; Ra R4a', R5a R5a', R6a, R6a', R7a and R7a are each independently hydrogen, a group , halogen. -NO2, -CN, -SR13, -S(O)R13, -S(O)2R13, -NR11C(O)R13, -OC(O)R13, -CO2R13, -NCO, -N3-, -OR1, -OC(O)NR11R12, -Si(R13)3, -NR11R12, -NR1¹C(O)R13 and -NR1¹C(O)OR¹³; or an optionally substituted radical selected from the group consisting of aliphatic C1-20; heteroaliphatic C1-20; aryl with 6 to 10 members; heteroaryl with 5 to 10 members; and heterocyclic of 3 to 7 members, where [R1a and R4aj, [R1a and R4Aa'], and any two adjacent groups R4a, R4a', R5a, R5a', R6a, R6a', R7a and R7a' can be taken together with intervening atoms to form one or more optionally substituted rings containing one or more heteroatoms; né 0 or an integer from 1 to 8 inclusive; and pé 0 or an integer from 1 to 4 inclusive.

In some embodiments, Rla, Rla', Ria, R4a', R6a, and R6a are each -H. In some embodiments, R5a, R5a', R7a, and R7a' are each optionally substituted C₁-C12 aliphatic molecules.

In some embodiments, R4a, R4a', R5a, R5a', R6a, R6a', R7a, and R7a' are each independently selected from the group consisting of: -H, -SiR3; methyl, ethyl, n-propyl, i-propyl, n-butyl, sec-butyl, t-butyl, isoamyl, t-amyl, texyl, and trityl. In some embodiments, R1a, R1a', R1a, R4a', R6a, and R6a' are each -H. In some embodiments, R7a is selected from the group consisting of -H; methyl; ethyl; n-propyl; i-propyl; n-butyl; sec-butyl; t-butyl; isoamyl; tamyl; texyl; and trityl. In some embodiments, R5a and R7a are independently selected from the group consisting of -H; methyl; ethyl; n-propyl; i-propyl; n-butyl; sec-butyl; t-butyl; isoamyl; t-amyl; texyl; and trityl. In certain embodiments, one or more of R5a, R5a', R7a, and R7a' is a group. In some disciplines, R5a and R5a' are each a group. In some sports, R5ª is a large and R5a' is aliphatic C1-8. In some modalities, R7 and R7a' are each a group In some sports, R7a is a group. and R7a is an aliphatic C1-8.

In certain embodiments, the supplied metal complexes have a selected group structure consisting of: where R1a through R7a are as defined above.

In certain embodiments, the supplied metal complexes have a selected group structure consisting of: where R5a, RSa', R7a and R7a' are as defined above. In certain embodiments, each pair of substituents on the salicaldehyde moieties of the above complexes are the same (i.e., R5a &R5a' are the same, and R7a & R7a are the same). In other embodiments, at least one of R5a &R5a' or R7a & R7a are different from each other.

In certain forms, a metal complex has the formula III:

In certain forms, a metal complex has the formula IV:

In certain embodiments, where a metal complex has the formula V: wherein: R, R, LI, meq are as described above, and each of R4, R4, R5, R5, R6, R6, and R are independently selected from the group consisting of: -H; -R20; -R21; an optionally substituted aliphatic C1 to C12; an optionally substituted 3 to 14 membered carbocycle; and an optionally substituted 3 to 14 membered heterocycle; wherein [R1 and R4], [R1' and R4'] and any two groups R4, R4', R5, R5', R5, R6', R7 and R7' may optionally be taken together with the intervening atoms to form one or more optionally substituted rings with one or more R20 groups.

In certain embodiments, where a metal complex has formula III, R1, R1', R4, R4', R6, and R6' are each -H. In certain embodiments, where a metal complex has formula III, R5, R5', R7, and R7' are each optionally substituted aliphatic C1-C12.

In certain embodiments, wherein a metal complex has formula III, R4, R4', R5, R5', Rs, R6', R7, and R7' are each independently selected from the group consisting of: -H, -Si(R13)3; -Si[(CH2)kR22]z(R13)(3-z); methyl, ethyl, n-propyl, i-propyl, n-butyl, sec-butyl, t-butyl, isoamyl, t-amyl, texyl, tritil, -C(CH3)Ph2, -(CH2)pC[(CH2)PR22]zH(3.z), and -Si(R13)(3-Z)[(CH2)kR22]z, where p is an integer from 0 to 12 inclusive, and R22 is selected from the group consisting of: a heterocycle; an amine; a guanidine;-N+(R11) 3X"; -P+(RI:L)3X' 10; -P (R11) 2=N+=P (R11) 3X”; -As+ (R11) 3X', and optionally substituted pyridinium.

In certain embodiments, where a metal complex has formula III, R7 is selected from the group consisting of -H; methyl; ethyl; n-propyl; i-propyl; n-butyl; sec-butyl; t-butyl; isoamyl; t-amyl; texyl; and tritil; and R5 is selected from the group consisting of -(CH2)PCH(3_Z)[(CH2)PR22]z and -Si(R13)(3_z)[(CH2)kR22]z.

In certain embodiments, a metal complex has formula IV, R1, R1', R4, R4', R6 and R6' are each -H. In 20 certain embodiments, where the complex is a metalosalenate complex of formula IV, R5, R5', R7 and R7' are each optionally substituted aliphatic C1-C12.

In certain embodiments, wherein a metal complex has formula IV, R4, R4', R5, R5', R6, R6', R7, and R7' are each independently selected from the group consisting of: -H, -Si(R13)3; -Si(R13)(3_Z)[(CH2)kR22]z; methyl, ethyl, n-propyl, i-propyl, n-butyl, sec-butyl, t-butyl, isoamyl, t-amyl, texyl, trityl, -(CH2)PC[(CH2)PR22]ZH(3_Z).

In certain embodiments, where a metal complex has formula IV, R7 is selected from the group consisting of - H; methyl; ethyl; n-propyl; i-propyl; n-butyl; sec-butyl; t-butyl; isoamyl; t-amyl; texyl; and tritil; and R5 is selected from the group consisting of - (CH2) pCH{3-z) [ (CH2) PR22] z θ -Si(R13)(3_ z) [(CH2)kR22]z.

In certain embodiments, where a metal complex has formula V, R1, R1', R4, R4', R6, and R6' are each -H. In certain embodiments, where a complex is a metalosalenate complex of formula V, R5, R5', R7, and R7' are each optionally substituted aliphatic C1-C12 groups.

In certain embodiments, wherein a metal complex has formula V, R4, R4', R5, R5', R6, R6', R7 and R7' are each independently selected from the group consisting of: -H, -Si(R13)3; -Si [ (CH2) kR21] z (R13) (3-Z) ; methyl, ethyl, n-propyl, i-propyl, n-butyl, sec-butyl, t-butyl, isoamyl, t-amyl, texyl, trityl, - (CH2) pCH(3.z) [(CH2) pR22] z and _-Si (R13)-^.-Z) í(CH2)kR22]z.

In certain embodiments, where a metal complex has formula V, R7 is selected from the group consisting of -H; methyl, ethyl; n-propyl; i-propyl; n-butyl; sec-butyl; t-butyl; isoamyl; t-amyl; texyl; and tritil; and R5 is selected from the group consisting of -(CH2)PCH(3-Z)[(CH2)PR22]z and -Si(R13)(3-z)[(CH2)kR22]z.

In some embodiments, a metal complex has an Lp-M-(Li)m structure, where Lp-M is selected from the group consisting of:

In other embodiments, the permanent linking group comprises a porphyrin ring and Lp-M has the following structure: wherein: M, Li, Rc and Rd are as defined above and any two adjacent Rc or Rd groups may be taken together to form one or more rings optionally replaced with one or more R20 groups.

In certain embodiments where the permanent linking group comprises a porphyrin ring, M is a metal atom selected from the group consisting of: cobalt; chromium; aluminum; titanium; ruthenium and manganese.

As mentioned above, in some embodiments of the present invention, the permanent linker group may comprise a plurality of discrete linkers. In certain embodiments, the permanent linker group includes two bidentate linkers. In certain embodiments, such bidentate linkers may have the structure where Rd and R11 are defined above. Metal complexes having two such ligands can adopt one of several geometries, and the present disclosure includes a complex with one of the possible geometries. as well—and mixtures of two or more geometric isomers.

In certain embodiments, metal complexes including two bidentate ligands may have structures selected from the group consisting of: in which each represents a ligand:

I.a.3 Initiation Ligands

In addition to a metal atom and a permanent linker group described above, metal complexes suitable for polymerization systems of the present invention optionally include one or more -Lx ligands. In some embodiments, these ligands act as polymerization initiators and become part of a growing polymer chain. In certain embodiments, there is one initiating ligand present (i.e., m = 1). In other embodiments, there are two initiating ligands present (i.e., m = 2). In certain embodiments, one initiating ligand may be absent (i.e., m = 0). In certain embodiments, a metal complex may be added to a reaction mixture without an initiating ligand, but may form an in situ species that includes one or two initiating ligands.

In certain embodiments, -L is any anion. In certain embodiments, -LI is a nucleophile. In some embodiments, -LI initiation ligands are nucleophiles capable of opening an epoxide ring. In some embodiments, an LI polymerization initiator is selected from the group consisting of: azides, halides, alkyl sulfonates, carboxylates, alkoxides, and phenolates.

In some embodiments, initial ligands include, but are not limited to, α-ORx, -SRX, -OC(O)RX, -OC(O)ORX, -OC(0)N(RX)2/-NRXC(0)Rx, -CN, halogen (e.g., -Br, -I, -Cl), -N3e-OSO2RX, wherein each Rx is independently selected from hydrogen, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aryl and optionally substituted heteroaryl and wherein two Rx groups may be taken together to form an optionally substituted ring optionally containing one or more additional heteroatoms.

In certain embodiments, -Lx is -OC(O)Rx, wherein Rx is selected from optionally substituted aliphatic, fluorinated aliphatic, optionally substituted heteroaliphatic, optionally substituted aryl, fluorinated aryl 5 and optionally substituted heteroaryl.

In certain embodiments, -Lx is-OC(O)Rx, wherein Rx is optionally substituted aliphatic. In certain embodiments, -Li is-OC(O)Rx, wherein Rx is optionally substituted alkyl or fluoroalkyl. In certain embodiments, Lx is-OC(O)CH3 or -OC(O)CF3.

Furthermore, in certain embodiments, Lx is -OC(O)RX, where Rx is optionally substituted aryl, fluoroaryl, or heteroaryl. In certain embodiments, -Lx is -OC(O)RX, where Rx is optionally substituted aryl. In certain embodiments, -15Li is -OC(O)RX, where Rx is optionally substituted phenyl. In certain embodiments, -Lx is -OC(O)CsH5 or -OC(O)C6F5.

In certain embodiments, Lx is -ORX, where Rx is selected from optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aryl, and optionally substituted heteroaryl.

For example, in certain embodiments, -Lx is -ORX, where Rx is optionally substituted aryl. In certain embodiments, Lx is -ORx, where Rx is optionally substituted phenyl. In some embodiments, -Lx is a 2,4-dinitrophenolate anion. In certain embodiments, -Lx is -OC6H5.

In certain modalities, Lx is halo. In certain modalities, -Lx is -Br. In certain modalities, Lx is-Cl. In certain modalities, -Lx is-I.

In certain modalities, -Lx is -O(SO2)RX. In certain modalities, -Lx is -OTs. In certain modalities, -Lj is OSO2Me. In certain modalities, -L∑ is -OSO2CF3.

In some embodiments, the LP-M-(Li)min metal complexes include one or more -Lx initiation ligands characterized in that each ligand is capable of initiating two or more polymer chains. In some embodiments, the initiation ligand is any of the molecules described above as being suitable as chain transfer agents. In certain embodiments, an initiation ligand is an anion derived from any of the chain transfer agents described above.

In some embodiments, a polymerization initiator - Li comprises a compound of formula -Q'-A'-(Z')n, wherein: -Q'- is a carboxy or alkoxy group, -A'- is a covalent bond or a multivalent moiety, each Z' is independently a functional group that can initiate a polymer chain, and n is an integer between 1 and 10 inclusive.

In certain embodiments where a polymerization initiator comprises a compound having the formula -Q'-A'(Z')n, each -Z' is a functional group selected independently from the group consisting of: -OH, -C(O)OH, C(ORy)OH, -OC(Ry)OH, -NHRy, -NHC(O)Ry' -NHC=NRy; -NRyC=NH; - 25 NRyC(NRy2)=NH, -NHC(NRy2)=NRy; -NHC(O)ORy, -NHC (O) NRy2,- C(O)NHRy, -C(S)NHRy, -OC(O)NHRy, -OC(S)NHRy, -SH,-C(0)SH,- B (ORy) OH, -P (0) a (Ry) b (0Ry) b (0Ry) c (OH) d, -0P (O) a (Ry) b (ORy) c (OH) d, -N (Ry) OH, -ON (Ry) H; =NOH, =NN(Ry)H, wherein each occurrence of Ry is an independent -H, or an optionally substituted radical selected from the group consisting of aliphatic C1-2O, heteroaliphatic C1-2O, 3- to 12-membered heterocycle, and 6- to 12-membered aryl, a and b each being independently Ooul, c is 0, 1 or 2, déOoul, and the sum of a, b and c is 1 or 2; and -A'-e selected from the group consisting of: a) aliphatic C2-C2O; b) carbocycle C3-C2O; c) 3- to 12-membered heterocycle; d) a saccharide; e) an oligosaccharide; f) a polysaccharide; and g) a polymer chain, wherein any of (a) through (g) are optionally substituted with one or more R groups.

In certain embodiments where a polymerization initiator comprises a compound having the formula -Q'-A'-(Z')n, each -Z' is independently selected from the group consisting of: -OH; and -C(O)OH-. In some embodiments, -A'- is a covalent bond.

In certain embodiments where a polymerization initiator comprises a compound having the formula -Q'-A'-(Z')n, -A'- is an aliphatic C2-20z group and n is an integer from 1 to 5.

In certain embodiments where a polymerization initiator comprises a compound having the formula -Q'- A' (Z')n, -A'- is an aliphatic C2-i2z group and n is an integer from 1 to 3.

In certain embodiments where a polymerization initiator comprises a compound having the formula -Q'- A'(Z')n, Q' is -OC(O)-; -A'- is an aliphatic C2-20 group; Z' is -OH; n is an integer from 1 to 3.

In certain embodiments, where a polymerization initiator has more than one site capable of coordinating with a metal atom, a single polymerization initiator can be shared by multiple metal complexes (each metal complex including a metal atom and a permanent linker group). For example, when Lx is a diacid, each carboxyl group of the diacid can be coordinated with a metal atom of a separate metal complex (i.e., a dimeric or pseudodimeric complex having the formula Lp-M-O2C-A'-CO2-M-LP, where A', M, and Lp are as defined previously). Similarly, a triacid can be coordinated to one, two, or three metal centers, or a hydroxy acid, a dialkoxide, an amino acid, or another polyfunctional compound can coordinate with two or more Lp-M groups.

In certain embodiments, an initiating ligand is a carboxylic acid with 2 to 4 carboxyl groups. In certain embodiments, an initiating ligand is a C2-20 diacid. In 15 certain embodiments, an initiating ligand is selected from the group consisting of 1-1 to 1-24:

In certain embodiments, an initiation ligand having a plurality of polymer initiation sites may be a hydroxy acid. In certain embodiments, a hydroxy acid is selected from the group consisting of:

In certain embodiments, a polymerization initiator having a plurality of polymer initiation sites is a polyhydric phenol derivative. In certain embodiments, a polymerization initiator is selected from the group consisting of:

In some embodiments, an initiating ligand is a polyalcohol. In certain embodiments, a polyalcohol is a diol. Suitable diols include, but are not limited to: 1,2-ethanediol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 2,2-dimethylpropane-1,3-diol, 2-butyl-2-ethylpropane-1,3-diol, 1,5-hexanediol, 1,6-hexanediol, 1,8-octanediol, 1,10-decanediol, 1,12-dodecanediol, 2,2,4,4-tetramethylcyclobutane-1,3-diol, 1,3-cyclopentanediol, 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol. 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol and 1,4-cyclohexanediethanol.

In some embodiments, an initiating ligand is an alkoxide derived from a compound selected from the group consisting of: diethylene glycol, triethylene glycol, tetraethylene glycol, pentaethylene glycol, higher poly(ethylene glycol), dipropylene glycol, tripropylene glycol, and higher (poly)propylene glycol. In some embodiments, higher (poly)ethylene glycol compounds are those with average molecular weights from 220 to about 2000 g/mol. In some embodiments, higher (poly)propylene glycol compounds are those with average molecular weights from 234 to about 2000 g/mol.

In some embodiments, suitable diols include 4,4'-(methylethylidene)bis[cyclohexanol], 2,2'-methylenebis[phenol], 4,4'-methylenebis[phenol], 4,4'-(phenylmethylene)bis[phenol], 4,4'-(diphenylmethylene)bis[phenol], 4,4'-(1,2-ethanediyl)bis[phenol], 4,4'-(1,2-cyclohexanediyl)bis[phenol], 4,4'-(1,3-cyclohexanediyl)bis[phenol], 4,4'-(1,4-cyclohexanediyl)bis[phenol], 4,4'-(1-phenylethylidene)bis[phenol], 4,4'-propylidenebis[phenol], 4,4'-cyclohexylidenebis[phenol], 4,4'- (methylethylidene)bis[phenol], 4,4'-(1-methylpropylidene)bis[phenol], 4,4'- (ethylpropylidene)bis[phenol], 4,4'-cyclohexylidenebis[phenol], 4,4'- (2,4,8,10-tetraoxaspiro[5.5]undecane-3,9-diyldi-2,1- ethanediyl)bis[phenol], 1,2-benzenedimethanol, 1,3-benzenedimethanol, 1,4-benzenedimethanol, 4,4'-[1,3-phenylenebis(1-methylethylidene)]bis[phenol], 4,4'-[1,4-phenylenebis(methylethylidene)]bis[phenol], phenolphthalephne, 4-,-4'-(l-methylidene) bis [2-methylphenol], 4,4'-(1-methylethylidene)bis[2-(1-methylethyl)phenol], 2,2'-methylenebis[4-methyl-6-(1-methylethyl)phenol.

In some embodiments, a polyol is a triol. Suitable triols may include, but are not limited to: aliphatic triols with a molecular weight less than 500, such as trimethylolethane; trimethylolpropane; glycerol; 1,2,4-butanetriol; 1,2,6-hexanetriol; tris(2-hydroxyethyl)isocyanurate; hexahydro-1,3,5-tris(hydroxyethyl)-s-triazine; 6-methylheptane-1,3,5-triol; polypropylene triol oxide; and polyester triols.

In certain embodiments, a polyol is a tetraol. Examples of suitable tetraols include, but are not limited to: erythritol, pentaerythritol; 2,2'-dihydroxymethyl-1,3-propanediol; and 2,2'-(oxydimethylene)bis-(2-ethyl-1,3-propanediol).

In certain modalities, a metallic coordination complex is selected from the group consisting of:

In some embodiments, a metal coordination complex is selected from compounds with formulas XLIX to LIV:

In some embodiments, the polymerization systems of the present invention also include at least one co-catalyst. In some embodiments, a co-catalyst is selected from the group consisting of: amines, guanidines, amidines, phosphines, nitrogen-containing heterocycles, ammonium salts, phosphonium salts, arson salts, bisphosphinoammonium salts, and a combination of two or more of the above options.

In embodiments where the co-catalyst is an "onium" salt, there is not necessarily an anion present to balance the charge of the salt. In certain embodiments, this is any anion. In certain embodiments, the anion is a nucleophile. In some embodiments, the anion is a nucleophile capable of opening the epoxide ring. In some embodiments, the anion is selected from the group consisting of: azides, halides, alkyl sulfonates, carboxylates, alkoxides, and phenolates.

In some embodiments, the ionic co-catalyst includes anions selected from the group consisting of: -ORx, -SRX, -5OC(O)Rx, -OC(O)0Rx, -OC(O)N(Rx)2z-NRXC(O)Rx, -CN, halogen (e.g., -Br, -I, -Cl), -N3e-OSO2RX, wherein each Rx is independently selected from hydrogen, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aryl and optionally substituted heteroaryl and wherein two Rx groups may be taken together to form an optionally substituted ring containing optionally one or more additional heteroatoms.

In certain embodiments, a co-catalyst anion is 15 OC(O)RX, wherein Rx is selected from optionally substituted aliphatic, fluorinated aliphatic, optionally substituted heteroaliphatic, optionally substituted aryl, fluorinated aryl, and optionally substituted heteroaryl.

In certain embodiments, a co-catalyst anion is -OC(O)RX, where Rx is optionally substituted aliphatic. In certain embodiments, a co-catalyst anion is -OC(O)Rx, where Rx is optionally substituted alkyl and fluoroalkyl. In certain embodiments, a co-catalyst anion is -OC(O)CH3 25 OR -OC(O)CF3.

Furthermore, in certain embodiments, a co-catalyst anion is -OC(O)Rx, where Rx is optionally substituted aryl, fluoroaryl, or heteroaryl. In certain embodiments, a co-catalyst anion is -OC(O)Rx, where Rx is optionally substituted aryl. In certain embodiments, a co-catalyst anion is -OC(O)Rx, where Rx is optionally substituted phenyl. In certain embodiments, a co-catalyst anion is -OC(O)C6H5 or -OC(O)C6F5.

In certain embodiments, a co-catalyst anion is -ORx, where Rx is selected from optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aryl, and optionally substituted heteroaryl.

For example, in certain embodiments, a co-catalyst anion is -ORx, where Rx is optionally substituted aryl. In certain embodiments, a co-catalyst anion is -ORx, where Rx is optionally substituted phenyl. In certain embodiments, a co-catalyst anion is -OC6H5 or -OC6H2(2,4-NO2).

In certain embodiments, a co-catalyst anion is -halogen. In certain embodiments, a co-catalyst anion is -Br. In certain embodiments, a co-catalyst anion is -Cl. In certain embodiments, a co-catalyst anion is -I.

In certain embodiments, a co-catalyst anion is -O(SO2)RX. In certain embodiments, a co-catalyst anion is -OTs. In certain embodiments, a co-catalyst anion is -OSO2Me. In certain embodiments, a co-catalyst anion is -OSO2CF3. In some embodiments, a co-catalyst anion is a 2,4-dinitrophenolate anion.

In certain embodiments, polymerization systems of the present invention include a cationic co-catalyst having a counter ion characterized in that the counter ion is capable of initiating polymerization at two or more sites. In some embodiments, a counter ion is any of the molecules described above as being suitable as initiation ligands (L∑). In certain embodiments, an anion is derived from any of the chain transfer agents described above.

In some embodiments, an anion of the ionic co-catalyst comprises an anion of formula ’Q’-A’ (Z’)n, θm where: -Q’- is a carboxy or alkoxy group, -A’- is a covalent bond or a multivalent moiety, each Z’ is independently a functional group that can initiate a polymer chain, and n is an integer between 1 and 10 inclusive.

In certain embodiments, where an anion of an ionic co-catalyst is a single polyfunctional compound, it is possible for a polyfunctional compound to be the counter ion of more than one cationic co-catalyst, or to be associated with either a co-catalyst cation or a metal complex. For example, if a co-catalyst is an ammonium salt and the counter ion is a diacid, the diacid may be doubly deprotonated and may be associated with two ammonium cations: N+R4'O2C-A'-CO2'N+R4. Similarly, two PPN+ cations may be associated with a single diacid. Alternatively, the diacid may be associated with either a co-catalytic cation or a metal complex: N+R4'O2C-A'-CO2'M+LP. It will be evident to the skilled practitioner that many such variations are possible, and it will also be understood that ionic compounds and coordination complexes can be in equilibrium. Therefore, the active species present at different times during the polymerization reactions can change. In some cases, known methods for producing monosalts of polyfunctional compounds can be used to influence the stoichiometry of the polymerization system.

In certain embodiments, anions present to balance the charge of the cationic co-catalysts and the initiating ligand in the metal complex are selected as being the same compound. In certain embodiments, an initiating ligand, a counter ion present in a cationic co-catalyst, and a chain transfer agent are chosen to be used as the chain transfer agent; the metal complex could be chosen to include glycolate as the initiating ligand; and a cationic co-catalyst including a glycolate counter ion (such as tetrabutylammonioglycolate) could be used as the co-catalyst. Such embodiments of the present invention provide polyol compositions that are highly homogeneous, since virtually all chains have the same chemical composition. The details of these compositions and methods for producing them are described in more detail below.

Ic. Stoichiometry of Polymerization Systems

Having described in detail each of the components of the polymerization system, we now turn to the relative proportions of those components. In certain embodiments, a metal complex Lp-M-(Li)m and a chain transfer agent Y-A-(Y)n are present in a defined ratio selected to maximize the conversion of the epoxide monomers and achieve the desired molecular weight of polycarbonate polyol. In embodiments where a co-catalyst is present, the ratios between a metal complex, a co-catalyst, and a chain transfer agent are selected to maximize the conversion of the epoxide monomers and achieve the desired molecular weight of polycarbonate polyol.

In some embodiments, a metal complex and a chain transfer agent are present in a molar ratio ranging from about 1:10 to about 1:1000. In certain embodiments, the ratio is between about 1:50 and about 1:500. In certain embodiments, the ratio is between 1:50 and about 250. In certain embodiments, the ratio is between about 1:20 and about 1:100. In certain embodiments, the ratio is between about 1:100 and about 1:250. In some embodiments, a metal complex and a chain transfer agent are present in a molar ratio greater than 1:1000. In some embodiments, a metal complex and a chain transfer agent are present in a molar ratio less than 1:1000.

In some embodiments, a metal complex and a co-catalyst are present in a molar ratio ranging from about 0.1:1 to about 1:10. In certain embodiments, the ratio is from about 0.5:1 to about 5:1. In other embodiments, the ratio is from about 1:1 to about 4:1. In certain embodiments, the ratio between the metal complex and the co-catalyst is about 1:1. In other embodiments, the molar ratio between a metal complex and a co-catalyst is about 1:2.

II. Polycarbonate Polyol Compositions

As described above, there are currently no methods available to produce aliphatic polycarbonate polyol resins that combine the characteristics of a high content of 30 carbonate linkages, a high percentage of hydroxyl end groups, and low molecular weight (e.g., less than about 20 kg/mol). In one aspect, the present invention encompasses these novel materials.

In some embodiments, the present invention encompasses 5 CO2 epoxide copolymers with a molecular weight number between about 400 and about 20,000, characterized in that the polymer chains have a carbonate content >90%, and at least 90% of the terminal groups are hydroxyl groups.

In certain embodiments, the carbonate linkage content of the polycarbonate chains of CO2 epoxide copolymers of the present invention is at least 90%. In some embodiments, more than 92% of the linkages are carbonate linkages. In certain embodiments, at least 95% of the linkages are carbonate linkages. In certain embodiments, at least 97% of the linkages are carbonate linkages. In some embodiments, more than 98% of the linkages are carbonate linkages, in some embodiments, at least 99% of the linkages are carbonate linkages. In some embodiments, essentially all the linkages are carbonate linkages (i.e., there are essentially only carbonate linkages detectable by typical methods such as OU13C NMR spectroscopy).

In certain embodiments, the ether linkage content of the 25 epoxide CO2 copolymer polycarbonate chains of the present invention is less than 10%. In some embodiments, less than 8% of the linkages are ether linkages. In certain embodiments, less than 5% of the linkages are ether linkages. In certain embodiments, no more than 3% of the linkages are ether linkages. In some embodiments, less than 2% of the linkages are ether linkages, in some embodiments, less than 1% of the linkages are ether linkages. In some embodiments, essentially none of the linkages are ether linkages (i.e., there are essentially no detectable ether linkages by typical methods such as 1H or 1C NMR spectroscopy).

In some embodiments, the CO2 epoxide copolymers of the present invention have average molecular weight numbers ranging from about 400 to about 400,000 g/mol. In some embodiments, the CO2 epoxide copolymers of the present invention have average molecular weight numbers ranging from about 400 to about 20,000 g/mol. In some embodiments, the copolymers have a Mn between about 500 and about 5,000 g/mol. In other embodiments, the copolymers have a Mn between about 800 and about 4,000 g/mol. In certain embodiments, where two or more epoxides are present, the copolymer is random with respect to the position of the epoxide moieties in the chain. In five other embodiments, where two or more epoxies are present, the copolymer is a tapered copolymer with respect to the incorporation of different epoxies. In some embodiments, where two or more epoxies are present, the copolymer is a block copolymer with respect to the incorporation of 10 different epoxies.

In certain embodiments, the polymer chains may contain incorporated polymerization initiators or may be a block copolymer with a non-polycarbonate segment. In certain examples of these embodiments, the established total carbonate content of the polymer chain may be less than the established carbonate content limitations described above. In these cases, the carbonate content refers only to the epoxide CO2 copolymer portions of the polymer composition. In other words, a polymer of the present invention may contain a polyester, polyether, or polyether-polycarbonate portion embedded in or bonded to it. The non-carbonate linkages in such portions are not included in the carbonate and ether linkage limitations described above.

In certain embodiments, polycarbonate polyols of the present invention are further characterized by the fact that they have limited polydispersity. In certain embodiments, the PDI of the provided polymer compositions is less than 2. In some embodiments, the PDI is less than 1.5. In other embodiments, the PDI is less than about 1.4. In certain embodiments, the PDI is less than about 1.2. In other embodiments, the PDI is less than about 1.1. In certain embodiments, the polycarbonate polyol compositions are further characterized by the fact that they have a unimodal molecular weight distribution.

In certain embodiments, the polycarbonate polyols of the present invention contain repeating units derived from epoxides that are not C2 symmetrical. In these cases, the epoxide can be incorporated into the growing polymer chain in one of several orientations. The regiochemistry of the linkage of adjacent monomers, in these cases, is characterized by the head-to-tail relationship of the composition. As used herein, the term "head-to-tail" refers to the regiochemistry of the linkage of a substituted epoxide in the polymer chain, as shown in the figure below for propylene oxide:

In certain embodiments, the disclosure covers polycarbonate polyol compositions characterized in that, on average, more than about 80% of the bonds between adjacent epoxide monomer units are head-to-tail bonds. In certain embodiments, on average, more than 85% of the bonds between adjacent epoxide monomer units are head-to-tail bonds. In certain embodiments, on average, more than 90% of the bonds between adjacent epoxide monomer units are head-to-tail bonds. In certain embodiments, more than 95% of the bonds between adjacent epoxide monomer units are head-to-tail bonds. In certain embodiments, more than 99% of the bonds between adjacent epoxide monomer units are head-to-tail bonds.

In certain embodiments, the polycarbonate polyols of the present invention contain repeating units derived from epoxides that contain a chiral center. In these cases, the epoxide can be incorporated into the growing polymer chain in defined orientations relative to adjacent monomer units. In certain embodiments, the adjacent stereocenters are randomly arranged in the polymer chains. In certain embodiments, the polycarbonate polyols of the present invention are atactic. In other embodiments, more than about 60% of the adjacent monomer units have the same stereochemistry. In certain embodiments, more than about 75% of the adjacent monomer units have the same stereochemistry. In certain embodiments, more than about 85% of the adjacent monomer units have the same stereochemistry. In certain embodiments, more than about 95% of the adjacent monomer units have the same stereochemistry. In certain embodiments, the polycarbonate polyols of the present invention are isotactic. In other embodiments, more than about 60% of adjacent monomer units have opposite stereochemistry. In certain embodiments, more than about 75% of adjacent monomer units have opposite stereochemistry. In certain embodiments, more than about 85% of adjacent monomer units have opposite stereochemistry. In certain embodiments, more than about 95% of adjacent monomer units have opposite stereochemistry. In certain embodiments, the polycarbonate polyols of the present invention are syndiotactic.

In certain embodiments, where a chiral epoxide is incorporated into the polycarbonate polyol compositions of the present invention, the polymers are enantioenriched. In other embodiments, where a chiral epoxide is incorporated into the polycarbonate polyol compositions of the present invention, the polymers are not enantioenriched.

In certain embodiments, the epoxide monomers incorporated into polycarbonate polyols of the present invention have a structure: wherein R21, R22, R23 and R24 are each independently selected from the group consisting of: -H; an optionally substituted group 20 selected from aliphatic C1-30; aryl C6-14; a 3 to 12 membered heterocycle, and a 5 to 12 membered heteroaryl, wherein two or more R21, R22, R23 and R24 may be taken together with intervening atoms to form one or more optionally substituted 3 to 12 membered rings 25, optionally containing one or more heteroatoms.

In certain embodiments, the polycarbonate polyols of the present invention incorporate one or more epoxides selected from the group consisting of: wherein each Rx is independently selected from optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aryl fluoroalkyl, and optionally substituted heteroaryl.

In certain embodiments, the polycarbonate polyols of the present invention comprise ethylene (poly)carbonate. In other embodiments, the polycarbonate polyols of the present invention comprise propylene (poly)carbonate. In other embodiments, the polycarbonate polyols of the present invention comprise cyclohexene (poly)carbonate. In other embodiments, the polycarbonate polyols of the present invention comprise epichlorohydrin (poly)carbonate. In certain embodiments, the polycarbonate polyols of the present invention incorporate a glycidyl ether or glycidyl ester. In certain embodiments, the polycarbonate polyols of the present invention incorporate phenyl glycidyl ether. In certain embodiments, the polycarbonate polyols of the present invention incorporate t-butylglycidyl ester.

In some embodiments, the polycarbonate polyols of the present invention comprise propylene-co-ethylene (poly)carbonate. In certain embodiments, the polycarbonate polyols of the present invention comprise propylene (poly)carbonate with the incorporation of about 0.1 to about 10% of a C4-C30 epoxide. In certain embodiments, the polycarbonate polyols of the present invention comprise propylene (poly)carbonate incorporating about 0.1 to about 10% of a glycidyl ether. In certain embodiments, the polycarbonate polyols of the present invention comprise propylene (poly)carbonate incorporating about 0.1 to about 10% of a glycidyl ester. In certain embodiments, the polycarbonate polyols of the present invention comprise ethylene (poly)carbonate incorporating about 0.1 to about 10% of a glycidyl ether. In certain embodiments, polycarbonate polyols of the present invention comprise ethylene (poly)carbonate incorporating from about 0.1 to about 10% of a glycidyl ester. In certain embodiments, polycarbonate polyols of the present invention comprise ethylene (poly)carbonate incorporating from about 0.1 to about 10% of a C4-C30 epoxide.

In certain embodiments, epoxide monomers incorporated into the polycarbonate polyols of the present invention comprise epoxides derived from natural materials such as epoxidized resins or oils. Examples of such epoxides include, but are not limited to: epoxidized soybean oil; epoxidized linseed oil; epoxidized octyl soyate; epoxidized PGDO; methylepoxyisoyate; butylepoxyisoyate; epoxidized octyl soyate; linseed methylepoxy; linseed butylepoxy; and linseed octylepoxy. These and other similar materials are commercially available from Arkema Inc. under the trade name Vikoflex®. Examples of such commercially available Vikoflex® materials include epoxidized soybean oil Vikoflex 7170, epoxidized linseed oil Vikoflex 7190, epoxidized octyl soyate Vikoflex 4050, epoxidized PGDO Vikoflex 5075, methyl epoxy soyate 7010, butyl epoxy soyate Vikoflex 7040, epoxidized ethyl soyate Vikoflex 7080, methyl linseed epoxy Vikoflex 9010, butyl linseed epoxy Vikoflex 9040, and octyl linseed epoxy 9080. In certain embodiments, the polycarbonate polyols of the present invention incorporate epoxidized fatty acids:

In certain embodiments of the present invention, polycarbonate polyols of the present invention incorporate epoxides derived from alpha-olefins. Examples of such epoxides include, but are not limited to, those derived from alpha-olefin C10, alpha-olefin C12, alpha-olefin C14, alpha-olefin C16, alpha-olefin C18< C2O₂C24, alpha-olefin C24-C28 and alpha-olefin C30+. These and similar materials are commercially available from Arkema Inc. under the brand name Vikolox®. Commercially available Vikolox® materials include those shown in Table 4 below. In certain embodiments, the supplied aliphatic polycarbonates derived from alpha-olefins are heteropolymers incorporating other simpler epoxide monomers, including, but not limited to: ethylene oxide, propylene oxide, butylene oxide, hexene oxide, cyclopentene oxide and cyclohexene oxide. These heteropolymers may include random copolymers, copolymers Tapered and block copolymers. Table 4

In certain embodiments, the present disclosure encompasses aliphatic polycarbonate compositions comprising a plurality of polymer chain types. In certain embodiments, these different chain types are derived from more than one type of initiating molecule. These compositions are described in more detail below. In each case, the polycarbonate chains contain one or more polymeric units resulting from the alternating copolymerization of CO2 and one or more epoxides. In the following descriptions of the various chain types that may be present in the compositions of the present invention, these alternating copolymer units are denoted T-, where each T- is a polycarbonate chain having a formula independently selected from the group consisting of: , where:

E is an optionally substituted C2 unit derived from an epoxide, where E can represent a monomeric unit derived from one type of epoxide, or from a mixture of two or more types of epoxide, and ranges from about 5 to about 10,000 p.

In some embodiments of the polymers encompassed by the present invention, -E- is: where R21, R22, R23, R24 are as defined above.

In certain modalities, -E- is selected from the group consisting of: and mixtures of two or more of these.

In certain embodiments, -E- includes units derived from natural materials such as epoxidized resins or oils. In certain embodiments, -E- includes units derived from C12_30 alpha-olefins.

In some embodiments, -E- consists predominantly of -CH2CH2- units derived from ethylene oxide. In certain embodiments, -E- includes units derived from ethylene oxide in combination with quantities of more complex -E- groups derived from other epoxides.

In other embodiments, -E- consists predominantly of -CH2CH(CH3)-groups derived from propylene oxide. In certain embodiments, -E- includes propylene oxide-derived units in combination with -E-groups derived from ethylene oxide. In certain embodiments, -E- includes propylene oxide-derived units in combination with 5 smaller amounts of more complex -E-groups derived from other epoxides.

In certain embodiments, the polycarbonate-polyol compositions described above include mixtures of various chain types. In general, these chain types 10 can be divided into two categories: namely, the first category including chains called P^- having two or more terminal OH groups and a second category of chains called P2- having only one terminal OH group per chain. As described above, in some embodiments the compositions of the present invention have at least 90% of the polymer chain ends terminating with OH groups. As such, the chains of the first category generally comprise a predominance of the chains present in the compositions. Polymer chains in a given composition 20 can arise from each of the various different chain initiation moieties present in a reaction mixture. In certain cases, each of these chain types will have a distinct structure that will differentiate it from other chain types present in the mixture that derive from other chain initiation moieties 25. The structures of each of the various chain types are described below, and the reasons why these components may be present are described next.

The aliphatic polycarbonate compositions of the present invention include polymer chains derived from the chain transfer agents described above. In certain embodiments, these polymer chains are called P1. In some embodiments, where the chain transfer agent has a formula Y-A-(Y)n, as described above, the P1 type polymer chains have the formula T-Y-A-(Y-T)n, wherein Y, A and n are as defined above in the description of the chain transfer agents, and each -T is an aliphatic polycarbonate chain covalently linked to a Y group, where -T is as defined above.

P1 type chains can also derive from polyfunctional initiation ligands described above. In certain embodiments, where the initiation ligand has a formula Q'-A'-(Z')n, as described above, these chains have the formula T-Q'-A'(Z'-T)n, where Q', A', Z' and n are as defined above in the description of the initiation ligands. Each -T is an aliphatic polycarbonate chain covalently linked to a Q' or Z' group, where T is as defined above.

Furthermore, P1-type chains can arise from an anion present in a co-catalyst. In certain embodiments, where the anion has a formula Q'-A'-(Z')n, as described above, these chains have the formula T-Q'-A'(Z'-T)n, where Q', A', Z' and n are as defined above in the description of co-catalyst anions, and each -T is an aliphatic polycarbonate chain covalently linked to a Q' or Z' group, where -T is as defined above.

An additional category of P1 chains can arise from the water present in the reaction mixtures. Under certain circumstances, under polymerization conditions, water will open an epoxide ring leading to the formation of a glycol corresponding to one or more epoxides present in the reaction mixture. In certain embodiments, this glycol (or mixture of glycols, if more than one type of epoxide is present) will lead to the formation of Plating-type chains, giving the structure: wherein -E- is an optionally substituted C2 unit derived from an epoxide, where E may represent a monomeric unit derived from a single type of epoxide or from a mixture of two or more types of epoxide, ep varies from about 5 to about 10,000.

In some embodiments, each of these P1 chain sources may have a different structure, and the compositions may include various types of P1 chains (e.g., P1 type derived from the chain transfer agent, P1’ type derived from polyfunctional initiation ligands, and P1” type derived from polyfunctional anions present in a co-catalyst). In certain embodiments, the chain transfer agent and co-catalyst anions may have the same structure (i.e., ionic forms of the same structure). In these cases, the polymeric compositions may comprise only one type of P1 chain, or, if water is present, a mixture of a single type of P1 chain along with a certain amount of Pla. In certain embodiments, a glycol corresponding to an epoxide present in the reaction mixture may be used as a chain transfer agent, in which case the P^’ polymeric chains arising from the chain transfer agent and Pla arising from water will be indistinguishable. In certain other embodiments, the Water can be strictly excluded from the polymerization mixture, in which case Plase-type chains will be substantially absent.

Furthermore, in certain embodiments, the polymeric compositions of the present invention include P2-type polymeric chains. These chains have only one terminal OH group. P2-type chains can arise from monofunctional initiating ligands present in metal complexes or from monofunctional ionic anions present in ionic co-catalysts. In certain cases, these chains can also arise from spurious sources, such as alcohols or halide ions present as impurities in the reaction mixtures. In certain embodiments, the P2-type chains have a formula selected from the group consisting of: , wherein: X is a linked form of an anion capable of initiating a polymer chain; 20 E is an optionally substituted C2 unit derived from an epoxide, where E may represent a monomeric unit derived from one type of epoxide, or from a mixture of two or more types of epoxide, and p ranges from about 5 to about 10,000.

In certain embodiments of P2-type polymer chains, X comprises a halogen atom, an azide, an ester group, an ether group, or a sulfonic ester group.

In some embodiments, the polymeric compositions of the present invention are characterized by the fact that at least 90% of the chain ends are -OH. In certain embodiments, at least 90% of the chains in a polymeric composition are of the P1 type. In certain embodiments, the P1 type chains are essentially identical. In other embodiments, there are two or more distinct types of P1 chains present. In certain embodiments, there are several types of P1 chains present, but at least 80% of the P1 chains have a structure with smaller amounts of one or more types of P1 chains that make up the remaining 20%.

In certain embodiments, the polymeric compositions of the present invention include more than 95% of P1-type chains. In other embodiments, the polymeric compositions of the present invention include more than 97% of P1-type chains. In certain embodiments, the polymeric compositions of the present invention include more than 99% of t±po- _BL_ chains.

It should be noted that, in certain embodiments, the polymeric compositions of the present invention are characterized by the fact that at least 90% of the chain ends are -OH groups and may include mixtures with less than 90% of the P1 type chains, for example, when a chain transfer agent capable of initiating three or more polymeric chains is used. For example, where a triol is used as a chain transfer agent, if 80% of the chains result from initiation by the triol (3-OH end groups per chain) and the remaining 20% of the chains have only one end -OH group, the composition as a whole will still have more than 90% end OH groups (92.3%).

In certain embodiments, the polymeric compositions of the present invention include PM-type chains derived from diol chain transfer agents. In certain embodiments, these chains have the formula: where E and ep are as defined above and -A- is an optionally substituted radical selected from the group consisting of: C2-30 aliphatic, C2-30 heteroaliphatic, 6-12 membered aryl, 3-12 membered heterocyclic, 5-12 membered heteroaryl.

In other embodiments, A- is a polymer selected from the group consisting of polyolefins, polyesters, polyethers, polycarbonates, polyoxymethylene and mixtures of two or more of these.

In certain embodiments, the polymeric compositions of the present invention include p¹-type chains derived from hydroxy acid chain transfer agents. In certain embodiments, these chains have the formula: defined above, -A- is an optionally substituted radical selected from the group consisting of: C2-30 aliphatic, C2-30 heteroaliphatic heteroaliphatic, aryl with 6 to 12 members, heterocyclic with 3 to 12 members, heteroaryl with 5 to 12 members.

In certain embodiments, the polymeric compositions of the present invention include P-type chains derived from diacid chain transfer agents. In certain embodiments, these chains have the formula: where E and p are as defined above and -A- is a covalent bond or an optionally substituted radical selected from the group consisting of: aliphatic C2-30, heteroaliphatic C2-30, aryl with 6 to 12 members, heterocyclic with 3 to 12 members, heteroaryl with 5 to 12 members.

In certain embodiments, the polymeric compositions of the present invention include P^'-type chains derived from trifunctional chain transfer agents. In certain embodiments, these chains have the formula: where Eep are as defined above, each -z- is undependently 0 or 1, and -A- is an optionally substituted radical selected from the group consisting of: aliphatic C3-30, heteroaliphatic C2-30, aryl of 6 to 12 members, heteroaliphatic of 3 to 12 members, heteroaryl of 5 to 12 members.

In another aspect, the present invention encompasses materials by crosslinking any of the polycarbonate polyol polymers. In certain embodiments, such crosslinked materials comprise polyurethanes. In certain embodiments, such polyurethanes include thermoplastics, foams, coatings, and adhesives.

III. Methods for Making Polycarbonate Polyols

In a third aspect, the present invention encompasses methods for the production of polycarbonate polyols.

In some embodiments, the methods include the steps of: a) providing a reaction mixture, including one or more epoxides and one or more chain transfer agents with a plurality of sites capable of supporting the chain growth of CO2 epoxide copolymers; b) contacting the reaction mixture with a metal complex, the metal complex including a coordination metal compound having a permanent linker group and at least one linker that is a polymerization initiator in the presence of carbon dioxide; c) allowing the polymerization reaction to continue until a desired molecular weight of the polymer is formed; and d) terminating the polymerization.

III.a Epoxies

In some embodiments, the epoxide monomers provided in step (a) include any of the epoxides described above with respect to the polymer compositions of the matter.

In some embodiments, the epoxide monomers provided in step (a) of the method described above have a structure: wherein R21, R22, R23 and R24 are each independently selected from the group consisting of: -H; an optionally substituted group selected from aliphatic C-30; aryl C-14; a 3- to 12-membered heterocycle, and a 5- to 12-membered heteroaryl, wherein two or more of R21, R22, R23 and R24 may be taken together with intervening atoms to form one or more optionally substituted 3- to 12-membered rings, optionally containing one or more heteroatoms.

In certain embodiments, the reaction mixtures include one or more epoxides selected from the group consisting of: where each Rx is independently selected from optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aryl, and optionally substituted heteroaryl.

In certain embodiments, the reaction mixtures include ethylene oxide. In other embodiments, the reaction mixtures include propylene oxide. In other embodiments, the reaction mixtures include cyclohexene oxide. In other embodiments, the reaction mixtures include epichlorohydrin. In certain embodiments, the reaction mixtures include a glycidyl ether or glycidyl ester. In certain embodiments, the reaction mixtures include phenylglycidyl ether. In certain embodiments, the reaction mixtures include t-butylglycidyl ether.

In certain embodiments, the reaction mixtures include ethylene oxide and propylene oxide. In certain embodiments, the reaction mixtures include propylene oxide along with about 0.1 to about 10% of a C4-C30 epoxide. In certain embodiments, the reaction mixtures include propylene oxide along with about 0.1 to about 10% of a glycidyl ether. In certain embodiments, the reaction mixtures include propylene oxide along with about 0.1 to about 10% of a glycidyl ester. In certain embodiments, the reaction mixtures include ethylene oxide along with about 0.1 to about 10% of a glycidyl ether. In certain embodiments, the reaction mixtures include ethylene oxide, along with from about 0.1 to about 10% of a glycidyl ester. In certain embodiments, the reaction mixtures include ethylene oxide, along with from about 0.1 to about 10% of a C4-C30 epoxide.

In certain embodiments, the reaction mixtures include epoxides derived from naturally occurring materials such as epoxidized resins or oils. Examples of such epoxides include, but are not limited to: epoxidized soybean oil; epoxidized linseed oil; epoxidized octyl soyate; epoxidized PGDO; methyl epoxy soyate; butyl epoxy soyate; epoxidized octyl soyate; linseed methyl epoxy; linseed butyl epoxy; and linseed octyl epoxy. These and other similar materials are commercially available from Arkema Inc. under the trade name Vikoflex®. Examples of such commercially available Vikoflex® materials include epoxidized soybean oil Vikoflex 7170, epoxidized linseed oil Vikoflex 7190, epoxidized octyl soyate Vikoflex 4050, epoxidized PGDO Vikoflex 5075, methyl epoxy soyate 7010, butyl epoxy soyate Vikoflex 7040, epoxidized octyl soyate Vikoflex 7080, methyl epoxy linseed oil Vikoflex 9010, butyl epoxy linseed oil Vikoflex 9040, and octyl epoxy linseed oil 9080. In certain embodiments, the polycarbonate polyols of the present invention incorporate epoxidized fatty acids.

In certain embodiments of the present invention, reaction mixtures include epoxides derived from alpha-olefins.

Examples of such epoxides include, but are not limited to, those derived from alpha-olefin C10, alpha-olefin C12, alpha-olefin C14, alpha-olefin C16, alpha-olefin C18, alpha-olefin C20-C24, alpha-olefin C24-C28, and alpha-olefin C30+. These and similar materials are commercially available from Arkema Inc. under the brand name Vikolox®. Commercially available Vikolox® materials include those shown in Table 4 below. In certain embodiments, the reaction mixtures including alpha-olefins also include other simpler epoxide monomers, including, but not limited to: ethylene oxide, propylene oxide, butylene oxide, hexene oxide, cyclopentene oxide, and cyclohexene oxide.

III. b. Chain Transfer Agents

In certain embodiments, a 20 chain transfer agent provided in step (a) of the method above is any of the chain transfer agents described herein above or mixtures of two or more of these.

In some embodiments, the chain transfer agents provided in step (a) of the methods above include one or more polyhydric alcohols. In certain embodiments, a polyhydric alcohol is a diol. In certain embodiments, diols include, but are not limited to: 1,2-ethanediol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 2,2-dimethylpropane-1,3-diol, 2-butyl-2-ethylpropane-1,3-diol, 1,5-hexanediol, 1,6-hexanediol, 1,8-octanediol, 1,10-decanediol, 1,12-dodecanediol, 2,2,4,4-tetramethylcyclobutane-1,3-diol, 1,3-cyclopentanediol, 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol and 1,4-cyclohexanediethanol. Other examples include polyalkylene glycols, such as: diethylene glycol, triethylene glycol, tetraethylene glycol, (poly)ethylene glycol (higher), such as those with an average molecular weight of 220 to about 2000 g/mol, dipropylene glycol, tripropylene glycol and (poly)propylene glycol (higher) such as those with an average molecular weight of 234 to about 2000 g/mol.

In certain embodiments, the diol chain transfer agents include hydroxyl-terminated polyolefins.

Such materials include polymers sold by Sartomer Inc. under the trade name Krasol®. In other embodiments, diol chain transfer agents may include hydroxyl-terminated polyisobutylenes (PIB-diols and triols) such as Polytail® H or Polytail® HA from Mitsubishi Chemical Co. Other examples include hydroxyl-terminated polybutadienestyrene (HTBS).

Still other examples of suitable diols that may be supplied in step (a) include 4,4'-(1-methylethylidene)bis[cyclohexanol], 2,2'-methylenebis[phenol], 4,4'-methylenebis[phenol], 4,4'-(phenylmethylene)bis[phenol], 4,4'-(diphenylmethylene)bis[phenol], 4,4'-(1,2-ethanediyl)bis[phenol], 4,4'-(1,2-cyclohexanediyl)bis[phenol], 4,4'-(1,3-cyclohexanediyl)bis[phenol], 4,4'-(1,4-cyclohexanediyl)bis[phenol], 4,4'-ethylidenebis[phenol], 4,4'-(1-phenylethylidene)bis[phenol], 4,4'-propylidenebis[phenol] - (2,4,8,10-tetraoxaspiro[5.5]undecane-3,9-diyldi-2,1-ethanediyl)bis[phenol], 1,2-benzenedimethanol, 1,3-benzenedimethanol, 1,4-benzenedimethanol, 4,4'-[1,3- phenylenebis(1-methylethylidene)]bis[phenol],4,4'-[1,4- phenylenebis(1-methylethylidene)]bis[phenol], phenolphthalein, 4,4'-(1-methylidene)bis[2-methylphenol], 4,4'-(1-methylethylidene)bis[2-(1-methylethyl)phenol], 2,2'-methylenebis[4-methyl-β-](1-methylethyl)phenol. In certain embodiments, a chain transfer agent provided in step (a) is a polyhydric phenol derivative. In certain embodiments, a polymerization initiator is selected from the group consisting of:

In some embodiments, a polyhydric alcohol provided as a chain transfer agent in step (a) of the above method is a triol, a tetraol, or a higher polyol. Suitable triols may include, but are not limited to: aliphatic triols with a molecular weight less than 500, such as trimethylolethane; trimethylolpropane; glycerol; 1,2,4-butanetriol; 1,2,6-hexanetriol; tris(2-hydroxyethyl)isocyanurate; hexahydro-1,3,5-tris(hydroxyethyl)-s-triazine; 6-methylheptane-1,3,5-triol; polypropylene triol oxide; and polyester triols.

In certain other embodiments, a polyol is a tetraol. Examples of suitable tetraols include, but are not limited to: erythritol, pentaerythritol, 2,2'-dihydroxymethyl-1,3-propanediol; and 2,2'-(oxydimethylene)bis-(2-ethyl-1,3-propanediol).

In still other forms, a polyol is a carbohydrate. Examples of suitable carbohydrates include sugar alcohols, monosaccharides, disaccharides, oligosaccharides and polysaccharides, and higher oligomers such as starch and starch derivatives.

In some embodiments, one -OH group of a diol is phenolic and the other is aliphatic. In other embodiments, each hydroxyl group is phenolic. In certain embodiments, the chain transfer agent is an optionally substituted catechol, resorcinol, or hydroquinone derivative.

In some embodiments, where a Y- is -OH group, the -OH group is an enolic tautomer of a carbonyl group. In some embodiments, where a Y- is -OH group, the -OH group is a carbonyl hydrate or a hemiacetal.

In certain embodiments, a chain transfer agent provided in step (a) includes a hydroxy acid. In certain embodiments, a chain transfer agent includes a diacid. In certain embodiments, a chain transfer agent includes a compound selected from the group consisting of:

In certain embodiments, diacid chain transfer agents include carboxy-terminated polyolefin polymers. In certain embodiments, carboxy-terminated polyolefins include materials such as the NISSO-PB C series resins produced by Nippon Soda Co. Ltd.

In certain embodiments, a provided chain transfer agent is a hydroxy acid. In certain embodiments, a hydroxy acid is selected from the group consisting of:

In certain embodiments where the provided chain transfer agent includes an acidic functional group, the compound is provided as a salt. In certain embodiments, a carboxylic chain transfer agent is provided as an ammonium salt.

III.c. Polymerization Catalysts

In some embodiments, a supplied metal complex is a polymerization catalyst. In certain embodiments, a polymerization catalyst with which the reaction mixture comes into contact in step (b) of the method described above includes any one or more of the catalysts previously described in this document.

In certain embodiments, the metal complexes of step 15(b) have the formula Lp-M-(L!)m, wherein Lp is a permanent ligand group, M is a metal atom and Lj is a ligand that is a polymerization initiator, and m is an integer between 0 and 2 inclusive, representing the number of initiating ligands present.

In certain embodiments, the metal complexes used in step (b) of the method have a structure 5 selected from the group consisting of: is selected from the group consisting of: where: M, Rc, R', Li, m R4a, R4a', R5a, R5a', R6a, R6a', R7a and R7a are 10 as defined above.

In certain embodiments of the metal complexes used in step (b), they have a selected group structure consisting of: where Rlaaté R7a's are as defined above.

In certain embodiments of the metal complexes used in step (b), they have a selected group structure consisting of: where R5a, R5a', R7a and R7a' are as defined above. In certain embodiments, each pair of substituents on the salicaldehyde moieties of the above complexes are the same (i.e., R5a' and R5a' are the same and R7a' and R7a' are the same). In other embodiments, at least one of R5a' and R5a' or R7a' and R7a' are different from each other.

In certain embodiments, a metal complex used in step (b) of the method has formula III:

In certain embodiments, a metal complex used in step (b) of the method has formula IV:

In certain embodiments, a metal complex used in step (b) of the method has formula V: wherein: Rc, Rd, Li, m, q, R4, R4', R5, R5', R6, R6, R7 and R7' are as described above, and where [R1 and R4], [R1' and R4'] and any two adjacent groups R4, R4, R5, R5', R6, R6', R7 and R7' may optionally be taken together with intervening atoms to form one or more optionally substituted common rings or more R20 groups.

In certain embodiments, where a given metal complex has formula III, R1, R1’, R4, R4, R6 and R6 are each H-. In certain embodiments, where the metal complex has formula III, R5, R5’, R7 and R7’ are each an aliphatic C1-C12 optionally substituted.

In certain methods where a given metal complex has formula III, R4, R4', R5, R5', R6, R6', R7, and R7' are each independently selected from the group consisting of: -H, -Si(R13)3; -Si[(CH2)kR22]z(R13)(3.z); methyl, ethyl, n-propyl, i-propyl, n-butyl, sec-butyl, t-butyl, isoamyl, t-amyl, texyl, trityl, -C(CH3)Ph2, (CH2)PC[(CH2)pR22]2H(3-z), and -Si(R13)(3-Z)[(CH2)kR22]z, where p is an integer from 0 to 12 inclusive, and R22 is selected from the group consisting of: a heterocycle; an amine; a guanidine; -N+ (R11) 3X'; -P+ (R11) 2=N+=P (R11) 3X‘; _∑AS1IR11L3X^ _e optionally substituted pyridinium.

In certain methods where a given metal complex has formula III, R7 is selected from the group consisting of -H; methyl; ethyl; n-propyl; i-propyl; n-butyl; sec-butyl; t-butyl; isoamyl; t-amyl; texyl; and trityl; and R5 is selected from the group consisting of -(CH2)pCH(3-z)[(CH2)PR22]z and -Si(R13)(3-z)[(CH2)kR22]z.

In certain methods, a given metal complex has formula IV, R1, R1', R4, R4', R6, and R6' are each -H. In 25 certain embodiments, where a complex is a metalosalenate complex of formula IV, R5, R5, R7, and R7' are each optionally substituted aliphatic C1-C12.

In certain methods where a metal complex has formula IV, R4, R4', R5, R5', Rs, R6', R7, and R7' are each independently selected from the group consisting of: -H, -Si(R13)3; -Si(R13)(3-z)[(CH2)kJR22]z7 methyl, ethyl, n-propyl, i-propyl, n-butyl, sec-butyl, t-butyl, isoamyl, t-amyl, texyl, tritil, -(CH2)PC[(CH2)PR22]ZH(3-Z)

In certain methods where a metal complex has formula IV, R7 is selected from the group consisting of -H; methyl; ethyl; n-propyl; i-propyl; n-butyl; sec-butyl; t-butyl; isoamyl; t-amyl; texyl and trityl; and R5 is selected from the group consisting of - (CH2)pCH(3-Z) [ (CH2)PR22] z and -Si(R13)(3- z) [ (CH2)kR22] z.

In methods where a metal complex has the formula V, R1, R1', R4, R4', R6 and R6' are each -H. In certain embodiments, where a complex is a metalolsalenate complex of formula V, R5, R5', R7 and R7' are each optionally substituted aliphatic C1-C12.

In certain methods in which a metal complex has the formula V, R4, R4', R5, R5', R6, R6', R7, and R7' are each independently selected from the group consisting of:-H, -Si(R13)3;-Si[(CH2)kR21]z(R13)(3-Z); methyl; ethyl; n-propyl, i-propyl, n-butyl, sec-butyl, t-butyl, isoamyl, t-amyl, texyl, trityl, - (CH2) pCH(3-z) [ (CH2)pR22] z e-Si (R13) (3-z) [ (CH2) kR22] z .

In certain methods where a metal complex has the formula V, R7 is selected from the group consisting of: -H; methyl; ethyl; n-propyl; i-propyl; n-butyl; sec-butyl; t-butyl; isoamyl; t-amyl; texyl and trityl; and R5 is selected from the group consisting of - (CH2) PCH(3-Z) [ (CH2) PR22] z and -Si(R13)(3- z) [ (CH2)kR22] z.

In some embodiments, a metallic complex has an Lp-M-djj)™ structure, where Lp-M is selected from the group consisting of:

It is also desirable to maintain the concentration of a metal complex in a polymerization at a low level relative to the epoxide. In certain embodiments, the molar ratio of the metal complex to epoxide ranges from about 1:100 to about 1:1,000,000. In certain embodiments, the ratio ranges from about 1:5,000 to about 1:500,000. In some embodiments, the ratio ranges from about 1:10,000 to about 1:200,000. In other embodiments, the ratio ranges from about 1:20,000 to about 1:100,000.

III.d Co-catalysts

In some embodiments, the methods of the present invention include the use of at least one co-catalyst. In some embodiments, a co-catalyst is present in step (b). In certain embodiments, a co-catalyst is any one or more of the co-catalytic species described above in the description of the polymerization systems of the present invention. In certain embodiments, a co-catalyst is selected from the group consisting of: amines, guanidines, amidines, phosphines, nitrogen-containing heterocycles, ammonium salts, phosphonium salts, arson salts, ammonium biphosphine salts, and a combination of two or more of the above options. In certain embodiments, a co-catalyst is covalently linked to the permanent ligand group of the metal complex.

In embodiments where a method includes a co-catalyst that is an "onion" salt, there is not necessarily an anion present to balance the charge of the salt. In certain embodiments, this is any anion. In certain embodiments, an anion is a nucleophile. In some embodiments, an anion is a nucleophile capable of opening an epoxide ring. In some embodiments, an anion is selected from the group consisting of: azides, halides, alkyl sulfonates, carboxylates, alkoxides, and phenolates. In certain embodiments, the methods include a catalyst and co-catalyst selected such that the initiating ligand in the metal complex and an anion present to balance the charge of a cationic co-catalyst are the same molecule.

III.e. Reaction Conditions

In certain embodiments, the steps of any of the above methods still comprise one or more solvents. In certain other embodiments, the polymerization steps are carried out in pure epoxide, without the addition of solvent.

In certain methods, where the polymerization solvent is present, the solvent is an organic solvent. In certain embodiments, the solvent is a hydrocarbon. In certain embodiments, the solvent is an aromatic hydrocarbon. In certain embodiments, the solvent is an aliphatic hydrocarbon. In certain embodiments, the solvent is a halogenated hydrocarbon.

In certain embodiments, the solvent is an ether. In certain embodiments, the solvent is an ester. In certain embodiments, the solvent is a ketone.

In certain embodiments, suitable solvents include, but are not limited to: methylene chloride, chloroform, 1,2-dichloroethane, propylene carbonate, acetonitrile, dimethylformamide, N-methyl-2-pyrrolidone, dimethyl sulfoxide, nitromethane, caprolactone, 1,4-dioxane and 1,3-dioxane.

In certain other embodiments, suitable solvents include, but are not limited to: methyl acetate, ethyl acetate, acetone, methyl ethyl ketone, propylene oxide, tetrahydrofuran, mongolize triglyceride, propionitrile, 1-nitropropane, cyclohexanone.

In certain embodiments, any of the above methods comprises an aliphatic oxide present in amounts of concentrations between about 0.5 M and about 20 M or the pure concentration of the aliphatic oxide. In certain embodiments, the aliphatic oxide is present in amounts between about 0.5 M and about 2 M. In certain embodiments, the aliphatic oxide is present in amounts between about 2 M and about 5 M. In certain embodiments, the aliphatic oxide is present in amounts between about 5 M and about 20 M. In certain embodiments, the aliphatic oxide is present in an amount of about 20 M.

In certain embodiments, the liquid aliphatic oxide comprises the reaction solvent.

In certain embodiments, CO2 is present at a pressure between approximately 30 psi and approximately 800 psi. In certain embodiments, CO2 is present at a pressure between approximately 30 psi and approximately 500 psi. In certain embodiments, CO2 is present at a pressure between approximately 30 psi and approximately 400 psi. In certain embodiments, CO2 is present at a pressure between approximately 30 psi and approximately 300 psi. In certain embodiments, CO2 is present at a pressure between approximately 30 psi and approximately 200 psi. In certain embodiments, CO2 is present at a pressure between approximately 30 psi and approximately 100 psi. In certain embodiments, CO2 is present at a pressure between approximately 30 psi and approximately 80 psi. In certain embodiments, CO2 is present at a pressure of approximately 30 psi. In certain modes, CO2 is present at a pressure of about 50 psi. In certain modes, CO2 is present at a pressure of about 100 psi. In certain modes, CO2 is supercritical.

In certain embodiments of the above methods, the reaction is carried out at a temperature between about 0 °C and about 150 °C. In certain embodiments, the reaction is carried out at a temperature between about 23 °C and about 100 °C. In certain embodiments, the reaction is carried out at a temperature between about 23 °C and about 80 °C. In certain embodiments, the reaction must be carried out at a temperature between about 23 °C and about 50 °C.

In certain embodiments, a polymerization step of any of the above methods produces cyclic carbonate as a byproduct in amounts less than about 20%. In certain embodiments, cyclic carbonate is produced as a byproduct in amounts less than about 15%. In certain embodiments, cyclic carbonate is produced as a byproduct in amounts less than about 10%. In certain embodiments, cyclic carbonate is produced as a byproduct in amounts less than about 5%. In certain embodiments, cyclic carbonate is produced as a byproduct in amounts less than about 1%. In certain embodiments, the reaction does not produce any detectable byproducts (e.g., as detectable by 1-NMR and/or liquid chromatography (LC)).

In certain embodiments, the polymerization time is between approximately 30 minutes and approximately 48 hours. In some embodiments, the reaction is allowed to proceed for less than 24 hours. In some embodiments, the reaction is allowed to progress for less than 12 hours. In some embodiments, the reaction is allowed to progress for between approximately 4 and approximately 12 hours.

In certain embodiments, a polymerization reaction is allowed to progress until the average molecular weight of the polymers formed is between about 500 and about 2,500 g/mol. In other embodiments, the average molecular weight is allowed to reach a value between 1,000 and 5,000 g/mol.

In certain embodiments, the methods provided further include the step of sampling the reaction and determining the molecular weight of the polymer at a given time. In certain embodiments, this sampling and molecular weight determination are performed at two or more time intervals. In certain embodiments, a graph of molecular weight gain over time is constructed, and the method further includes the step of determining the time graph during which a polymer of the desired molecular weight will be present. In certain embodiments, the moment when the polymerization is finished is determined by this method.

In certain embodiments, a polymerization reaction proceeds until between about 20% and about 100% of the supplied epoxide is consumed. In certain embodiments, the conversion is between about 40% and about 90%. In certain embodiments, the conversion is at least 50%. In other embodiments, the conversion is at least 60%, at least 80%, or at least 85%. In certain embodiments, at least 80% of the supplied epoxide is converted into polymer.

In certain embodiments, a method further includes step 25 of choosing the ratios in which the catalyst, chain transfer agent, and epoxide substrate are provided. In certain embodiments, these ratios are selected to provide high epoxide conversion while providing polyol of desired molecular weight in a selected time period. In some embodiments, this selection of ratios includes the substeps of: i) selecting a desired time period for the reaction to occur, ii) multiplying the selected time period for which the polymerization reaction is carried out by the catalyst turnover frequency under reaction conditions, iii) multiplying this result by the intended conversion in mol% of epoxide, and iv) using the inverse of this result as the catalyst-to-epoxide ratio used for the reaction. In some embodiments, the chain transfer agent-to-catalyst ratio is determined by the following additional steps; v) taking the value from step (iii) above and multiplying this result by the molecular weight of the repeating unit of polycarbonate; vi) select a desired molecular weight for the polyol and divide the result of step (v) by e_s_te — number; and vii) subtract the number of chains produced by the catalyst molecule from the result of step (vi), taking the result as the transfer agent ratio for the catalyst used in step (1). To make the steps of the method described above clear, the following example is provided: in a copolymerization of propylene oxide and CO2 using a catalyst that has a TOF of 1000 h⁻¹ and that produces two polymer chains per catalyst molecule, a polymer with Mn of 2000 g/mol is to be produced, and it is desirable that 80% of the supplied epoxide be converted during a reaction time of 10 hours, one could perform the following steps to obtain the necessary ratios:

First, carrying out 10 hours as the selected time interval and performing step (ii) multiplying the selected interval of 10 hours by the TOF of 1000 hr-1 gives 10,000 turnovers per catalyst molecule; then multiplying this number by 80% desired conversion (step (iii)) and then inverting (step (iv)) gives a value of 1.25 x 10'4 corresponding to a catalyst to epoxide ratio of 1:8,000.

Moving on to determining the chain transfer agent charge, in step (iv) one multiplies the result from step (iii) by the molecular weight of the repeating unit of polycarbonate (in this case C4H6O3 = 102 g/mol) and divides by the desired Mn of 2,000 to give a value of 408. Subtracting the two chains by the catalyst from this result gives a chain transfer to catalyst ratio of 406:1. Therefore, for this example, the molar ratio of catalyst to epoxide to chain transfer agent should be approximately 1:8,000:406.

It will be perceived that the method described above is simplified in certain respects. For example, the calculation described assumes that the reaction rate is linear throughout the duration of the polymerization. The calculation described also disregards the contribution that the mass of the chain initiator adds to the molecular weight of the polymer chains. In certain embodiments, namely those in which a polymer chain transfer agent, such as a polyether, is used, or when a very low molecular weight oligomer is produced, the contribution of the initiator mass to the Mn of the polymer can be significant. It will be understood by those skilled in the art that the additional chain transfer agent can be added to account for this effect, and more specifically, that the calculations described above can be modified to account for this effect. Similarly, more detailed kinetic data could be used to explain the changes in the reaction rate over time as the reaction proceeds. For cases where a mixture of epoxides is present, the molecular weight of the repeating unit can be approximated by means of a weighted average of the molecular weights of the epoxides present in the mixture. This could be further improved by means of copolymer analysis performed under similar conditions to determine the percentage mole incorporation of the different monomers (e.g., using NMR spectroscopy), since not all epoxides may be incorporated into the polymer with equal efficiency.

These and other modifications will be readily grasped by the skilled professional and are specifically encompassed by the methods provided herein.

In certain embodiments, it has been found that the turnover frequency of some catalysts decreases as the chain transfer agent to catalyst ratio increases. This effect can be particularly noticeable at ratios greater than about 100:1. In such cases, the methods described above may not produce the expected Mn and monomer conversion within a given time interval. In such cases, it may be necessary to measure the TOF of the catalyst at various chain transfer agent ratios before performing the calculations described above. In general, these cases require that the reaction interval be extended by an amount proportional to the drop in catalytic activity at the catalyst to chain transfer agent ratio used or, in some embodiments, the catalyst loading may be increased by a compensating amount.

As mentioned above, the water present in the reaction mixtures of the described methods can also act as a chain transfer agent. In certain embodiments, the calculations described above further include the method of measuring the water content of the reaction (preferably after the reaction flask has been loaded with epoxy, chain transfer agent and any solvent to be used, but before the addition of the catalyst). The molar equivalents of water relative to the catalyst are then calculated and the ratio of chain transfer agent to catalyst can be reduced appropriately. If this is not done and there is water present in significant quantity, the Mn will be lower than expected at a given % conversion.

IV. Higher Polymers

This disclosure encompasses superior polymers derived from the polycarbonate polyols described above. In certain embodiments, such superior polymers are formed by the reaction of the polyols with suitable crosslinking agents. In certain embodiments, the crosslinkers, including functional groups reactive to the hydroxyl groups, are selected, for example, from epoxy and isocyanate groups. In certain embodiments, such crosslinking agents are polyisocyanates.

In some embodiments, a bifunctional isocyanate or 30 of higher functionality is selected from diisocyanates, the biuretes and cyanurates of diisocyanates, and the adducts of diisocyanates to polyols. Suitable diisocyanates generally have from 4 to 22 carbon atoms. Diisocyanates are typically selected from aliphatic, cycloaliphatic, and aromatic diisocyanates, for example, 1,4-diisocyanatobutane, 1,6-diisocyanatohexane, 1,6-diisocyanato-2,2,4-trimethylhexane, 1,6-diisocyanato-2,4,4-trimethylhexane, 1,2-, 1,3- and 1,4-diisocyanatocyclohexane, 2,4- and 2,6-diisocyanato-1-methylcyclohexane, 4,4'-bis(isocyanatocyclohexyl)methane, diisocyanatoisophorone (= 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane), 2,4- and 2,6-tolylene diisocyanate, tetramethylene-p-xylylene diisocyanate (= 1,4-bis(2-isocyanatoprop-2-yl)benzene), 4,4'-diisocyanatodiphenylmethane, preferably 1,6-diisocyanatohexane and isophorone diisocyanate, and mixtures thereof. In certain embodiments, the crosslinking compounds comprise aliphatic diisocyanate cyanurates and biuretes. In certain embodiments, the crosslinking compounds are isophorone diisocyanate diisocyanate and biurete, and 1,6-diisocyanatohexane isocyanate and biurete. Examples of diisocyanate adducts to polyols are the diisocyanate adducts mentioned above to glycerol, trimethylolethane, and trimethylolpropane, for example, the tolylene diisocyanate adduct to trimethylolpropane, or the 1,6-diisocyanatohexane or isophorone diisocyanate adducts to trimethylpropane and/or glycerol.

In some embodiments, a polyisocyanate used may, for example, be an aromatic polyisocyanate, such as tolylene diisocyanate, diphenylmethane diisocyanate or polymethylene polyphenylisocyanate, an aliphatic polyisocyanate such as hexamethylene diisocyanate, xylylene diisocyanate, dicyclohexylmethane diisocyanate, lysine diisocyanate or tetramethylxylylene diisocyanate, an alicyclic polyisocyanate such as isophorone diisocyanate, or a modified product thereof.

In some embodiments, a modified polyisocyanate product is a modified prepolymer product that is a reaction product of a low molecular weight diol with a low molecular weight triol, a burette product that is a reaction product with water, or a trimer with an isocyanurate structure.

The isocyanate-terminated prepolymer can be produced by reacting a stoichiometrically excess amount of a polyisocyanate with the polyol composition. It can be produced by the thermal reaction of a polyol composition with the polyisocyanate at a temperature of 60 to 100 °C for 1 to 30 hours in a dry nitrogen stream in the presence or absence of a solvent and, optionally, in the presence of a urethane-forming catalyst. In some embodiments, a urethane-forming catalyst is an organometallic compound of tin, lead, or titanium. In some embodiments, a urethane-forming catalyst is an organotin compound, such as dibutyltin dilaurate, dibutyltin dioctoate, or stannous octoate.

An isocyanate group-terminated prepolymer of the present invention can be used for applications known in the art and familiar to the skilled professional. In some embodiments, it can be used for a moisture-curable composition that is cured by a reaction with moisture in the air, a two-part curable composition to react with a curing agent such as a polyamine, a polyol or a low molecular weight polyol, a casting polyurethane elastomer, or other applications.

The present invention also provides a polyurethane resin obtained by reacting the above polyol composition with a polyisocyanate. Such polyurethane resin can be produced by a known method, and a curing agent, such as a polyamine or a low molecular weight polyol, or the aforementioned urethane-forming catalyst can optionally be used.

In the production of polyurethanes, polyols of the invention can react with polyisocyanates using conventional techniques that have been fully described in the prior art. Depending on whether the product is homogeneous or a microcellular elastomer, a flexible or rigid foam, an adhesive, coating or other form, the reaction mixture may contain other conventional additives, such as chain extenders, for example, 1,4-butanediol or hydrazine, catalysts, for example, tertiary amines or tin compounds, surfactants, for example, siloxane-oxyalkylene copolymers, blowing agents, for example, water and trichlorofluoromethane, crosslinking agents, for example, triethanolamine, fillers, pigments, flame retardants and the like.

To accelerate the reaction between the isocyanate-reactive groups of the polyol resin and the isocyanate groups of the crosslinking agent, known catalysts can be used, for example, dibutyltin, tin(II) octoate, 1,4-diazabicyclo[2.2.2]-octane, or amines such as triethylamine. These are typically used in an amount of 10⁵ to 10² g, based on the weight of the crosslinking agent.

The crosslinking density can be controlled by varying the functionality of the polyisocyanate, the molar ratio of the polyisocyanate to the polyol resin, or through the additional use of monofunctional compounds reactive with the isocyanate groups, such as monohydric alcohols, for example, ethylhexanol or propyleptanol.

A crosslinking agent is generally used in an amount corresponding to an NCO:OH equivalent ratio of 0.5 to 2, preferably 0.75 to 1.5, and more preferably 0.8 to 1.2.

Suitable crosslinking agents are also epoxy compounds having at least two epoxide groups in the molecule, and their extension products formed by preliminary extension (prepolymers for epoxy resins, as described, for example, in the Ullmann Encyclopedia of Industrial Chemistry, 6th Edition, 2000, Electronic Work, in the chapter "Epoxy Resins"). Epoxy compounds having at least two epoxide groups in the molecule include, in particular: (i) Polyglycidyl and poly(p-methylglycidyl) esters, which are obtained by reacting a compound having at least two carboxyl groups, such as an aliphatic or aromatic polycarboxylic acid, with epichlorohydrin or beta-methylepichlorohydrin.

The reaction is preferably carried out in the presence of a base. Suitable aliphatic polycarboxylic acids are oxalic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, azelaic acid, dimerized or trimerized linolenic acid, tetrahydrophthalic acid, hexahydrophthalic acid, or 4-methylhexahydrophthalic acid. Suitable aromatic polycarboxylic acids are, for example, phthalic acid, isophthalic acid, or terephthalic acid. (ii) Polyglycidyl or (poly)β-methylglycidyl ethers derived, for example, from acyclic alcohols such as ethylene glycol, diethylene glycol, (poly)oxyethylene glycols, propane-1,2-diol, (poly)oxypropylene glycols, propane-1,3-diol, butane-1,4-diol, (poly)(oxytetramethylene) glycols, pentane-1,5-diol, hexane-1,6-diol, hexane-2,4,6-triol, glycerol, 1,1,1-trimethylolpropane, pentaerythritol, sorbitol; or cyclic alcohols such as 1,4-hexanedimethanol, bis(4-hydroxycyclohexyl)methane or 2,2-bis(4-hydroxycyclohexyl)propane; or comprises aromatic rings, such as N,N-bis(2-hydroxyethyl)aniline or p,p-bis(2-hydroxyethylamino)diphenylmethane. Glycidyl ethers can also be derived from monocyclic phenols such as resorcinol and hydroquinone, or polycyclic phenols, such as bis(4-hydroxyphenyl)methane, 4,4'-dihydroxybiphenyl, bis(4-hydroxyphenyl)sulfone, 1,1,2,2-tetrakis(4-hydroxyphenyl)ethane, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(3,5-dibromo-4-hydroxyphenyl)propane, or from novolaks, which are obtained by the condensation of aldehydes, such as formaldehyde, acetaldehyde, chloral or furfural, with phenols, such as phenol, 4-chlorophenol, 2-methylphenol, 4-tert-butylphenol or bisphenols. (iii) Poly(N-glycidyl) compounds that can be obtained by dehydrochlorination of the reaction products of epichlorohydrin with amines having at least two amine hydrogen atoms, such as aniline, n-butylamine, bis(4-aminophenyl)methane, m-xylylenediamine or bis(4-methylaminophenyl)methane. Poly(N-glycidyl) compounds also include triglycidyl isocyanurates, N,N'-diglycidyl derivatives of alkyleneureas such as ethyleneurea or 1,3-propyleneurea, and diglycidyl derivatives or hydantoins, such as 5,5-dimethylhydantoin. (iv) Poly(S-glycidyl) compounds such as di-S-glycidyl derivatives derived from dithiols, such as ethane-1,2-dithiol or bis(4-mercaptomethylphenyl) ether. (v) Cycloaliphatic epoxy compounds such as bis(2,3-epoxycyclopentyl ether), 2,3-epoxycyclopentylglycidyl ether, 1,2-bis(2,3-epoxycyclopentloxy)ethane or 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexanecarboxylate; or mixed cycloaliphatic-aliphatic epoxy compounds such as limonene diepoxide.

In some embodiments, the present disclosure encompasses superior polymers formed with polyol resins of the present invention which additionally comprise a hardening polymer comprising (meth)acryloyl and/or vinylaromatic units. Rigidity is obtained by free-radical polymerization of the (meth)acrylic monomers or vinylaromatic monomers. Examples of suitable monomers are styrene, alkylated ring styrenes with preferably C1-4 alkyl radicals such as α-methylstyrene, β-methylstyrene, acrylonitrile, methacrylonitrile, acrylamide or methacrylamide, acrylates and alkyl methacrylates having from 1 to 4 carbon atoms in the alkyl radical, in particular methyl methacrylate. Preference is given to the use of mixtures of monomers and monomers, which give rise to a polymer or copolymer having a glass transition temperature of more than +20 °C and, preferably, more than +50 °C. The hardening polymer may, in addition to (meth)acrylic monomers or vinylaromatic monomers, comprise several monomers. The (meth)acrylic monomer(s) or vinylaromatic monomers generally comprise at least 20% by weight, preferably at least 50% by weight, especially at least 70% by weight of the constituent monomers.

The included superior polymer compositions may also include common adjuvants such as fillers, diluents or stabilizers.

Suitable fillers include, for example, silica, colloidal silica, calcium carbonate, carbon black, titanium dioxide, mica, and others.

Suitable diluents include, for example, polybutene, liquid polybutadiene, hydrogenated polybutadiene, paraffin oil, naphthenates, atactic polypropylene, dialkyl phthalates, and reactive diluents, for example, alcohols and oligoisobutenes.

Suitable stabilizers include, for example, 2-benzothiazole sulfide, benzothiazole, thiazole, dimethylacetylenedicarboxylate, diethylacetylenedicarboxylate, BHT, butylated hydroxyanisole, and vitamin E. Additional superior polymeric materials that can be obtained from the polyols of the invention include vinyl-type polymers made by polymerizing ethylenically unsaturated derivatives of the polyols. Such derivatives can be obtained, for example, by reacting the polyols with ethylenically unsaturated carboxylic acids, for example, acrylic, methacrylic, and itaconic acids, or ester-forming derivatives thereof.

Another useful method for forming ethylenically unsaturated derivatives of polyols is to react said polyols with organic polyisocyanates, for example, with those mentioned above, and then react the isocyanate-terminated products obtained with hydroxyalkylacrylates or methacrylates, for example, 2-hydroxyethyl or 2-hydroxypropyl compounds.

Alternatively, polyols can react with isocyanate acrylates obtained by reacting a diisocyanate with a hydroxyalkylacrylate or methacrylate.

Ethylenically unsaturated derivatives of fluorinated polyols can be polymerized, preferably in the presence of comonomers such as acrylonitrile, styrene, ethyl acrylate, butyl acrylate or methyl methacrylate, using the conditions that have been fully described in the prior art for vinyl polymerizations. Useful molded plastic articles can be made in this way.

Additional superior polymeric materials that can be obtained from the polyols of the invention include epoxy resins prepared conventionally from epoxy derivatives of the polyols. Such derivatives can be obtained, for example, by reacting the polyols with epichlorohydrin in the presence of bases.

Articles of manufacture comprising polycarbonate-polyol and/or polyurethane compositions can be made using known methods and procedures described in the art. A skilled professional, after reading this disclosure, will be able to manufacture such articles using well-known protocols and techniques.

Examples EXAMPLE 1

This example demonstrates the use of the polymerization system of the present invention with a chain transfer agent YA-(Y)n and an Lp-M-(Li)m catalyst. Using a PPN+C1- co-catalyst, where n is 1, each -Y is -OH, -A is -Lp is a salcy-type ligand. -M- is Co(III), -LT is a chain transfer agent -Q'-A'(Z')n, where Q' is COO', -A- is -CH2- and Z' is -OH, and 24 mg of El catalyst (0.04 mmol), 0.45 g (3.1 mmol) of 1,4-cyclohexanedimethanol and 20 mg (0.04 mmol) of PPN+C1 were kept under vacuum in a Fisher-Potter flask. The flask was filled with nitrogen and 20 mL of propylene oxide was added. The flask was pressurized with 100 psi of CO2. After 41 h at 30 °C the flask was opened and the polymer was isolated by pouring in methanol. GPC analysis indicated the formation of a polymer with Mn = 4460, Mw = 4610, PDI = 1035. The polymer has a carbonate content of >97%. The resulting polycarbonate polyol composition consists predominantly of three types of polymer chains: P^' chains arising from initiation by cyclohexanedimethanol, P1' chains arising from initiation by glycolic acid (LT), and P2' chains arising from the chloride counter ion in the PPN co-catalyst. where each p is, on average, about 20-21.

In this particular composition, the ratio of P1 to P1’ to P2 is approximately 89:1:1. The polycarbonate polyol composition contains approximately 99% OH end groups.

EXAMPLE 2

This example demonstrates the use of the polymerization system of the present invention with a chain transfer agent YA-(Y)ne and an Lp-M-(Li)ra catalyst using a PPN+C1- co-catalyst, where n is 3, each -Y is -OH, n is 3, each -Y is -OH, -A is Lp is a salcy-type ligand. - M- is Co(III), - Li is trifluoroacetate. 51 mg of catalyst E2 (0.07 mmol), 0.5 g (1.4 mmol) of propoxylated pentaerythritol and 41 mg (0.08 mmol) of PPN+C1' were kept under vacuum in a Fisher-Potter bottle.

The bottle was filled with nitrogen and 20 mL of propylene oxide was added. The bottle was pressurized with 100 psi of CO2. After 22 hours at 30 °C, the bottle was opened and the polymer was isolated by pouring it into methanol. GPC analysis indicated the formation of a polymer with Mn = 13660, Mw = 15420, PDI = 1129. The polymer has a content of

The resulting polycarbonate polyol composition consists predominantly of three types of polymer chains: P1 chains arising from initiation by propoxylated pentaerythritol, P2a chains arising from initiation by trifluoroacetate (LT), and P2 chains arising from the chloride counter ion in the PPN co-catalyst. where each foot, on average, is about 30-32.

In this particular composition, the ratio of Pla to P2a to P2 is approximately 20:1:1. The polycarbonate polyol composition contains approximately 97% OH end groups.

EXAMPLE 3

Example 3 was performed under conditions similar to Example 2, except that (poly)caprolactonediol with a Mn of 530 g/mol was used as a chain transfer agent.

EXAMPLE 4

Example 4 was performed under conditions similar to...

Example 3, except that (poly)ethylene glycol with a Mn of 400 g/mol was used as a chain transfer agent.

EXAMPLE 5

Example 5 was performed using conditions similar to Example 3, except that (poly)propylene glycol having a Mn of 760 g/mol was used as a chain transfer agent.

EXAMPLE 6

Example 6 was performed using conditions similar to Example 3, except that 1,2-cyclohexanediol was used as a chain transfer agent.

EXAMPLE 7

This example demonstrates the use of the polymerization system of the present invention with a YA-(Y)n chain transfer agent and an Lp-M-ÍLJm catalyst using a PPN+C1- co-catalyst, where n is 1, each -Y is -OH, -A is Lp is a salcy-type ligand. - M- is Co(III), - Lj is trifluoroacetate.

A glass flask dried in an oven was charged with 11.5 mg of catalyst E2 (0.016 mmol) and 9.2 mg of PPN+C1' (0.016 mmol). The flask was purged with nitrogen and 1,4-butanol (0.073 g, 0.8 mmol) was added as a solution in dry THF (0.5 mL). Propylene oxide (4.5 mL, 64 mmol) was then added. The reaction flask was pressurized with 300 psig of dry carbon dioxide gas and stirred at 30 °C for 3 hours. The reaction was stopped with acid, diluted in 25 mL of acetone, and concentrated to yield 2.6 g of crude polymer. The polymer had a Mn of 4.072 g/mol and a PDI of 1.04. It had 0-polymer e—no-detectable ether links and more than 98% -OH end groups.

The resulting polycarbonate polyol composition consists predominantly of three types of polymer chains: Pla chains arising from initiation by 1,4-butanediol, P2a chains arising from initiation by trifluorine (LT), and P2 chains arising from the chloride counter ion in the PPN co-catalyst. , where each p is, on average, about 20. In this particular composition, the ratio of

Plapara P2a to P2 is approximately 50:1:1.

EXAMPLE 8

This example demonstrates the use of the polymerization system of the present invention with a YA-(Y)n chain transfer agent and an Lp-M-(Li)m catalyst using a PPN+C1- co-catalyst, where n is 1, each -Y is -OH, -A is -Lp is a salcy-type ligand. -M- is Co(III), -Lj is trifluoroacetate. An oven-dried glass flask was charged with 11.5 mg of catalyst E2 (0.016 mmol) and 9.2 mg of PPN+Cl15 (0.016 mmol). The flask was purged with nitrogen and 1,4-propanediol (0.061 g, 0.8 mmol) was added as a solution in dry THF (0.5 mL). Propylene oxide (4.5 mL, 64 mmol) was then added. The reaction flask was pressurized with 300 psig of dry carbon dioxide gas and stirred at 30 °C for 3 hours. The reaction was stopped with acid, diluted in 25 mL of acetone, and concentrated to yield 2.7 g of crude polymer. The polymer had a Mn density of 4336 g/mol and a PDI of 1.04. The polymer contained no detectable ether linkages and had more than 98% of -OH terminal groups.

The resulting polycarbonate polyol composition consists predominantly of three types of polymer chains: Pla chains arising from initiation by 1,3-propanediol, P2a chains arising from initiation by trifluoroacetate (Lj), and P2 chains arising from the chloride counter ion in the PPN co-catalyst. where each p is, on average, about 21. In this particular composition, the ratio to P2a to P2 is approximately 50:1:1.

EXAMPLE 9

This example demonstrates the use of the polymerization system of the present invention with a chain transfer agent YA-(Y)ne and an Lp-M-fLjJm catalyst using a PPN+C1- co-catalyst, where each -Y is -OH, -A is Lp is a salcy-type ligand. - M- is Co(III), - Lx is trifluoroacetate.

A glass flask dried in an oven was charged with 11.5 mg of catalyst E2 (0.016 mmol) and 9.2 mg of PPN+C1’ (0.016 mmol). The flask was purged with nitrogen and 1,4-butene (0.079 g, 0.8 mmol) was added as a solution in dry THF (0.5 mL). Propylene oxide (4.5 mL, 64 mmol) was then added. The reaction flask was pressurized with 300 psig of dry carbon dioxide gas and stirred at 30 °C for 3 hours. The reaction was stopped with acid, diluted with 25 mL of acetone, and concentrated to yield 1.5 g of crude polymer. The polymer had a Mn of 2431 g/mol and a PDI of 1.06. The polymer contained no detectable ether linkages and had over 98% -OH end groups.

The resulting polycarbonate polyol composition consists predominantly of three types of polymer chains: Pla chains arising from initiation by 1,4-butenediol, P2a chains arising from initiation by trifluoroacetate (LT), and P2 chains arising from the chloride counter ion in the PPN co-catalyst. where each p is, on average, about 12. In this particular composition, the ratio of pla to p2a to P2 is approximately 50:1:1.

EXAMPLE 10

This example demonstrates the use of the polymerization system of the present invention with a chain transfer agent YA-(Y)n and a catalyst Lp-M-(LI)m using a co-catalyst PPN+C1-, where n is 1, each -Y is -CO2H, -A is -Lp is a salcy-type ligand. -M- is CO(III), -LÍ is trifluoroacetate.

A glass flask dried in an oven was charged with 11.5 mg of catalyst E2 (0.016 mmol); 9.2 mg of PPN+C1' (0.016 mmol); succinic acid (0.095 g, 0.8 mmol) and 0.5 mL of THF. Propylene oxide (4.5 mL, 64 mmol) was then added. The reaction flask was pressurized with 300 psig of dry carbon dioxide gas and stirred at 30 °C for 3 hours. The reaction was stopped with acid, diluted with 25 mL of acetone and concentrated to yield 3.0 g of crude polymer. The polymer had a Mn of 13.933 g/mol, and a PDI of 1.04. The polymer contained no detectable ether linkages and had more than 98% -OH end groups.

The resulting polycarbonate polyol composition consists predominantly of three types of polymer chains: Pla chains arising from initiation by succinic acid, P2a chains arising from initiation by trifluoroacetate (Lx), and P2 chains arising from the chloride counter ion in the PPN co-catalyst. where each foot, on average, is about 68. In this particular composition, the ratio of Pla to P2a to P2 is approximately 50:1:1.

EXAMPLE 11

This example demonstrates the use of the polymerization system of the present invention with a chain transfer agent YA-(Y)n and an Lp-M-(Li)m catalyst using a PPN+C1- co-catalyst, where n is 1, each -Y is -CO2H, -A is Lp is a salcy-type ligand. - M- is Co(III), - Li is trifluoroacetate.

A glass flask dried in an oven was charged with 10 11.5 mg of catalyst E2 (0.016 mmol); 9.2 mg of PPN+C1' (0.016 mmol); adipic acid (0.12 g, 0.8 mmol) and 0.5 mL of THF. Propylene oxide (4.5 mL, 64 mmol) was then added. The reaction flask was pressurized with 300 psig of dry carbon dioxide gas and stirred at 30 °C for 3 15 hours. The reaction was stopped with acid, diluted with 25 mL of acetone and concentrated to yield 3.0 g of crude polymer. The polymer had a Mn of 13.933 g/mol, and a PDI of 1.04. The polymer contained no detectable ether linkages and had more than 98% -OH end groups.

The resulting polycarbonate polyol composition consists predominantly of three types of polymer chains: Pla chains arising from initiation by succinic acid, P2a chains arising from initiation by trifluoroacetate (Lx), and P2 chains arising from the chloride counter ion in the PPN co-catalyst. where each foot, on average, is about 68. In this particular composition, the ratio of Pla to P2a to P2 is approximately 50:1:1.

EXAMPLE 12

This example demonstrates the use of the polymerization system of the present invention with a chain transfer agent YA-(Y)ne and an Lp-M-(LI)m catalyst using a PPN+C1- co-catalyst, where n is 1, each -Y is -CO2H, -A is -Lp is a salcy-type ligand. -M- is Co(III), -Li is trifluoroacetate.

A glass flask dried in an oven was charged with 11.5 mg of catalyst E2 (0.016 mmol); 9.2 mg of PPN+C1‘ (0.016 mmol); terephthalic acid (0.13 g, 0.8 mmol) and 0.5 mL of THE. Propylene oxide (4.5 mL, 64 mmol) was then added. The reaction flask was pressurized with 300 psig of dry carbon dioxide gas and stirred at 30 °C for 3 hours. The reaction was stopped with acid, diluted with 25 mL of acetone and concentrated to yield 1.52 g of crude polymer. The polymer had a Mn of 13.621 g/mol, and a PDI of 1.35. The polymer contained no detectable ether linkages and had more than 98% -OH end groups.

The resulting polycarbonate polyol composition consists predominantly of three types of polymer chains: Pla chains arising from initiation by terephthalic acid, P2a chains arising from initiation by trifluoroacetate (LT), and P2 chains arising from the chloride counter ion in the PPN co-catalyst. where each foot, on average, is about 68. In this particular composition, the ratio of Pla to P2a to P2 is approximately 50:1:1.

EXAMPLE 13

This example demonstrates the use of the polymerization system of the present invention with a chain transfer agent YA-(Y)ne and an Lp-M-ÍLjJm catalyst using a PPN+C1- co-catalyst, where n is 1, each -Y is -CO2H, -A is Lp is a salcy-type ligand. - M- is Co(III), and - Lj is trifluoroacetate.

A glass flask dried in an oven was charged with 11.5 mg of catalyst E2 (0.016 mmol); 9.2 mg of PPN+C1' (0.016 mmol); maleic acid (0.095 g, 0.8 mmol) and 0.5 mL of THF. Propylene oxide (4.5 mL, 64 mmol) was then added. The reaction flask was pressurized with 300 psig of dry carbon dioxide gas and stirred at 30 °C for 3 hours. The reaction was stopped with acid, diluted with 25 mL of acetone and concentrated to yield 3.3 g of crude polymer 5. The polymer had a Mn of 5919 g/mol, and a PDI of 1.03. The polymer contained no detectable ether linkages and had more than 98% -OH end groups.

The resulting polycarbonate polyol composition consists predominantly of three types of polymer chains: Pla chains arising from initiation by succinic acid, P2a chains arising from initiation by trifluoroacetate (Lx), and P2 chains arising from the chloride counter ion in the PPN co-catalyst. where each p is, on average, about 29. In this particular composition, the ratio of Pla to P2a to P2 is approximately 50:1:1.

EXAMPLE 14

This example demonstrates the use of the polymerization system of the present invention with a YA-(Y)n chain transfer agent and an Lp-M-(Li)m catalyst using a PPN+C1- co-catalyst, where each -Y is -CO2H, -A is Lp is a salcy-type ligand. - M- is Co(III), and - Lj is trifluoroacetate.

A glass flask dried in an oven was charged with 11.5 mg of catalyst E2 (0.016 mmol) and 9.2 mg of PPN+C1' (0.016 mmol). The reaction flask was purged with nitrogen and isosorbide (0.12 g, 0.8 mmol) was added as a solution in dry THF (0.5 mL). Propylene oxide (4.5 mL, 64 mmol) was then added. The reaction flask was pressurized with 300 psig of dry carbon dioxide gas and stirred at 30 °C for 3 hours. The reaction was stopped with acid, diluted with 25 mL of acetone, and concentrated to yield 1.53 g of crude polymer. The polymer had a Mn content of 2342 g/mol and a PDI of 1.05. The polymer contained no detectable ether linkages and had over 98% -OH end groups.

The resulting polycarbonate polyol composition consists predominantly of three types of polymer chains: Pla chains arising from isosorbide initiation, P2a chains arising from trifluoroacetate (Lj) initiation, and P2 chains arising from the chloride counter ion in the PPN co-catalyst. where each foot, on average, is about 11.

In this particular composition, the ratio of Pla to P2a to P2 is approximately 50:1:1.

EXAMPLE 14

This example demonstrates the use of the polymerization system of the present invention with a chain transfer agent YA-(Y)n and an Lp-M-(Li)m catalyst using a PPN+Cl- co-catalyst, where n is 1, each -Y is -CO2H, -A is , where n' is 10 to 30 and the average MW is 600 g/mol; - Lp is a salcy-type ligand. - M- is Co(III), and - Lj is trifluoroacetate.

A glass flask dried in an oven was charged with 11.5 mg of catalyst E2 (0.016 mmol) and 9.2 mg of PPN+C1' (0.016 mmol); paraformaldehyde (24 mg, 0.04 mmol); and dry THF (0.5 mL). Propylene oxide (4.5 mL, 64 mmol) was then added. The reaction flask was pressurized with 300 psig of dry carbon dioxide gas and stirred at 30 °C for 3 hours. The reaction was stopped with acid, diluted with 25 mL of acetone, and concentrated to yield 1.0 g of crude polymer. The polymer had a Mn of 13.262 g/mol and a PDI of 1.18.

The resulting polycarbonate polyol composition consists predominantly of three types of polymer chains: Pla chains arising from isosorbide initiation, P2a chains arising from trifluoroacetate (LT) initiation, and P2 chains arising from the chloride counter ion in the PPN co-catalyst. , where n' is 0a30 and each p is, on average, about 60.

In this particular composition, the ratio of Pla to P2a to P2 is approximately 2:1:1.

EXAMPLE 15

This example demonstrates the use of the polymerization system of the present invention with a chain transfer agent YA-(Y)ne and an Lp-M-(Li)m catalyst using a PPN+C1- co-catalyst, where ne 1, each -Y is -CO2H, -A is (mixture of isomers); -Lp is where each is trifluoroacetate. -M- is Co(III), and -Li is trifluoroacetate.

In a sealed container, catalyst (5.4 mg, 1.0 equiv) was loaded into a 20 mL oven-dried glass jacket. The jacket was inserted into a high-pressure stainless steel reactor. The system was purged with N2 five times and purged with CO2 twice. While under the positive CO2 flow, a solution of dipropylene glycol (75 μL) in propylene oxide (5 mL, 25,000 equiv) was loaded into the reaction vessel. The reaction was heated to 50 °C, then pressurized with carbon dioxide (300 psi) and stirred.

After 6 h, the reaction was vented and suppressed with acid methanol (0.2 mL). The reaction was cooled to room temperature, and the resulting polymer was diluted with acetone (5 mL) and transferred to a 15 mL aluminum crucible. Unreacted propylene oxide and acetone were removed by evaporation to yield 2.19 g of a dirty-white polymer (Mw = 5600, Mw/Mn = 1.03).

The polycarbonate polyol composition thus obtained is composed predominantly of two types of polymeric chains: P1 chains that arise from initiation by dipropylene glycol, and P2 chains that arise from initiation by trifluoroacetate (from L1 and X). where each p is, on average, about 27.

In this particular composition, the ratio of P1 to P2 is approximately 4:1.

Other Modalities

The foregoing was a description of some non-limiting embodiments of the invention. Therefore, it is important to understand that the embodiments of the invention described herein are merely illustrative of the application of the principles of the invention.

Reference here to details of the embodiments illustrated is not intended to limit the scope of the claims, which themselves cite those features considered essential to the invention.

Claims (23)

1. A polycarbonate polyol composition comprising an epoxide and CO2 copolymer, characterized in that the copolymer has: a Mn between 400 and 20,000; and more than 90% carbonate linkages; wherein the polycarbonate polyol composition comprises: polymer chains denoted P1 having the formula TY-A-(YT)n, derived from a chain transfer agent (CTA) having the formula YA-(Y)n, with Y as defined below wherein: each -T is a polycarbonate chain having a formula independently selected from the group consisting of: where: p varies from 5 to 10,000, each -Y group is independently a functional group capable of initiating the growth of the CO2 epoxide copolymer chain selected from the group consisting of -OH, -C(O)OH, -C(ORy)OH, -OC(Ry)OH, -NHRy, -NHC(O)Ry, -NHC=NRY; -NRyC=NH; -NRyC(NRy2)=NH; -NHC(NRy2)=NRy; -NHC(O)ORy, -NHC(O)NRy2; -C(O)NHRy, -C(S)NHRy, -OC(O)NHRy, -OC(S)NHRy, SH, -C(O)SH, -B(ORy)OH, -P(O)a(Ry)b(ORy)c(O)dH, - OP(O)a(Ry)b(ORy)c(O)dH, -N(Ry)OH, -ON(Ry)H; =NOH, =NN(Ry)H, where each occurrence of Ry is independently -H, or an optionally substituted radical selected from the group consisting of C1-20 aliphatic, C1-20 heteroaliphatic, 3- to 12-membered heterocyclic, and 6- to 12-membered aryl, a and b are each independently 0 or 1, c is 0, 1 or 2, d is 0 or 1, and the sum of a, b and c is 1 or 2 and where an acidic hydrogen atom bonded to any of the above functional groups may be substituted by a metal atom or an organic cation and each Y group may be the same or different, -A- is a covalent bond or a multivalent moiety; en is an integer between 1 and 10 inclusive; further comprising polymer chains denoted P2 having a formula selected from the group consisting of: where: X is a linked form of an anion capable of initiating only one polymer chain, comprising a halogen atom, an azide, an ester group, an ether group, or a sulfonic ester group, -E- is an optionally substituted C2 unit derived from an epoxide, where E may represent a monomeric unit derived from one type of epoxide, or a mixture of two or more types of epoxide, wherein each E is I, R21, R22, R23 and R24 are each independently selected from the group consisting of: -H; and an optionally substituted group selected from aliphatic C1-30; aryl C6-14; 3- to 12-membered heterocycle, and 5- to 12-membered heteroaryl, wherein any two or more of R21, R22, R23 and R24 may be taken together with intervening atoms to form one or more optionally substituted 3- to 12-membered rings, optionally containing one or more heteroatoms, wherein -E- predominantly comprises -CH2CH2- units derived from ethylene oxide or comprises -CH2CH(CH3)- groups derived from propylene oxide; wherein the ratio of P1 polymer chains to P2 polymer chains is greater than 40:1. 2. Polycarbonate polyol composition according to claim 1, characterized in that the ratio of P1 polymer chains to P2 polymer chains is greater than 100:1. 3. Polycarbonate polyol composition, according to claim 1 or 2, characterized in that it further comprises polymer chains denoted P1a having the formula: preferably where the ratio of P1 polymer chains to P1a polymer chains is greater than 20:1. 4. Polycarbonate polyol composition, according to any one of claims 1 to 3, characterized in that the P1 type chains have the formula: in which P1 type chains have the formula: in which P1 type chains have the formula: in which P1 type chains have the formula: wherein each z is independently 0 or 1, or wherein -A- comprises a polymer chain or oligomer selected from the group consisting of polyolefins, polyethers, polyesters, polycarbonates, polyether polycarbonates and polyoxymethylene, or wherein -A- comprises a structure derived from a compound selected from the group consisting of: sugar alcohols, carbohydrates, saccharides, polysaccharides, starch, starch derivatives, lignins, lignans, partially hydrolyzed triglycerides and derivatives of any of these materials. 5. Polycarbonate polyol composition, according to any one of claims 1 to 3, characterized in that T-Y-A-(Y-T))n comprises a chain transfer agent Y-A-(Y)n, which is a polyhydric alcohol, preferably a diol or a triol or a tetraol or a larger polyol, preferably wherein n is 1 and both Y groups are hydroxyl groups, further preferably wherein two hydroxyl groups are on adjacent carbons, further preferably wherein two hydroxyl groups are on non-adjacent carbons, further preferably wherein two hydroxyl groups are at opposite ends of a chain, further preferably such α-o diols including aliphatic chains from C3 to C20, further preferably such α-w diols comprising a polyether. 6. Polycarbonate polyol composition, according to any one of claims 1 to 3, characterized in that T-Y-A(Y-T))n comprises a chain transfer agent Y-A-(Y)n, wherein said chain transfer agent is a diacid, a triacid or a higher polyacid, preferably: wherein said chain transfer agent is a diacid, more preferably wherein n is 1, and both Y groups present are carboxylic acids, more preferably wherein said diacid is phthalic acid, isophthalic acid, terephthalic acid, or wherein said diacid is maleic acid, succinic acid, malonic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, or azelaic acid, or wherein said chain transfer agent is a triacid, preferably citric acid, isocitric acid, cis- or trans-aconitic acid, propane-1,2,3-tricarboxylic acid or trimesic acid. 7. Polycarbonate polyol composition, according to any one of claims 1 to 3, characterized in that T-Y-A(Y-T))n comprises a chain transfer agent Y-A-(Y)n, wherein said chain transfer agent is a hydroxy acid, preferably: wherein said hydroxy acids are alpha-hydroxy acids, preferably wherein the alpha-hydroxy acids are selected from the group consisting of: glycolic acid, DL-lactic acid, D-lactic acid, L-lactic acid, citric acid and mandelic acid or wherein said hydroxy acid is a beta-hydroxy acid, preferably wherein said beta-hydroxy acid is selected from the group consisting of: 3-hydroxypropionic acid, DL-3-hydroxybutyric acid, D-3-hydroxybutyric acid, L-3-hydroxybutyric acid, DL-3-hydroxyvaleric acid, D-3-hydroxyvaleric acid, acid L-3-hydroxyvaleric acid, salicylic acid, and salicylic acid derivatives; or wherein said hydroxy acid is an α-w hydroxy acid, preferably wherein said α-w hydroxy acids are selected from the group consisting of optionally substituted C3-20 aliphatic α-w hydroxy acids, or wherein said α-w hydroxy acid is an oligomeric ester polyester; or wherein at least one Y group is a carboxylic acid or carboxylate and one or more additional Y groups are -OH. 8. Polycarbonate polyol composition according to claim 5, characterized in that said chain transfer agents include: (a) one or more polyhydric alcohols, preferably wherein said polyhydric alcohol is a diol, including but not limited to: 1,2-ethanediol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 2,2-dimethylpropane-1,3-diol, 2-butyl-2-ethylpropane-1,3-diol, 1,5-hexanediol, 1,6-hexanediol, 1,8-octanediol, 1,10-decanediol, 1,12-dodecanediol, 2,2,4,4- tetramethylcyclobutane-1,3-diol, 1,3-cyclopentanediol, 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol and 1,4-cyclohexanediethanol, or said chain transfer agents include (b) polyalkylene glycols such as: diethylene glycol, triethylene glycol, tetraethylene glycol, higher poly(ethylene glycol), such as those with average molecular weights of 220 to 2000 g/mol, dipropylene glycol, tripropylene glycol and higher (poly)propylene glycols, such as those with average molecular weights of 234 to 2000 g/mol, or said chain transfer agents include (c) hydroxyl-terminated polyolefins, hydroxyl-terminated polybutadienestyrene (HTBS), or said chain transfer agents include (d): 4,4'-(1-methylethylidene)bis[cyclohexanol], 2,2'-methylenebis[phenol], 4,4'-methylenebis[phenol], 4,4'-(phenylmethylene)bis[phenol], 4,4'-(diphenylmethylene)bis[phenol], 4,4'-(1,2-ethanediyl)bis[phenol], 4,4'-(1,2-cyclohexanediyl)bis[phenol], 4,4'-(1,3-cyclohexanediyl)bis[phenol], 4,4'-(1,4-cyclohexanediyl)bis[phenol], 4,4'-ethylidenebis[phenol], 4,4'-(1-phenylethylidene)bis[phenol], 4,4'-propylidenebis[phenol], 4,4'-cyclohexylidenebis[phenol], 4,4'-(1-methylethylidene)bis[phenol], 4,4'-(1-methylpropylidene)bis[phenol], 4,4'-(1-ethylpropylidene)bis[phenol], 4,4'-cyclohexylidenebis[phenol], 4,4'-(2,4,8,10-tetraoxaspiro[5.5]undecane-3,9-diyldi-2,1-ethanediyl)bis[phenol], 1,2-benzenedimethanol, 1,3-benzenedimethanol, 1,4-benzenedimethanol, 4,4'-[1,3-phenylenebis(1-methylethylidene)]bis[phenol], 4,4'-[1,4- phenylenebis(1-methylethylidene)]bis[phenol], phenolphthalein, 4,4'-(1-methylidene)bis[2-methylphenol], 4,4'-(1-methylethylidenol)bis[2-(1-methylethyl)phenol] and 2,2'-methylenebis[4-methyl-6-](1-methylethyl)phenol, or said chain transfer agents include (e) a polyhydric phenol derivative, or said chain transfer agent is selected from (f): , or said chain transfer agents include (g) a triol, a tetraol or a higher polyol, including, but not limited to: aliphatic triols having a molecular weight less than 500 such as trimethylolethane; trimethylolpropane; glycerol; 1,2,4-butanetriol; 1,2,6-hexanetriol; tris(2-hydroxyethyl)isocyanurate; hexahydro-1,3,5-tris(hydroxyethyl)-s-triazine; 6-methylheptane-1,3,5-triol; polypropylene oxide triol; and polyester triol; tetraols including, but not limited to: erythritol, pentaerythritol; 2,2'-dihydroxymethyl 1-1,3-propanediol; and 2,2'-(oxydimethylene)bis-(2-ethyl-1,3-propanediol), or; the said chain transfer agent is (h) a catechol, resorcinol or hydroquinone derivative optionally substituted. 9. Polycarbonate polyol composition according to claim 6, characterized in that said chain transfer agent includes (a) a diacid, preferably including a compound selected from the group consisting of: said chain transfer agent includes (b) an acidic functional group, wherein the compound is provided as a salt, preferably wherein said carboxylic chain transfer agent is provided as an ammonium salt; more preferably said diacid chain transfer agents include carboxy-terminated polyolefin polymers. 10. Polycarbonate polyol composition according to claim 7, characterized in that said chain transfer agent is (a) a hydroxy acid, preferably wherein a hydroxy acid is selected from the group consisting of: Or the said chain transfer agent includes (b) an acidic functional group, wherein the compound is provided as a salt, preferably wherein said carboxylic chain transfer agent is provided as an ammonium salt. 11. Polycarbonate polyol composition, according to claim 1, comprising a CO2 epoxide copolymer, characterized in that the copolymer has: at least 99% of the terminal groups are hydroxyl groups. 12. Polycarbonate polyol composition, according to any one of claims 1 to 11, characterized in that the PDI of the polycarbonate polyol is less than 1.6, or the PDI of the polycarbonate polyol is less than 1.2. 13. Polycarbonate polyol composition, according to any one of claims 1 to 12, characterized in that, on average, in the composition, the polycarbonate polyol polymer chains comprise more than 92% carbonate linkages, or more than 95% carbonate linkages, or more than 97% carbonate linkages, or more than 99% carbonate linkages. 14. Polycarbonate polyol composition, according to any one of claims 1 to 13, characterized in that it has a Mn content between 500 and 5000 g/mol, or has a Mn content between 800 and 4000 g/mol, or has a Mn content between 1000 and 3000 g/mol, or has a Mn content of 1000 g/mol, or has a Mn content of 2000 g/mol, or has a Mn content of 4000 g/mol, or has a Mn content of 8000 g/mol. 15. Polymerization system for the copolymerization of CO2 and epoxides to produce polycarbonate polyol resins, as defined in any one of claims 1 to 14, with a high proportion of -OH end groups, characterized in that it comprises: a metal-salenate complex; wherein the metal-salenate complex is a cobalt salt complex, or wherein the metal-salenate complex comprises a metal atom selected from groups of the periodic table 3-13 inclusive, or wherein the metal-salenate complex comprises a metal atom selected from groups of the periodic table 5-12 inclusive, or wherein the metal-salenate complex comprises a metal atom selected from the group consisting of Cr, Mn, V, Fe, Co, Mo, W, Ru, Al and Ni, or wherein the metal-salenate complex comprises a Cr atom, or wherein the metal-salenate complex comprises a Mn atom, or wherein the metal-salenate complex comprises a Co atom, or wherein the metal-salenate complex has a formula selected from the group consisting of: wherein M is a metal atom; LI is a ligand that is a polymerization initiator; m' is an integer between 0 and 2 inclusive, representing the number of initiating ligands present; Rc, in each occurrence, is independently selected from the group consisting of: -H, aliphatic C1 to C12 optionally substituted; optionally substituted 3 to 14 membered carbocycle; optionally substituted 3 to 14 membered heterocycle, R20; and R21, wherein two or more Rc groups may be taken together with intervening atoms to form one or more optionally substituted rings and, wherein two Rc groups are attached to the same carbon atom, they may be taken together with the carbon atom to which they are attached to form a selected portion of the group consisting of: an optionally substituted 3 to 8 membered spirocyclic ring, a carbonyl, an oxime, a hydrazone and an imine; R4a, R4a', R5a, R5a', R6a, R6a', R7a and R7a' are each independently hydrogen, a group , halogen, -NO2, -CN, -SR13, -S(O)R13, -S(O)2R13, -NR11C(O)R13, -OC(O)R13, -CO2R13, -NCO, -N3-, -OR10, -OC(O)NR11R12, -Si(R13)3, -NR11R12, -NR11C(O)R13 and -NR11C(O)OR13; or an optionally substituted radical selected from the group consisting of C1-20 aliphatic; C1-20 heteroaliphatic; 6- to 10-membered aryl; 5- to 10-membered heteroaryl; and a 3- to 7-membered heterocyclic group, where [R1a and R4a], [R1a' and R4Aa'], and any two adjacent groups R4a, R4a', R5a, R5a', R6a, R6a', R7a, and R7a' can be taken together with intervening atoms to form one or more optionally substituted rings containing one or more heteroatoms; R1a and R1a' are hydrogen when not taken together with R4a and R4a';R' is Rd or a group , where two or more adjacent R' groups may be taken together to form a saturated, partially unsaturated, or optionally substituted aromatic 3- to 12-membered ring containing 0 to 4 heteroatoms; Rd is selected from the group consisting of: optionally substituted C1- to C12 aliphatic; optionally substituted 3- to 14-membered carbocycle; optionally substituted 3- to 14-membered heterocycle; R20; and R21; R10, in each occurrence, is independently selected from the group consisting of: -H; optionally substituted C1-12 aliphatic; an optionally substituted 3- to 14-membered carbocycle; an optionally substituted 3- to 14-membered heterocycle; -S(O)2R13; -Si(R15)3; -C(O)R13; and a hydroxyl protecting group, R11 and R12, in each occurrence, are independently selected from the group consisting of: -H; aliphatic C1 to C12 optionally substituted; a 3 to 14 membered carbocycle optionally substituted; a 3 to 14 membered heterocycle optionally substituted; where two or more R11 or R12 groups may optionally be taken together with intervening atoms to form a 3 to 10 membered optionally substituted ring, R13, in each occurrence, is independently selected from the group consisting of: -H, aliphatic C1 to C12 optionally substituted; a 3 to 14 membered optionally substituted carbocycle; and a 3 to 14 membered optionally substituted heterocycle; where two or more R13 groups in the same molecule may optionally be taken together to form a ring; R14, in each occurrence, is independently selected from the group consisting of: halogen; aliphatic C1 to C12 optionally substituted; 3 to 14 membered carbocycle optionally substituted; 3 to 14 membered optionally substituted heterocycle; -OR10; -OC(O)R13; -OC(O)OR13; - OC(O)NR11R12; -CN; -CNO; -C(R13)zH(3-Z); -C(O)R13; -C(O)OR13; - C(O)NR11R12; -NR11R12; -NR11C(O)R13; -NR11C(O)OR13; -NR11SO2R13; - N+R11R12R13X-; -P+(R11)3X-; -P(R11)3=N+=P(R11)3X-; -As+R11R12R13X-; - NCO; -N3; -NO2; -S(O)xR13; e-SO2NR11R12, R15, in each occurrence, is independently selected from the group consisting of: optionally substituted aliphatic C1 to C12; an optionally substituted 3 to 14 membered carbocycle; and an optionally substituted 3 to 14 membered heterocycle, R16, in each occurrence, is independently selected from the group consisting of: optionally substituted aliphatic C1 to C12; an optionally substituted 3 to 14 membered carbocycle; and an optionally substituted 3 to 14 membered heterocycle; and -C(R17)zH(3-z), R17, in each occurrence, is independently selected from the group consisting of: -H; optionally substituted aliphatic C1 to C12; an optionally substituted 3 to 14 membered carbocycle; and an optionally substituted 3 to 14 membered heterocycle, R20, in each occurrence, is independently selected from the group consisting of: halogen; -OR10; - OC(O)R13; -OC(O)OR13; -N+(R11)3X-; -P+(R11)3X-; - P(R11)3=N+=P(R11)3X-; -As+R11R12R13X-; -OC(O)NR11R12; -CN; -CNO; - C(O)R13; -C(O)OR13; -C(O)NR11R12; -C(R13)zH(3-z); -NR11R12; - NR11C(O)R13; -NR11C(O)OR13; -NCO; -NR11SO2R13; -S(O)xR13; - S(O)2NR11R12; -NO2; -N3; e -Si(R13)(3-z)[(CH2)kR14]z, R21, in each occurrence, is independently selected from the group consisting of: -(CH2)kR20; -(CH2)kZ- (CH2)kR20; -C(R17)zH(3-z); -(CH2)kC(R17)zH(3-z); -(CH2)mZ- (CH2)mC(R17)zH(3-z); -(CH2)kZ-R16; X- is any anion, k is independently an integer from 1 to 8 inclusive in each occurrence, x is 0, 1, or 2, z is 1, 2, or 3; m is 0 or an integer from 1 to 8 inclusive, p is 0 or an integer from 1 to 4 inclusive, where a group comprises a covalent ligand containing one or more atoms selected from the group consisting of C, O, N, S, and Si; “Z” is an activating functional group with co-catalytic activity in the copolymerization of epoxide CO2, ep is an integer from 1 to 4, indicating the number of individual activating functional groups present in a given group. , or wherein n is 1, one group Y is -OH, and the other group Y is -P(O)a(Ry)b(ORy)cOH, preferably wherein a is 1, b is 0 and c is 1 or a is 1, b is 1, and c is 0, more preferably wherein Ry is hydrogen or aryl of 6 to 12 members; and a chain transfer agent having a plurality of sites capable of initiating copolymerization of epoxides and CO2; wherein the chain transfer agent has a structure YA-(Y)n, where: each group -Y is independently selected from the group consisting of: -OH, -C(O)OH, -C(ORy)OH, -OC(Ry)OH, -NHRy, -NHC(O)Ry, -NHC=NRY; -NRyC=NH; -NRyC(NRy2)=NH; -NHC(NRy2)=NRy; -NHC(O)ORy, -NHC(O)NRy2; -C(O)NHRy, -C(S)NHRy, -OC(O)NHRy, - OC(S)NHRy, SH, -C(O)SH, -B(ORy)OH, -P(O)a(Ry)b(ORy)c(O)dH, - OP(O)a(Ry)b(ORy)c(O)dH, -N(Ry)OH, -ON(Ry)H; =NOH, =NN(Ry)H, where each occurrence of Ry is independently -H, or an optionally substituted radical selected from the group consisting of C1-20 aliphatic, C1-20 heteroaliphatic, 3- to 12-membered heterocyclic, and 6- to 12-membered aryl, a and b are each independently 0 or 1, c is 0, 1 or 2, d is 0 or 1, and the sum of a, b and c is 1 or 2 and where an acidic hydrogen atom bonded to any of the above functional groups may be substituted by a metal atom or an organic cation; -A- is a covalent bond or a multivalent moiety; en is an integer between 1 and 10 inclusive wherein the chain transfer agent and metal complex are present in a molar ratio ranging from 50:1 to 500:1, 500:1 to 1000:1, or more than 1000:1. 16. Polymerization system according to claim 15, characterized in that each group Y is independently selected from the group consisting of: -OH, and -C(O)OH, or wherein -A- is an optionally substituted radical selected from the group consisting of: C230 aliphatic, C2-30 heteroaliphatic, 6- to 12-membered aryl, 3- to 12-membered heterocyclic, 5- to 12-membered heteroaryl, polyolefins, polyesters, polyethers, polycarbonates, polyoxymethylene and mixtures of two or more of these, or wherein n is 1 to 4, or wherein n is 1, or wherein n is 2, or wherein n is 3, or wherein the chain transfer agent is selected from the group consisting of: water; polyhydric alcohols; polyacids; hydroxy acids; primary amines; polyamines; amino alcohols, amino acids, aldehyde hydrates, ketone hydrates, formaldehyde, polyhydric thiols, hydroxythiols, aminothiols and mercaptoacids, boronic acids and mixtures of two or more of these, or wherein the chain transfer agent is water, a polyhydric alcohol, a polyacid, a hydroxy acid, or any mixture thereof; wherein the chain transfer agent is a polyhydric alcohol, or wherein the chain transfer agent is a diol, or wherein the chain transfer agent is selected from the group consisting of: 1,2-ethanediol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 2,2-dimethylpropane-1,3-diol, 2-butyl-2-ethylpropane-1,3-diol, 1,5-hexanediol, 1,6-hexanediol, 1,8-octanediol, 1,10-decanediol, 1,12-dodecanediol, 2,2,4,4-tetramethylcyclobutane-1,3-diol, 1,3-cyclopentanediol, 1,2- cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol and 1,4-cyclohexanediethanol, or wherein the chain transfer agent is selected from the group consisting of: diethylene glycol, triethylene glycol, tetraethylene glycol, higher poly(ethylene glycol), preferably those with an average molecular weight of 220 to 2000 g/mol, dipropylene glycol, tripropylene glycol and higher (poly)propylene glycols, preferably those with an average molecular weight of 234 to 2000 g/mol, or wherein the chain transfer agent is selected from the group consisting of: 4,4'-(1-methylethylidene)bis[cyclohexanol], 2,2'-methylenebis[phenol], 4,4'-methylenebis[phenol], 4,4'-(phenylmethylene)bis[phenol], 4,4'-(diphenylmethylene)bis[phenol], 4,4'-(1,2-ethanediyl)bis[phenol], 4,4'-(1,2-cyclohexanediyl)bis[phenol], 4,4'-(1,3-cyclohexanediyl)bis[phenol], 4,4'-(1,4-cyclohexanediyl)bis[phenol], 4,4'-ethylidenebis[phenol], 4,4'-(1-phenylethylidene)bis[phenol], 4,4'-propylidenebis[phenol], 4,4'-cyclohexylidenebis[phenol], 4,4'-(1- methylethylidene)bis[phenol], 4,4'-(1- methylpropylidene)bis[phenol], 4,4'-(1-ethylpropylidene)bis[phenol], 4,4'-cyclohexylidenebis[phenol], 4,4'-(2,4,8,10-tetraoxaspiro[5.5]undecane-3,9-diyldi-2,1-ethanediyl)bis[phenol], 1,2-benzenedimethanol, 1,3- benzenedimethanol, 1,4-benzenedimethanol, 4,4'-[1,3- phenylenebis(1-methylethylidene)]bis[phenol], 4,4'-[1,4- phenylenebis(1-methylethylidene)]bis[phenol], phenolphthalein, 4,4'-(1-methylidene)bis[2-methylphenol], 4,4'-(1- methylethylidenol)bis[2-(1-methylethyl)phenol] and 2,2'-methylenebis[4-methyl-6-](1-methylethyl)phenol, or wherein the chain transfer agent is selected from the group consisting of: wherein the chain transfer agent is selected from the group consisting of: 1,3-propanediol, 1,4-butanediol, dipropylene glycol, diethylene glycol, and isosorbide, or wherein the chain transfer agent is a hydroxy acid, preferably wherein the hydroxy acid is an alpha-hydroxy acid, a beta-hydroxy acid, an α-w hydroxy acid, optionally substituted C3-20 aliphatic α-w hydroxy acids, polyester oligomeric esters, or wherein the hydroxy acid is selected from the group consisting of: preferably wherein the hydroxy acid is selected from the group consisting of: 3-hydroxypropionic acid, DL-3-hydroxybutyric acid, D-3-hydroxybutyric acid, L-3-hydroxybutyric acid, DL-3-hydroxyvaleric acid, D-3-hydroxyvaleric acid, L-3-hydroxyvaleric acid, salicylic acid, and glycolic acid derivatives, salicylic acid, DL-lactic acid, D-lactic acid, L-lactic acid, citric acid and mandelic acid, or wherein the chain transfer agent is a polycarboxylic acid, or wherein the chain transfer agent is a diacid, preferably wherein the chain transfer agent is selected from the group consisting of: phthalic acid, isophthalic acid, terephthalic acid, maleic acid, succinic acid, malonic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, and azelaic acid, or where the chain transfer agent is selected from the group consisting of: 17. Polymerization system according to claim 15 or 16, characterized in that the metal-metal-salenate complex has a formula selected from the group consisting of: wherein: M is a metal atom; LI is a ligand that is a polymerization initiator; m' is an integer between 0 and 2 inclusive, representing the number of initiating ligands present; Rc, in each occurrence, is independently selected from the group consisting of: -H; optionally substituted C1 to C12 aliphatic; optionally substituted 3 to 14 membered carbocycle; optionally substituted 3 to 14 membered heterocycle; R20; and R21, wherein two or more Rc groups may be taken together with intervening atoms to form one or more optionally substituted rings and, wherein two Rc groups are attached to the same carbon atom, they may be taken together with the carbon atom to which they are attached to form a selected portion of the group consisting of: an optionally substituted 3 to 8 membered spirocyclic ring, a carbonyl, an oxime, a hydrazone and an imine; R4a, R4a', R5a, R5a', R6a, R6a', R7a and R7a' are each independently hydrogen, a group , halogen, -NO2, -CN, -SR13, -S(O)R13, -S(O)2R13, -NR11C(O)R13, -OC(O)R13, -CO2R13, -NCO, -N3-, -OR10, -OC(O)NR11R12, -Si(R13)3, -NR11R12, -NR11C(O)R13 and -NR11C(O)OR13; or an optionally substituted radical selected from the group consisting of aliphatic C1-20; heteroaliphatic C1-20; aryl with 6 to 10 members; heteroaryl with 5 to 10 members; and a 3- to 7-membered heterocyclic compound, where [R1a and R4a], [R1a' and R4Aa'], and any two adjacent groups R4a, R4a', R5a, R5a', R6a, R6a', R7a, and R7a' can be taken together with intervening atoms to form one or more optionally substituted rings containing optionally one or more heteroatoms; R1a and R1a' are hydrogen when not taken together with R4a and R4a';R' is Rd or a group , where two or more adjacent R' groups can be taken together to form a saturated, partially unsaturated, or optionally substituted aromatic 3-12 membered ring containing 0 to 4 heteroatoms; Rd is selected from the group consisting of: optionally substituted C1 to C12 aliphatic; optionally substituted 3 to 14 membered carbocycle; optionally substituted 3 to 14 membered heterocycle; R20; and R21; R10, in each occurrence, is independently selected from the group consisting of: -H; optionally substituted C1-12 aliphatic; an optionally substituted 3 to 14 membered carbocycle; an optionally substituted 3 to 14 membered heterocycle; -S(O)2R13; -Si(R15)3; -C(O)R13; and a hydroxyl protecting group, R11 and R12, in each occurrence, are independently selected from the group consisting of: -H, aliphatic C1 to C12 optionally substituted; a 3 to 14 membered carbocycle optionally substituted; a 3 to 14 membered heterocycle optionally substituted; where two or more R11 or R12 groups may optionally be taken together with intervening atoms to form a 3 to 10 membered optionally substituted ring, R13, in each occurrence, is independently selected from the group consisting of: -H aliphatic C1 to C12 optionally substituted; a 3 to 14 membered carbocycle optionally substituted; and a 3 to 14 membered optionally substituted heterocycle, where two or more R13 groups in the same molecule may optionally be taken together to form a ring; R14, in each occurrence, is independently selected from the group consisting of: halogen; optionally substituted C1 to C12 aliphatic; optionally substituted 3- to 14-membered carbocycle; optionally substituted 3- to 14-membered heterocycle; -OR10; -OC(O)R13; -OC(O)OR13; - OC(O)NR11R12; -CN; -CNO; -C(R13)zH(3-Z); -C(O)R13; -C(O)OR13; - C(O)NR11R12; -NR11R12; -NR11C(O)R13; -NR11C(O)OR13; -NR11SO2R13; - N+R11R12R13X-; -P+(R11)3X-; -P(R11)3=N+=P(R11)3X-; -As+R11R12R13X-; - NCO; -N3; -NO2; -S(O)xR13; and -SO2NR11R12, R15, in each occurrence, is independently selected from the group consisting of: optionally substituted C1-12 aliphatic; an optionally substituted 3- to 14-membered carbocycle; and an optionally substituted 3- to 14-membered heterocycle, R16, in each occurrence, is independently selected from the group consisting of: optionally substituted C1-12 aliphatic; an optionally substituted 3- to 14-membered carbocycle; an optionally substituted 3- to 14-membered heterocycle; and -C(R17)zH(3-z), R17, in each occurrence, is independently selected from the group consisting of: -H; optionally substituted C1- to C12 aliphatic; an optionally substituted 3- to 14-membered carbocycle; and optionally substituted 3- to 14-membered heterocycle, R20, in each occurrence, is independently selected from the group consisting of: halogen; -OR10; -OC(O)R13; -OC(O)OR13; -N+(R11)3X-; -P+(R11)3X-; -P(R11)3=N+=P(R11)3X-; -As+R11R12R13X-; -OC(O)NR11R12; -CN; -CNO; -C(O)R13; -C(O)OR13; -C(O)NR11R12; -C(R13)zH(3-z); -NR11R12; -NR11C(O)R13; -NR11C(O)OR13; -NCO; -NR11SO2R13; -S(O)xR13; - S(O)2NR11R12; -NO2; -N3; and -Si(R13)(3-z)[(CH2)kR14]z, R21, in each occurrence, is independently selected from the group consisting of: -(CH2)kR20; -(CH2)kZ- (CH2)kR20; -C(R17)zH(3-z); -(CH2)kC(R17)zH(3-z); -(CH2)mZ- (CH2)mC(R17)zH(3-z); -(CH2)kZ-R16; X- is any anion, k is independently an integer from 1 to 8 inclusive at each occurrence, x is 0, 1, or 2, z is 1, 2, or 3, m is 0 or an integer from 1 to 8 inclusive, p is 0 or an integer from 1 to 4 inclusive; and where a group comprises a covalent ligand containing one or more atoms selected from the group consisting of C, O, N, S, and Si; “Z” is an activating functional group having co-catalytic activity in the copolymerization of epoxide CO2, ep is an integer from 1 to 4 indicating the number of individual activating functional groups Z present in a given group. , or wherein n is 1, one group Y is -OH, and the other group Y is -P(O)a(Ry)b(ORy)cOH, preferably wherein a is 1, b is 0, and c is 1 or a is 1, b is 1, and c is 0, even more preferably wherein Ry is hydrogen or aryl of 6 to 12 members. 18. Polymerization system according to claim 17, characterized in that R1a, R1a', R4a, R4a', R6a, and R6a' are each -H, or in that R5a, R5a', R7a, and R7a' are each optionally substituted aliphatic C1-C12, or in that R4a, R4a', R5a, R5a', R6a, R6a', R7a, and R7a' are each independently selected from the group consisting of: -H, -SiR3; methyl, ethyl, n-propyl, i-propyl, n-butyl, sec-butyl, t-butyl, isoamyl, t-amyl, texyl, and tritil, or in that R7a is selected from the group consisting of: -H, methyl; ethyl; n-propyl; i-propyl; n-butyl; sec-butyl; t-butyl; isoamyl; t-amyl; texyl; and tritil, or wherein one or more of R5a, R5a', R7a and R7a' is a group , or where R5a and R5a' are each a group , or where R5a is a group and R5a' is aliphatic C1-8, or wherein the metallosalenate complex has a formula selected from the group consisting of: preferably where M is cobalt, or where the initiating ligand (IL) is any anion, or where the initiating ligand (IL) is selected from the group consisting of: azides, halides, alkyl sulfonates, carboxylates, alkoxides and phenolates, or where the initiating ligand (IL) is selected from the group consisting of: -ORx, -SRx, -OC(O)Rx, -OC(O)ORx, -OC(O)N(Rx)2, -NRxC(O)Rx, -CN, halogen (e.g., -Br, -I, -Cl), -N3 and -OSO2Rx, wherein each Rx is independently selected from hydrogen, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aryl and optionally substituted heteroaryl and wherein two Rx groups may be taken together to form an optionally substituted ring containing one or more additional heteroatoms, or wherein the initiating ligand (IL) is -OC(O)Rx, where Rx is selected from optionally substituted aliphatic, fluorinated aliphatic, optionally substituted heteroaliphatic, optionally substituted aryl, fluorinated aryl and optionally substituted heteroaryl, or wherein the initiating ligand (IL) comprises a compound of the formula -Q'-A'(Z')n-, wherein: -Q'- is a carboxy or alkoxy group, -A'- is a multivalent moiety, each Z' is independently a functional group that can initiate a polymer chain, and n' is an integer between 1 and 10 inclusive, or wherein the ligand that is a polymerization initiator and the chain transfer agent are the same compound or ionic forms of the same molecule. 19. Polymerization system, according to any one of claims 15 to 18, characterized in that it further comprises a co-catalyst, preferably wherein the co-catalyst is selected from the group consisting of: amines, guanidines, amidines, phosphines, nitrogen-containing heterocycles, ammonium salts, phosphonium salts, arson salts, bisphosphine ammonium salts and a combination of two or more of these, or preferably wherein the co-catalyst comprises an “onium” salt, preferably further wherein the “onium” salt includes a counter ion that is a polyfunctional polymerization initiator, preferably further wherein the counter ion that is a polyfunctional polymerization initiator and the chain transfer agent are the same compounds, or ionic forms of the same compounds, or preferably wherein the co-catalyst is present in a molar ratio from 0.1:1 to 10:1, or 0.5:1 up to 5:1 or 1:1 up to 4:1, or 1:1, up to 2:1 in relation to the metal complex. 20. Method for the synthesis of aliphatic polyol polycarbonates, as defined in any one of claims 1 to 14, characterized in that it comprises the steps of: a) contacting i) a reaction mixture comprising one or more epoxides comprising ethylene oxide or propylene oxide with ii) a polymerization system, as defined in any one of claims 15 to 19, in the presence of carbon dioxide; b) allowing the polymerization reaction to proceed until a desired molecular weight of aliphatic polyol polycarbonate has formed; and c) terminating the polymerization. 21. A method according to claim 20, characterized in that the molar ratio of the metal complex to the epoxide varies from 1:100 to 1:1,000,000, or in that the molar ratio of the chain transfer agent to the metal complex is greater than 1000:1, or in that at least 98% of the terminal groups of the polycarbonate polyol formed are OH groups, or in that at least 99% of the terminal groups of the polycarbonate polyol formed are OH groups, or in that the PDI of the polycarbonate polyol formed is less than 1.6, or in that the PDI of the polycarbonate polyol formed is less than 1.2, or in that more than 95% of the bonds formed by the metal complex are carbonate bonds, or in that more than 98% of the bonds formed by the metal complex are carbonate bonds, or in that more than 99% of the bonds formed by the metal complex are carbonate bonds, or in that the epoxide comprises propylene oxide, preferably in which the head-to-tail ratio of the polycarbonate polyol is greater than 80%, or in which the head-to-tail ratio of the polycarbonate polyol is greater than 90%, or in which the head-to-tail ratio of the polycarbonate polyol is greater than 95%, or in which less than 5% of cyclic carbonate is formed, or in which less than 1% of cyclic carbonate is formed, or in which the chain transfer agent is selected from the group consisting of: water; polyhydric alcohols; polyacids; hydroxy acids; primary amines; polyamines; amino alcohols, amino acids, aldehyde hydrates, ketone hydrates, formaldehyde, polyhydric thiols, hydroxythiols, aminothiols and mercaptoacids, boronic acids and mixtures of two or more of these, preferably wherein the chain transfer agent is selected from the group consisting of: water; polyhydric alcohols; polyacids; and hydroxyacids, and mixtures of two or more of these. 22. Polyurethane composition, characterized in that it is formed by the reaction of one or more isocyanates with one or more aliphatic polyol polycarbonates, as defined in any of claims 1 to 14, preferably wherein the composition comprises a foam or coating. 23. A manufactured article, characterized in that it comprises a polycarbonate polyol composition, as defined in any one of claims 1 to 14, or a manufactured article comprising a polyurethane composition, as defined in claim 22.