CN106574008B

CN106574008B - Polycyclic alkene block polymer and the osmotic evaporation film being produced from it

Info

Publication number: CN106574008B
Application number: CN201580043759.0A
Authority: CN
Inventors: A·贝尔; O·布托夫; 滝川圭美
Original assignee: Sumitomo Bakelite Co Ltd
Current assignee: Sumitomo Bakelite Co Ltd
Priority date: 2014-08-15
Filing date: 2015-08-17
Publication date: 2018-06-19
Anticipated expiration: 2035-08-17
Also published as: KR20170036799A; WO2016025942A1; JP6225294B2; CN106574008A; JP2017525808A; KR101800195B1

Abstract

The present invention discloses a series of vinyl addition block polymers of the norbornene monomer of derived from highly functionalized and advocates right to it.Specifically, open a series of diblocks and triblock polymer derived from norbornene monomer.Be also disclosed this block polymer preparation method and they manufacture show the film of unique separating property in purposes.Specifically, film disclosed herein is useful in the organic volatile that separation includes butanol, phenol etc. from biomass and/or organic waste materials.

Description

Polycycloolefinic block polymers and pervaporation membranes made therefrom

Cross reference to related applications

This application claims priority to U.S. provisional patent application No. 62/037,823, filed on 8/15/2014, U.S. provisional patent application No. 62/037,828, filed on 8/15/2014, and U.S. provisional patent application No. 62/073,013, filed on 10/31/2014, which are incorporated herein by reference in their entirety.

Technical Field

The present invention relates to a series of block polymers derived from cyclic olefin monomers. More particularly, the present invention relates to a series of block polymers derived from various functionalized norbornene-type monomers. The invention also relates to a pervaporation membrane formed from such a block polymer and to the use of such a membrane in a pervaporation process.

Background

Cycloolefin polymers such as Polynorbornene (PNB) are widely used in various electronic, optoelectronic and other applications, and therefore methods for manufacturing such PNB on an industrial scale are becoming increasingly important. It is well known in the literature that various functionalized PNBs can be synthesized by addition polymerization with suitable starting norbornene monomers using various transition metal catalysts and procatalysts (procatalysts). See, for example, U.S. patent No. 7,989,570, the relevant portions of which are incorporated herein by reference.

However, in order to manufacture functionalized PNBs on an industrial scale, catalysts or catalyst systems are required to meet certain desired characteristics. Several such characteristics include: a) an active catalyst polymerization system, i.e., the catalyst retains its activity even after reaching an extremely high degree of chain growth directed to an extremely high molecular weight polymer; b) catalyst systems that are highly active even at very high monomer to catalyst molar ratios; c) efficient chain transfer for molecular weight control; d) good catalyst stability during polymerization including thermal and chemical stability, i.e., no termination of polymerization activity; e) fast polymerization kinetics, i.e., fast chain growth preferably around room temperature; and f) storage-stable components for highly reactive catalyst systems, for example stable A and B components.

U.S. Pat. No. 6,936,672 discloses various catalysts, procatalysts and catalyst systems for the polymerization of polycyclic olefins. However, these catalyst systems may not be suitable for preparing highly ordered block copolymers as described herein.

Disclosure of Invention

Technical problem to be solved by the invention

It is therefore an object of the present invention to provide a series of substituted or unsubstituted bicyclic olefin-palladium compounds that have utility as addition polymerization catalysts as either single component or two-component systems.

In addition, it is an object of the present invention to provide a process for preparing the substituted bicycloalkene-palladium compounds disclosed herein.

It is also an object of the present invention to provide a series of novel block copolymers for forming films having unique properties for various applications, and for use in the manufacture of electronic and optoelectronic devices.

Other objects and further scope of applicability of the present invention will become apparent from the detailed description given hereinafter.

Means for solving the technical problem

Advantageously, it has now been found that the various block copolymers described herein can be prepared by some organopalladium compounds as described herein as well as various other catalysts known in the art. It has further been found that the block copolymers of the present invention provide unique advantages and are therefore useful in a variety of applications, including but not limited to the formation of film materials and a variety of other optical and electronic applications. Membranes formed from block copolymers are useful, for example, for separating organic matter from biomass or other organic waste materials.

Thus, there is provided a block copolymer of the general formula (VI):

(A)_m-b-(B)_n(VI)

wherein m and n are integers of at least 15, but in other embodiments m and n may range from 20 to 4000 or from 50 to 3000 or from 100 to 2000, and in other embodiments m and n may also be higher than 4000, depending on the intended use;

b represents the bond between the two blocks of homopolymers A and B;

a and B are different from each other and are independently selected from recurring units represented by general formula (IVA) derived from a monomer of general formula (IV):

wherein:

represents a position bonded to another repeating unit;

p is an integer of 0,1 or 2;

R₃、R₄、R₅and R₆Are identical or different and are each, independently of one another, selected from hydrogen, linear or branched (C)₁-C₁₆) Alkyl, hydroxy (C)₁-C₁₆) Alkyl, perfluoro (C)₁-C₁₂) Alkyl, (C)₃-C₁₂) Cycloalkyl group, (C)₆-C₁₂) Bicycloalkyl, (C)₇-C₁₄) Tricycloalkyl group, (C)₆-C₁₀) Aryl group, (C)₆-C₁₀) Aryl radical (C)₁-C₃) Alkyl, perfluoro (C)₆-C₁₀) Aryl, perfluoro (C)₆-C₁₀) Aryl radical (C)₁-C₃) Alkyl, di (C)₁-C₂) Alkyl maleimide (C)₃-C₆) Alkyl, di (C)₁-C₂) Alkyl maleimide (C)₂-C₆) Alkoxy (C)₁-C₂) Alkyl, hydroxy, (C)₁-C₁₂) Alkoxy group, (C)₃-C₁₂) Cycloalkoxy, (C)₆-C₁₂) Bicyclic alkoxy group, (C)₇-C₁₄) Tricycloalkoxy, (C)₆-C₁₀) Aryloxy radical (C)₁-C₃) Alkyl, (C)₅-C₁₀) Heteroaryloxy (C)₁-C₃) Alkyl, (C)₆-C₁₀) Aryloxy group, (C)₅-C₁₀) Heteroaryloxy or (C)₁-C₆) Acyloxy, wherein each of the above substituents is optionally substituted with a group selected from halogen or hydroxy.

In another aspect of the present invention, there is also provided a triblock polymer represented by formula (VII):

(A)_m-b-(B)_n-b-(C)_o(VII)；

wherein m, n and b are as defined above, and o is an integer of at least 15, but in other embodiments o may range from 20 to 4000 or 50 to 3000 or 100 to 2000, and in other embodiments o may also be higher than 4000, depending on the intended use of the block polymer. C is the same or different from a or B and is independently selected from a repeating unit represented by formula (IVA) derived from a monomer of formula (IV) as defined herein.

Drawings

Hereinafter, embodiments according to the present invention are described with reference to the drawings and/or images. When provided, the drawings are to be simplified as part of various embodiments of the invention and are provided for illustrative purposes only.

FIG. 1 depicts a pervaporation module according to an embodiment of the present invention.

FIG. 2 depicts a pervaporation system according to an embodiment of the present invention.

FIGS. 3 to 5 show Atomic Force Micrographs (AFMs) of a film formed from a BuNB-HFANB (1:2) block copolymer (FIG. 3), a film formed from a BuNB-HFANB (2:1) block copolymer (FIG. 4), and a film formed from a HFANB-BuNB-HFANB (1:1:1) block copolymer (FIG. 5), respectively.

FIG. 6(a) shows HFANB (W) in a block polymer according to an embodiment of the present invention_HFANB) Graphical relationship between normalized flux (normalized flux) and various weight fractions, and HFANB (W) in the vinyl-addition block copolymer (a-BCP)_HFANB) The Separation Factor (SF) of (a) and various weight fractions.

FIG. 6(b) shows HFANB (W) in the vinyl-addition block copolymer (a-BCP) according to one embodiment of the present invention_HFANB) A graphical relationship between the swelling ratio of (a) and the various weight fractions.

FIG. 7(a) shows the normalized flux and Separation Factor (SF) obtained for one of the vinyl addition block copolymers of the present invention (a-BCP81) compared to the block polymer produced by the Ring Opening Metathesis Polymerization (ROMP) method (r-BC P81) and the random vinyl addition block copolymer (a-BCP 81).

FIG. 7(b) shows the swelling ratio observed for one of the vinyl addition copolymers (a-RCP81) of the present invention, compared with the block polymer (r-BC P81) and the random vinyl addition copolymer (a-RCP81) produced by the ring-opening metathesis polymerization (ROMP) method.

Detailed Description

The terms used herein have the following meanings:

as used herein, the articles "a," "an," and "the" include plural referents unless expressly limited otherwise to one referent.

As all numbers, values, and/or expressions referring to quantities of ingredients, reaction conditions, and so forth, used herein and in the appended claims are to be understood as modified in all instances by the term "about (about)" unless otherwise indicated, subject to the uncertainty of various measurements made to obtain the foregoing values.

When a range of values is disclosed herein, the range is considered to be continuous and includes both the minimum and maximum values of the range, as well as each value between such minimum and maximum values. Further, when a range refers to an integer, each integer between the minimum and maximum values of the range is included. Further, when multiple range-describing features or characteristics are provided, the ranges may be combined. In other words, unless otherwise indicated, all ranges disclosed herein are to be understood to encompass any and all subranges subsumed therein. For example, a stated range from "1 to 10" should be considered to include any and all subranges between the minimum value of 1 and the maximum value of 10. Exemplary subranges of the range 1 to 10 include, but are not limited to, 1 to 6.1, 3.5 to 7.8, 5.5 to 10, and the like.

As used herein, a symbolRepresents a position where bonding to another repeating unit or another atom or molecule or group or part thereof occurs, such as suitably having the structure of the group shown.

As used herein, "hydrocarbyl" refers to a group containing carbon and hydrogen atoms, non-limiting examples being alkyl, cycloalkyl, aryl, aralkyl, alkaryl, and alkenyl groups. The term "halohydrocarbyl" refers to a hydrocarbyl group in which at least one hydrogen is replaced by a halogen. The term "perhalohydrocarbyl (perhalocarbyl)" is a hydrocarbyl group in which all of the hydrogens are replaced with halogens.

As used herein, the expression "(C)₁-C₆) Alkyl "includes methyl and ethyl, and straight or branched propyl, butyl, pentyl and hexyl. Specific alkyl groups are methyl, ethyl, n-propyl, isopropyl and tert-butyl. The derivation is expressed as ` (C)₁-C₄) Alkoxy group "," (C)₁-C₄) Thioalkyl "," (C)₁-C₄) Alkoxy (C)₁-C₄) Alkyl group "," hydroxy group (C)₁-C₄) Alkyl group "," (C)₁-C₄) Alkyl-carbonyl "," (C)₁-C₄) Alkoxycarbonyl (C)₁-C₄) Alkyl group "," (C)₁-C₄) Alkoxycarbonyl group and amino group (C)₁-C₄) -alkyl "," (C)₁-C₄) Alkylamino "," (C)₁-C₄) Alkylcarbamoyl (C)₁-C₄) Alkyl group "," (C)₁-C₄) Dialkylcarbamoyl- (C)₁-C₄) Alkyl, mono-or di- (C)₁-C₄) Alkylamino radical (C)₁-C₄) Alkyl group "," amino group (C)₁-C₄) Alkylcarbonyl group and diphenyl group (C)₁-C₄) Alkyl group "," phenyl group (C)₁-C₄) Alkyl group, phenyl carbonyl group (C)₁-C₄) Alkyl and phenoxy- (C)₁-C₄) Alkyl "should be interpreted accordingly.

As used herein, the expression "cycloalkyl" includes all known cyclic groups. Representative examples of "cycloalkyl" include, without limitation, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, and the like. Derivatisation expressions such as "cycloalkoxy", "cycloalkylalkyl", "cycloalkylaryl", "cycloalkylcarbonyl" are to be interpreted accordingly.

As used herein, the expression "(C)₂-C₆) Alkenyl "includes ethenyl and straight or branched propenyl, butenyl, pentenyl and hexenyl. Likewise, the expression "(C)₂-C₆) Alkynyl includes ethynyl and propynyl, as well as straight or branched butynyl, pentynyl and hexynyl.

As used herein, the expression "(C)₁-C₄) Acyl "should have an alkyl group with" (C)₁-C₄) Alkanoyl "has the same meaning and may also be structurally represented as" R-CO- ", wherein R is (C) as defined herein₁-C₃) An alkyl group. Further, "(C)₁-C₃) The alkylcarbonyl group "should have the general formula (C)₁-C₄) Acyl has the same meaning. Specifically, "(C)₁-C₄) The "acyl" may be acyl, acetyl, propionyl, n-butyryl, etc. The derivation is expressed as ` (C)₁-C₄) Acyloxy "and" (C)₁-C₄) Acyloxyalkyl "should be construed accordingly.

As used herein, the expression "(C)₁-C₆) Perfluoroalkyl "means that all of the hydrogen atoms in the alkyl group are replaced with fluorine atoms. Illustrative examples include trifluoromethyl and pentafluoroethyl, and straight or branched heptafluoropropyl, nonafluorobutyl, undecafluoropentyl and tridecafluorohexyl. Derivative expression "(C)₁-C₆) Perfluoroalkoxy "should be construed accordingly.

As used herein, the expression "(C)₆-C₁₀) Aryl "means a substituted or unsubstituted phenyl or naphthyl. Specific examples of the substituted phenyl group or naphthyl group include o-, p-, m-tolyl, 1,2-, 1,3-, 1, 4-xylyl, 1-methylnaphthyl, 2-methylnaphthyl and the like. "substituted phenyl" or "substituted naphthyl" also includes any possible substituent as further defined herein or known in the art. Derivative expression "(C)₆-C₁₀) Arylsulfonyl "should be construed accordingly.

As used herein, the expression "(C)₆-C₁₀) Aromatic hydrocarbonRadical (C)₁-C₄) Alkyl "means (C) as defined herein₆-C₁₀) Aryl is further attached to (C) as defined herein₁-C₄) An alkyl group. Representative examples include benzyl, phenylethyl, 2-phenylpropyl, 1-naphthylmethyl, 2-naphthylmethyl and the like. It should further be noted that the expressions "arylalkyl" and "aralkyl" mean the same and are used interchangeably. Therefore, the expression "(C)₆-C₁₀) Aryl radical (C)₁-C₄) Alkyl may also be interpreted as "(C)₆-C₁₄) Aralkyl ".

As used herein, the expression "heteroaryl" includes all known aromatic groups containing heteroatoms. Representative 5-membered heteroaryl groups include furyl, thienyl (thienyl or thiophenyl), pyrrolyl, isopyrrolyl, pyrazolyl, imidazolyl, oxazolyl, thiazolyl, isothiazolyl and the like. Representative 6-membered heteroaryl groups include pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, triazinyl, and the like. Representative examples of bicyclic heteroaryl groups include benzofuranyl, benzothienyl, indolyl, quinolinyl, isoquinolinyl, cinnolinyl (cinnnolyl), benzimidazolyl, indazolyl, pyridofuranyl, pyridothienyl, and the like.

As used herein, the expression "heterocycle" includes all known cyclic groups containing further heteroatoms. Representative 5-membered heterocyclic groups include tetrahydrofuranyl, tetrahydrothienyl, pyrrolidinyl, 2-thiazolinyl, tetrahydrothiazolyl, tetrahydrooxazolyl, and the like. Representative 6-membered heterocyclic groups include piperidinyl, piperazinyl, morpholinyl, thiomorpholinyl, and the like. Various other heterocyclic groups include, without limitation, aziridinyl, azepanyl, diazepanyl, diazabicyclo [2.2.1] hept-2-yl, triazacyclooctanyl (triazocanyl), and the like.

"halogen" or "halo" refers to chlorine, fluorine, bromine, and iodine.

In a broad sense, the term "substituted" is contemplated to include all permissible substituents of organic compounds. As herein describedIn some embodiments disclosed, the term "substituted" means being independently selected from C by more than one_1-6Alkyl radical, C_2-6Alkenyl radical, C_1-6Perfluoroalkyl, phenyl, hydroxy, -CO₂H. Esters, amides, C₁-C₆Alkoxy radical, C₁-C₆Sulfanyl, C₁-C₆Perfluoroalkoxy, -NH₂Cl, Br, I, F, -NH-lower alkyl and-N (lower alkyl)₂The substituent (1) is substituted. However, any other suitable substituent known to those skilled in the art may also be used in these embodiments.

It should be noted that any atom having an unsaturated valence in the text, schemes, examples and tables herein is assumed to have the appropriate number of hydrogen atoms to saturate such valence.

As used herein, the term "living polymerization" refers to chain growth polymerization in which the ability of the growing polymer chain to terminate has been removed. In other words, in this system, there are no chain termination and chain transfer reactions, and the chain initiation rate is also much greater than the chain growth rate, which results in polymer chains growing at a more constant rate than seen in conventional chain polymerization, and their lengths remain very similar (i.e., they have very low polydispersity index, PDI).

As used herein, the terms "block copolymer" or "block polymer" are used interchangeably and denote the same, i.e., two or more homopolymer subunits are linked by a covalent bond. Thus, a "diblock copolymer" may be composed of_m-b-(B)_n-represents, wherein the homopolymer of formula a is linked to the homopolymer of formula B by a single bond, and m and n are the respective numbers of monomeric repeating units. Thus, in the expression "diblock copolymer", b "represents the aforementioned homopolymer (A)_mThe "block" of (A) is covalently bonded to the later-described homopolymer (B)_nAnd (4) connecting. Thus, the notation "-b-" should be interpreted as a bond between the designated polymer blocks. Likewise, "triblock copolymer", "tetrablock copolymer", and the like should be appropriately construed as the case may be. In addition, the "Diblock copolymers "or" diblock polymers "may be used interchangeably.

As used herein, the terms "polymer composition", "copolymer composition", "terpolymer composition" or "tetrapolymer composition" are used interchangeably herein and refer to a residue comprising at least one synthetic polymer, copolymer, terpolymer or tetrapolymer, and other ingredients from the synthesis of initiators, solvents or accompanying such polymers, which means that such residue is understood not to necessarily be covalently bonded to the polymer. However, some catalysts or initiators may sometimes be covalently bonded to a portion of the polymer chain at the beginning and/or end of the polymer chain. Such residues and other ingredients considered to be part of the "polymer" or "polymer composition" are typically mixed or blended with the polymer such that they tend to remain with the polymer as these are transferred between containers or between solvents or dispersion media. The polymer composition may also include substances added after synthesis of the polymer to provide or modify specific properties of such composition. Such materials include, but are not limited to, solvents, antioxidants, photoinitiators, sensitizers, and others, as will be discussed in more detail below.

The term "derivatized monomer repeat unit" means that the polymer repeat unit is polymerized (formed) from, for example, a polycyclic norbornene-type monomer, wherein the resulting polymer is formed by 2, 3-matched linkage (ench aiment) of the norbornene-type monomer, as shown below:

thus, in accordance with an embodiment of the present invention, there is provided a compound of formula I:

wherein:

is (C)₅-C₁₀) Cycloalkenyl radical, (C)₇-C₁₂) A bicycloalkenyl group or (C)₈-C₁₂) A tricycloalkenyl group;

m is nickel, palladium or platinum;

LB is a Lewis Base;

is a weakly coordinating anion;

y is PR₃Or O ═ PR₃Wherein R is independently selected from methyl, ethyl, (C)₃-C₆) Alkyl, substituted or unsubstituted (C)₃-C₇) Cycloalkyl group, (C)₆-C₁₀) Aryl group, (C)₆-C₁₀) Aralkyl, methoxy, ethoxy, (C)₃-C₆) Alkoxy, substituted or unsubstituted (C)₃-C₇) Cycloalkoxy, (C)₆-C₁₀) Aryloxy or (C)₆-C₁₀) An aralkyloxy group; and

R₁is methyl, ethyl, straight chain or branched (C)₃-C₆) Alkyl, (C)₆-C₁₀) Aryl group, (C)₆-C₁₀) Aralkyl or R₂CO, wherein R₂Is methyl, ethyl or (C)₃-C₆) An alkyl group.

In another embodiment of the present invention, various cycloalkenyls, bicycloalkenyls or tricycloalkenyls may be used as in the compounds of formula (I)A group. (C)₅-C₁₀) Representative examples of cycloalkenyl radicals include, without limitation, cyclopentene, cyclohexene, cycloheptene, cyclooctene, cyclononeneOr cyclodecene. However, other suitable cycloalkenyl radicals including cycloundecene, cyclododecene, and the like may also be used. (C)₇-C₁₂) Representative examples of the bicycloalkenyl group include, without any limitation, bicyclo [2,2, 1]]Heptene, bicyclo [3,2, 1]]Octene, bicyclo [2,2 ]]Octene, bicyclo [3,2 ]]Nonene, bicyclo [3,3, 1]]Nonene, 1,2,3,3a,4,6 a-hexahydropentalene, 3a,4,5,6,7,7 a-hexahydro-1H-indene, 1,2,3,4,4a,5,8,8 a-octahydronaphthalene, 2,3,4,4a,5,6,9,9 a-octahydro-1H-benzo [7 ] n]Rotaxanes, and the like. (C)₈-C₁₂) Representative examples of tricycloalkenyl groups include, without limitation, dicyclopentadiene, (4s,7s) -3a,4,5,6,7,7 a-hexahydro-1H-4, 7-ethanoindene, and the like. Furthermore, any of the substituted cycloalkenes, bicycloalkenes or tricycloalkenes described above may also be used.

In another embodiment of the present invention, M may not be nickel, palladium or platinum. Suitable M include any group X transition metal or group IX metal, such as cobalt, rhodium or iridium.

In another embodiment of the invention, the compound of formula (I) comprises a Lewis base, which is coordinately bound to the metal atom M. That is, the lewis base bonds to the metal atom by sharing its two arc pair electrons. Any lewis base known in the art may be used for this purpose. Advantageously, it has now been found that readily dissociable lewis bases generally provide more suitable compounds of formula (I) as polymerization catalysts, i.e., initiators, under the polymerization conditions described in further detail below. Thus, in one aspect of the invention, judicious selection of lewis bases will provide for modulation of the catalytic activity of the compounds of the invention.

Thus, it has now been found that suitable LBs which may be used include, without limitation, substituted and unsubstituted nitriles, including alkyl, aryl or aralkyl nitriles; phosphine oxides, including substituted and unsubstituted trialkyl phosphine oxides, triaryl phosphine oxides, and various combinations of alkyl, aryl, and aralkyl phosphine oxides; substituted and unsubstituted pyrazines; substituted and unsubstituted pyridines; phosphites, including substituted and unsubstituted trialkyl phosphites, triaryl phosphites, and various combinations of alkyl, aryl, and aralkyl phosphites; phosphines, including substituted and unsubstituted trialkyl phosphines, triaryl alkyl phosphines, and various combinations of alkyl, aryl, and aralkyl phosphines. Various other LBs that may be used include various esters, alcohols, ketones, amines and anilines, arsine (arsine), stibine (stibine), and the like.

In some embodiments of the invention, LB is selected from acetonitrile, propionitrile, n-butyronitrile, tert-butyronitrile, benzonitrile (C)₆H₅CN), 2,4, 6-trimethylbenzonitrile, phenylacetonitrile (C)₆H₅CH₂CN) pyridine, 2-methylpyridine, 3-methylpyridine, 4-methylpyridine, 2, 3-dimethylpyridine, 2, 4-dimethylpyridine, 2, 5-dimethylpyridine, 2, 6-dimethylpyridine, 3, 4-dimethylpyridine, 3, 5-dimethylpyridine, 2, 6-di-tert-butylpyridine, 2, 4-di-tert-butylpyridine, 2-methoxypyridine, 3-methoxypyridine, 4-methoxypyridine, pyrazine, 2,3,5, 6-tetramethylpyrazine, diethyl ether, di-n-butyl ether, dibenzyl ether, tetrahydrofuran, tetrahydropyran, benzophenone, triphenylphosphine oxide, PR₃Wherein R is independently selected from methyl, ethyl, (C) or a salt of a phosphonic acid or a phosphite ester of (A) or (B)₃-C₆) Alkyl, substituted or unsubstituted (C)₃-C₇) Cycloalkyl group, (C)₆-C₁₀) Aryl group, (C)₆-C₁₀) Aralkyl, methoxy, ethoxy, (C)₃-C₆) Alkoxy, substituted or unsubstituted (C)₃-C₇) Cycloalkoxy, (C)₆-C₁₀) Aryloxy group and (C)₆-C₁₀) An aralkyloxy group. PR₃Representative examples of (A) include, without any limitation, trimethylphosphine, triethylphosphine, tri-n-propylphosphine, triisopropylphosphine, tri-n-butylphosphine, triisobutylphosphine, tri-tert-butylphosphine, tricyclopentylphosphine, triallylphosphine, tricyclohexylphosphine, triphenylphosphine, trimethylphosphite, triethylphosphite, tri-n-propylphosphite, triisopropylphosphite, tri-n-butylphosphite, triisobutylphosphite, tri-tert-butylphosphite, tricyclopentylphosphite, triallyl phosphitePhosphite esters, tricyclohexyl phosphite, triphenyl phosphite, and the like. It should be noted, however, that various other known LBs that will produce the desired activity may also be used in this embodiment of the present invention.

The phosphine ligand may also be selected from phosphine compounds which are water soluble and which impart solubility in the resulting catalyst in aqueous media. Selected phosphines of this type include, but are not limited to, carboxy-substituted phosphines such as 4- (diphenylphosphino) benzoic acid and 2- (diphenylphosphino) benzoic acid, sodium 2- (dicyclohexylphosphino) ethanesulfonate, 4'- (phenylphosphino) bis (benzenesulphonic acid) dipotassium salt, 3' -phosphinidenetris (benzenesulphonic acid) trisodium salt, 4- (dicyclohexylphosphino) -1, 1-dimethylpiperidinium chloride, 4- (dicyclohexylphosphino) -1, 1-dimethylpiperidinium iodide, quaternary amine-functionalized salts of phosphines such as 2- (dicyclohexylphosphino) -N, N, N-trimethylethanaminium chloride, 2'- (cyclohexyl-phosphino) bis [ N, N, N-trimethylethanaminium dichloride, 2' - (cyclohexylphosphino) bis, 2,2' - (cyclohexylphosphinylidine) -bis (N, N, N-trimethylethanaminium) diiodide and 2- (dicyclohexylphosphino) -N, N, N-trimethylethanaminium iodide.

Other examples of organophosphorus compounds suitable as LB include phosphinite (phosphonite) and phosphonate ligands. Representative examples of phosphinite ligands include, but are not limited to, methyl diphenyl phosphinite, ethyl diphenyl phosphinite, isopropyl diphenyl phosphinite, and phenyl diphenyl phosphinite. Representative examples of phosphonite ligands include, but are not limited to, diphenylphenylphosphonite, dimethylphenylphosphite, diethylmethylphosphonite, diisopropylphenylphosphonite, and diethylphenylphosphonite.

In a further aspect of the invention, it has now been found that there is a counter anionThe compounds of formula (I), which are Weakly Coordinating Anions (WCA), provide better catalytic (i.e., initiator) activity. That is, the WCA is an anion that is only weakly coordinated to the cationic complex. It is soluble to neutral Lewis baseAgent or monomer displacement is sufficiently unstable. More specifically, the WCA anion acts as a stabilizing anion to the cationic complex and does not form a covalent bond with the metal atom M. The WCA anion is relatively inert because it is non-oxidizing, non-reducing, and non-substantive.

Generally, the WCA can be selected from borate, phosphate, arsenate, antimonate, aluminate, boratobenzene (boratobenzene) anions, carborane, halocarborane anions, sulfamate (sulfo namide), and sulfonate.

Broadly speaking, suitable borate anions can be represented by formula a, phosphate, arsenate and antimonate anions can be represented by formula B, and aluminate anions can be represented by formula C:

[M_a(R_a)(R_b)(R_c)(R_d)]A

[M_b(R_a)R_b)(R_c)(R_d)(R_e)(R_f)]B

[M_c(OR_a)(OR_b)(OR_c)(OR_d)]C

wherein, in the formula A, M_aIs boron, M in the formula B_bIs phosphorus, arsenic or antimony, M in the formula C_cIs aluminum. R_a、R_b、R_c、R_d、R_eAnd R_fIndependently represent fluorine, straight chain and branched chain C₁-C₁₀Alkyl, straight and branched C₁-C₁₀Alkoxy, straight and branched C₃-C₅Haloalkenyl, straight and branched C₃-C₁₂Trialkylsiloxy radical, C₁₈-C₃₆Triarylsiloxy, substituted and unsubstituted C₆-C₃₀Aryl and substituted and unsubstituted C₆-C₃₀Aryloxy group, wherein R_aTo R_fNot all of them simultaneously represent an alkoxy group or an aryloxy group. When substituted, the aryl group may be mono-or polysubstituted, wherein the substituents areIndependently selected from straight and branched C₁-C₅Alkyl, straight and branched C₁-C₅Haloalkyl, straight and branched C₁-C₅Alkoxy, straight and branched C₁-C₅Haloalkoxy, straight and branched C₁-C₁₂Trialkylsilyl group, C₆-C₁₈Triarylsilyl groups, and a halogen selected from chlorine, bromine, and fluorine.

Representative borate anions of formula A include, but are not limited to, tetrafluoroborate, tetraphenylborate, tetrakis (pentafluorophenyl) borate, tetrakis (3, 5-bis (trifluoromethyl) phenyl) borate, tetrakis (2-fluorophenyl) borate, tetrakis (3-fluorophenyl) borate, tetrakis (4-fluorophenyl) borate, tetrakis (3, 5-difluorophenyl) borate, tetrakis (2,3,4, 5-tetrafluorophenyl) borate, tetrakis (3,4,5, 6-tetrafluorophenyl) borate, tetrakis (3,4, 5-trifluorophenyl) borate, methyltris (perfluorophenyl) borate, ethyltris (perfluorophenyl) borate, phenyltris (perfluorophenyl) borate, tetrakis (1,2, 2-trifluorovinyl) borate, tetrakis (4-triisopropylsilyltetrafluorophenyl) borate, tetrakis (3, 5-trifluorophenyl) borate, tetrakis (perfluorophenyl) borate, tetrakis (1,2, 2-trifluorovinyl) borate, tetrakis (4-triisopropylsilyltetrafluorophenyl) borate, and mixtures thereof, Tetrakis (4-dimethyl-tert-butylsilyltetrafluorophenyl) borate, (triphenylsiloxy) tris (pentafluorophenyl) borate, (octyloxy) tris (pentafluorophenyl) borate, tetrakis [3, 5-bis [ 1-methoxy-2, 2, 2-trifluoro-1- (trifluoromethyl) ethyl ] phenyl ] borate, tetrakis [3- [ 1-methoxy-2, 2, 2-trifluoro-1- (trifluoromethyl) ethyl ] -5- (trifluoromethyl) phenyl ] borate and tetrakis [3- [2,2, 2-trifluoro-1- (2,2, 2-trifluoroethoxy) -1- (trifluoromethyl) ethyl ] -5- (trifluoromethyl) phenyl ] borate.

Representative phosphates, arsenates, antimonates of formula B include, but are not limited to, hexafluorophosphate, hexaphenylphosphate, hexakis (pentafluorophenyl) phosphate, hexakis (3, 5-bis (trifluoromethyl) phenyl) phosphate, hexafluoroarsenate, hexakis phenyl arsenate, hexakis (pentafluorophenyl) arsenate, hexakis (3, 5-bis (trifluoromethyl) phenyl) arsenate, hexafluoroantimonate, hexakis phenyl antimonate, hexakis (pentafluorophenyl) antimonate, hexakis (3, 5-bis (trifluoromethyl) phenyl) antimonate, and the like.

Representative aluminate anions of formula C include, but are not limited to, tetrakis (pentafluorophenyl) aluminate, tris (nonafluorobiphenyl) fluoroaluminate, (octyloxy) tris (pentafluorophenyl) aluminate, tetrakis (3, 5-bis (trifluoromethyl) phenyl) aluminate, and methyltris (pentafluorophenyl) aluminate.

In the embodiment of the present invention, it is appropriateIs selected from And

in another embodiment of the present invention, the compound of formula (I) has the following substituents:

is cyclooctene, bicyclo [3,3,0 ]]Octene, bicyclo [2,2, 1]]Hept-2-ene, bicyclo [2,2 ] 2]Oct-2-ene or tricyclo [5,2,1,0^2,6]Dec-3-ene;

m is palladium;

LB is acetonitrile, tert-butyronitrile, C₆H₅CN, 2,4, 6-trimethylbenzonitrile, pyridine, 4-methylpyridine, 3, 5-dimethylpyridine, 4-methoxypyridine, benzophenone, or triphenylphosphine oxide;

is selected fromOr

Y is PR₃Or O ═ PR₃Wherein R is independently selected from isopropyl, sec-butyl, tert-butyl, cyclohexyl, phenyl, benzyl, isopropoxy, sec-butoxy, tert-butoxy, cyclohexyloxy, phenoxy or benzyloxy; and is

R₁Is methyl, ethyl, isopropyl, sec-butyl, tert-butyl, phenyl, phenoxy or acetyl (CH)₃CO)。

In another embodiment of the present invention, the compounds of the present invention are represented by general formula (II):

wherein:

LB is selected from pyridine, acetonitrile or C₆H₅CN；

Is selected fromOr

R is independently selected from methyl, ethyl and (C)₃-C₆) Alkyl, substituted or unsubstituted (C)₃-C₇) Cycloalkyl group, (C)₆-C₁₀) Aryl group, (C)₆-C₁₀) Aralkyl, methoxy, ethoxy, (C)₃-C₆) Alkoxy, substituted or unsubstituted (C)₃-C₇) Cycloalkoxy, (C)₆-C₁₀) Aryloxy or (C)₆-C₁₀) Aralkyloxy radical(ii) a And is

R₁Is methyl, ethyl, straight chain or branched (C)₃-C₆) Alkyl, (C)₆-C₁₀) Aralkyl or R₂CO, wherein R₂Is methyl, ethyl or (C)₃-C₆) An alkyl group.

In a further embodiment of the invention, the compounds of general formula (II) have the following substituents:

LB is acetonitrile;

is composed of

R is n-propyl, isopropyl, tert-butyl or phenyl; and is

R₁Is n-propyl, isopropyl, tert-butyl or-COCH₃。

In another embodiment of the present invention, the compounds of the present invention are represented by formula (IIA):

wherein:

LB is acetonitrile or pyridine;

is selected fromOrAnd

R₁is isopropyl or-COCH₃。

In this aspect of the invention, the compound of formula (IIA) has the following substituents:

LB is acetonitrile or pyridine;is composed ofOrAnd R is₁Is isopropyl.

In yet another embodiment of the present invention, the compounds of the present invention are represented by formula (IIB):

in yet another embodiment of the present invention, the compounds of the present invention are represented by formula (IIC):

wherein Py is pyridine.

In yet another embodiment of the present invention, the compounds of the present invention are represented by formula (IID):

wherein Py is pyridine.

In another aspect of the present invention, there is also provided a compound of formula (III):

wherein:

m is nickel, palladium or platinum;

x is halogen, triflate, mesylate or tosylate;

y is PR₃Or O ═ PR₃Wherein R is independently selected from methyl, ethyl, (C)₃-C₆) Alkyl, substituted or unsubstituted (C)₃-C₇) Cycloalkyl group, (C)₆-C₁₀) Aryl group, (C)₆-C₁₀) Aralkyl, methoxy, ethoxy, (C)₃-C₆) Alkoxy, substituted or unsubstituted (C)₃-C₇) Cycloalkoxy, (C)₆-C₁₀) Aryloxy or (C)₆-C₁₀) An aralkyloxy group; and is

R₁Is methyl, ethyl, straight chain or branched (C)₃-C₆) Alkyl, (C)₆-C₁₀) Aryl group, (C)₆-C₁₀) Aralkyl or R₂CO, wherein R₂Is methyl, ethyl or (C)₃-C₆) An alkyl group; and is

When R is phenyl, R₁Is not methyl.

It should be noted that some compounds of the general formula (III) are known. More specifically, compounds of the general formula (III) are disclosed in Crociani et al, J.Chem.Soc.A (1968)2869, wherein,is dicyclopentadienyl or cyclooctenyl, wherein R₁Is methoxy, M is palladium, X is chlorine or bromine, and Y is triphenylphosphine. Thus, the following compounds are excluded from the compounds of general formula (III):

[Pd(C₈H₁₂.OCH₃)(P(C₆H₅)₃)Cl]；

[Pd(C₈H₁₂.OCH₃)(P(C₆H₅)₃)Br]；

[Pd(C₁₀H₁₂.OCH₃)(P(C₆H₅)₃)Cl]；

[Pd(C₁₀H₁₂.OCH₃)(P(C₆H₅)₃)Br]；

[Pt(C₈H₁₂.OCH₃)(P(C₆H₅)₃)Cl]；

[Pt(C₈H₁₂.OCH₃)(P(C₆H₅)₃)Br]；

[Pt(C₁₀H₁₂.OCH₃)(P(C₆H₅)₃)Cl](ii) a And

[Pt(C₁₀H₁₂.OCH₃)(P(C₆H₅)₃)Br]。

in one embodiment of the present invention, the compound of formula (III) has the following substituents:

is cyclooctene, bicyclo [3,3,0 ]]Octene, bicyclo [2,2, 1]]Hept-2-ene, bicyclo [2,2 ] 2]Oct-2-ene or tricyclo [5,2,1,0^2,6]Dec-3-ene, the latter commonly known as dicyclopentadiene;

m is palladium;

x is chlorine or triflate;

R₁Is methyl, ethyl, n-propyl, isopropyl, sec-butyl, tert-butyl, phenyl or acetyl.

In another embodiment of the invention, the compound of this aspect of the invention is represented by general formula (III a):

wherein:

x is chlorine or triflate; and is

R₁Is n-propyl, isopropyl or-COCH₃。

In a further embodiment of the invention, the compound of formula (III) comprises wherein R₁Is isopropyl; or wherein R is₁Is n-propyl; or wherein R is₁is-COCH₃。

Non-limiting exemplary compounds of formula (III) can be represented by formula (IIIB), (IIIC), or (IIID):

in another embodiment of the present invention, other representative compounds are included in the compounds of formula (III), which may be represented by formula (IIIE):

wherein R and X are as defined above. R_gSelected from acetoxy, methoxy, ethoxy, phenoxy and substituted or unsubstituted phenyl. Wherein a substituent comprises any moiety known to those skilled in the art. Non-limiting examples of suitable substituents include (C)₁-C₆) Alkyl, (C)₁-C₆) Alkoxy group, (C)₇-C₁₀) Aralkyl, (C)₆-C₁₀) Aralkyloxy, (C)₆-C₁₀) Aryl group, (C)₆-C₁₀) Aralkyloxy, and the like. In another embodiment, compounds of formula (IIIE) include the following: wherein X is Cl, Br or I; r is independently isopropyl, tert-butyl or phenyl; and R is_gIs acetoxy, methoxy or phenyl. In another embodiment, compounds of formula (IIIE) include the following: wherein X is Cl, Br or I; r is independently isopropyl, tert-butyl or phenyl; and R is_gIs methoxyphenyl.

In a further aspect of the invention there is also provided a series of compounds of general formula (IIIX) or (IIIY) useful as procatalysts:

wherein, R, R_gAnd X is as defined above. R_hAre suitable functional groups that contribute to chain growth by intercalating into the olefin undergoing polymerization. Examples of such groups include hydroxyl, alkenyl groups such as vinyl, and the like.

The compounds of the present invention can be synthesized by any procedure known to those skilled in the art. In particular, as mentioned above, some compounds of the general formula (III) and several starting materials for the preparation of the compounds of the invention are known or are commercially available per se. The compounds of the invention and several precursor compounds can also be prepared by methods for preparing analogous compounds as reported in the literature and further described herein. See, e.g., j.chatt, et al, j.chem.soc. (1957) 3413-; m.green, et al, j.chem.soc. (a) (1967) 2054-; hiraki, et al, Bull, chem, Soc, Japan,53,1980, 1976-1981; all relevant portions of these patents are incorporated herein by reference.

More specifically, the compounds disclosed herein can be synthesized according to the following procedure of schemes 1-2, wherein, R, R₁LB, M, X and Y are as defined for formulae I and III, respectively, unless otherwise indicated.

Scheme 1

In step 1 of scheme I, a suitable cyclodiene complexed metal compound of formula (IA) is reacted with an appropriate alcohol or acid to form a compound of formula (IB). The reaction can be carried out by any procedure known in the art. For example, a solution of a compound of formula (IA) can be reacted with a suitable alcohol or acid at room temperature or higher to form a compound of formula (IB). In step 2 of scheme 1, the compound of formula (IB) is further reacted with a suitable phosphine or phosphine oxide to form a compound of formula (III). The reaction can again be carried out using any known literature procedure. Typically, this reaction is carried out in a suitable solvent at or above room temperature. Finally, in step 3 of scheme I, the compound of formula (III) is reacted with a suitable salt of a weakly coordinating anion of formula A-Z to form the compound of formula (I), wherein A is any suitable cation, such as an alkali metal cation or the like, that readily exchanges the anion Z with the compound X of formula (III).

Scheme 2 illustrates the synthesis of some specific compounds as exemplified herein. Specifically, the compounds of the general formula (II) and their precursors, the compounds of the general formula (IIC) can be synthesized from the salts of the dicyclopentadiene complexes/Pd (II) of the general formula (IIA). As illustrated in step 1 of scheme 2, the compound of formula (IIA) can be in a suitable solvent,with various alcohols or carboxylic acids (i.e., R) at room temperature or at elevated temperatures₁OH, wherein R₁Alkyl, aryl or acetyl as defined herein) to obtain a compound of general formula (IIB). In step 2 of scheme 2, a compound of formula (IIB) is reacted with a compound of formula PR₃With a suitable phosphine or phosphite to give a compound of formula (IIC). The reaction can again be carried out in a suitable solvent at or above room temperature to give the compound of formula (IIC). Finally, in step 3 of scheme 2, the compound of formula (IIC) is further reacted with a suitable salt of a weakly coordinating anion, such as lithium salt LiZ, to form a compound of formula (II). Typically, this reaction is carried out in a suitable solvent at room temperature. It should be noted that all of these reaction steps are carried out in an inert atmosphere, such as nitrogen, helium or argon. Any solvent can be used in these reactions, including but not limited to alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, t-butanol, and the like; alkane solvents such as hexane, heptane or petroleum ether; combinations thereof.

Scheme 2

As described herein, the compounds of the present invention, especially the compounds of formula (I), more especially the compounds of formula (II), are highly effective as single component vinyl addition polymerization catalysts as described in further detail below and as illustrated in the specific examples below. Likewise, compounds of formula (III), more particularly compounds of formula (IIG), still more particularly compounds of formulae (IIIA) to (IIIE), (IIIX) and (IIIY), are effective as two-component catalysts for the vinyl addition polymerization of various olefins as described in further detail below and as illustrated in the specific examples below.

Polymer and method of making same

The compound of the present invention can be used as a vinyl addition polymerization initiator for preparing various cycloolefin addition polymers. In one aspect of the invention, the compounds of the invention of the general formula (I) or (II) are used as one-component systems (unicomponent systems), which are regarded as initiators, in which the initiating group, for example the Pd-C bond, replicates the properties of the propagating species as closely as possible. Therefore, there is a possibility that the polydispersity decreases and the number of active sites increases in both solution polymerization and bulk polymerization. In contrast, some of the hitherto known compounds such as Pd-allyl complexes require a transition from sigma-pi to sigma-bonded configuration, and then the catalyst center must produce an intervening cycloalkyl building block, for example a norbornene building block if norbornene is a cyclic olefin monomer. Thus, the compounds of the present invention provide heretofore unavailable benefits as initiators for the preparation of certain cyclic olefin polymers described herein.

In another aspect of the invention, the compounds of formula (III) are mixed in situ with certain compounds of formula (VI) to form a very active two-component catalyst system, which is further activated by a solvent or monomer. It has now been surprisingly found that such catalyst systems are very useful for the preparation of various polymers from certain cyclic olefin monomers described herein, and avoid exogenous ligands such as acetonitrile.

Accordingly, there is provided a polymeric composition comprising:

a compound of the general formula (I),

wherein:

m is nickel, palladium or platinum;

LB is a Lewis base;

is a weakly coordinating anion;

R₁Is methyl, ethyl, straight chain or branched (C)₃-C₆) Alkyl, (C)₆-C₁₀) Aryl group, (C)₆-C₁₀) Aralkyl or R₂CO, wherein R₂Is methyl, ethyl or (C)₃-C₆) An alkyl group; and

a monomer of formula (IV):

wherein:

p is an integer of 0,1 or 2;

R₃、R₄、R₅and R₆Are identical or different and are each, independently of one another, selected from hydrogen, linear or branched (C)₁-C₁₆) Alkyl, hydroxy (C)₁-C₁₆) Alkyl, perfluoro (C)₁-C₁₂) Alkyl, (C)₃-C₁₂) Cycloalkyl group, (C)₆-C₁₂) Bicycloalkyl, (C)₇-C₁₄) Tricycloalkyl group, (C)₆-C₁₀) Aryl radicals、(C₆-C₁₀) Aryl radical (C)₁-C₃) Alkyl, perfluoro (C)₆-C₁₀) Aryl, perfluoro (C)₆-C₁₀) Aryl radical (C)₁-C₃) Alkyl, di (C)₁-C₂) Alkyl maleimide (C)₃-C₆) Alkyl, di (C)₁-C₂) Alkyl maleimide (C)₂-C₆) Alkoxy (C)₁-C₂) Alkyl, hydroxy, (C)₁-C₁₂) Alkoxy group, (C)₃-C₁₂) Cycloalkoxy, (C)₆-C₁₂) Bicyclic alkoxy group, (C)₇-C₁₄) Tricycloalkoxy, (C)₆-C₁₀) Aryloxy radical (C)₁-C₃) Alkyl, (C)₅-C₁₀) Heteroaryloxy (C)₁-C₃) Alkyl, (C)₆-C₁₀) Aryloxy group, (C)₅-C₁₀) Heteroaryloxy or (C)₁-C₆) Acyloxy, wherein each of the above substituents is optionally substituted with a group selected from halogen or hydroxy.

It should be noted that in this aspect of the invention, all compounds of formula (I), including all compounds of formula (II), as described herein can be used without any limitation. It should also be noted that any known monomer of formula (IV) can be used in this aspect of the invention. Representative examples of monomers of formula (IV) include, without limitation, the following:

bicyclo [2.2.1] hept-2-ene (NB);

5-methylbicyclo [2.2.1] hept-2-ene (MeNB);

5-ethylbicyclo [2.2.1] hept-2-ene (EtNB);

5-n-butylbicyclo [2.2.1] hept-2-ene (BuNB);

5-hexylbicyclo [2.2.1] hept-2-ene (HexNB);

5-octylbicyclo [2.2.1] hept-2-ene (OctNB);

5-decylbicyclo [2.2.1] hept-2-ene (DecNB);

5-Trifluoromethylbicyclo [2.2.1]Hept-2-ene (CF)₃NB)；

5-Perfluoroethylbicyclo [2.2.1]Hept-2-ene (C)₂F₅NB)；

5-n-perfluorobutylbicyclo [2.2.1]Hept-2-ene (C)₄F₉NB)；

5-perfluorohexylbicyclo [ 2.2.1%]Hept-2-ene (C)₆F₁₃NB)；

5-perfluorooctylbicyclo [2.2.1] hept-2-ene (OctNB);

5-perfluorodecybicyclo [2.2.1] hept-2-ene (PerfluoroDecNB);

norbornenyl-2-trifluoromethyl-3, 3, 3-trifluoropropan-2-ol (HFANB);

5- ((2- (2-methoxyethoxy) ethoxy) methyl) bicyclo [2.2.1] hept-2-ene (NBTON);

1- (bicyclo [2.2.1] hept-5-en-2-yl) -2,5,8, 11-tetraoxadodecane (NBTODD);

5- (2- (2-ethoxyethoxy) ethyl) bicyclo [2.2.1] hept-2-ene;

5- (2- (2- (2-propoxyethoxy) ethoxy) bicyclo [2.2.1] hept-2-ene;

1- (bicyclo [2.2.1] hept-5-en-2-ylmethyl) -3, 4-dimethyl-1H-pyrrole-2, 5-dione (MeDMMINB);

1- (3- (bicyclo [2.2.1] hept-5-en-2-yl) propyl) -3, 4-dimethyl-1H-pyrrole-2, 5-dione (PrDMMINB);

1- (4- (bicyclo [2.2.1] hept-5-en-2-yl) butyl) -3, 4-dimethyl-1H-pyrrole-2, 5-dione (BuDMMINB);

1- (6- (bicyclo [2.2.1] hept-5-en-2-yl) hexyl) -3, 4-dimethyl-1H-pyrrole-2, 5-dione (hexdmamnb);

2- ((bicyclo [2.2.1] hept-5-en-2-ylmethoxy) methyl) oxirane (MGENB);

2- (bicyclo [2.2.1] hept-5-en-2-yl) oxirane;

2- (7- (bicyclo [2.2.1] hept-5-en-2-yl) heptyl) oxirane;

5-phenethylbicyclo [2.2.1] hept-2-ene (PENB);

5-benzylbicyclo [2.2.1] hept-2-ene (BnNB);

2- (bicyclo [2.2.1] hept-5-en-2-yl) bicyclo [2.2.1] heptane (also referred to herein as NBANB);

ethyl 3- (bicyclo [2.2.1] hept-2-en-2-yl) propionate (EPEsNB); and

2- (bicyclo [2.2.1] hept-5-en-2-yl) -5-phenyl-bicyclo [2.2.1] heptane (also referred to herein as NBNBAPh).

In one embodiment, the polymerizable composition of the present invention comprises a compound of formula (I) selected from the following:

wherein Py is pyridine; and the polymerizable monomer is selected from the following:

bicyclo [2.2.1] hept-2-ene (NB);

norbornenyl-2-trifluoromethyl-3, 3, 3-trifluoropropan-2-ol (HFANB);

5-hexylbicyclo- [2.2.1] hept-2-ene (HexNB);

5-octylbicyclo [2.2.1] hept-2-ene (OctNB);

5-decylbicyclo [2.2.1] hept-2-ene (DecNB);

5-perfluorobutylbicyclo [2.2.1]]Hept-2-ene (C)₄F₉NB)；

5-phenethylbicyclo [2.2.1] hept-2-ene (PENB);

5-benzylbicyclo [2.2.1] hept-2-ene (BnNB); and

2- (bicyclo [2.2.1] hept-5-en-2-yl) bicyclo [2.2.1] heptane (NBANB).

In a further aspect of the present invention, there is also provided a polymeric composition comprising:

a compound of the general formula (III):

wherein:

m is nickel, palladium or platinum;

x is halogen, triflate, mesylate or tosylate;

R₁Is methyl, ethyl, straight chain or branched (C)₃-C₆) Alkyl, (C)₆-C₁₀) Aryl group, (C)₆-C₁₀) Aralkyl or R₂CO, wherein R₂Is methyl, ethyl or (C)₃-C₆) An alkyl group;

a compound of the general formula (V):

wherein,

is selected from lithium, sodium, potassium, cesium, barium, ammonium or straight or branched chain tetra (C)₁-C₄) A cation in an alkylammonium;

is selected from OrWeakly coordinating anion of (a); and

a monomer of formula (IV):

wherein:

p is an integer of 0,1 or 2;

In this aspect of the invention, the polymerizable composition comprises a compound of formula (III) selected from the following:

furthermore, the compound of formula (V) is selected from the following:

lithium tetrafluoroborate;

lithium trifluoromethanesulfonate;

lithium tetrakis (pentafluorophenyl) borate;

lithium tetrakis (pentafluorophenyl) borate ([ Li (OEt) ]₂)_2.5][B(C₆F₅)₄])(LiFABA)；

Lithium tetraphenyl borate;

lithium tetrakis (3, 5-bis (trifluoromethyl) phenyl) borate;

lithium tetrakis (2-fluorophenyl) borate;

lithium tetrakis (3-fluorophenyl) borate;

lithium tetrakis (4-fluorophenyl) borate;

lithium tetrakis (3, 5-difluorophenyl) borate;

lithium hexafluorophosphate;

lithium hexaphenylphosphate;

lithium hexakis (pentafluorophenyl) phosphate;

lithium hexafluoroarsenate;

lithium hexaphenyl arsenate;

lithium hexakis (pentafluorophenyl) arsenate;

lithium hexa (3, 5-bis (trifluoromethyl) phenyl) arsenate;

lithium hexafluoroantimonate;

lithium hexaphenyl antimonate;

lithium hexa (pentafluorophenyl) antimonate;

lithium hexa (3, 5-bis (trifluoromethyl) phenyl) antimonate;

lithium tetrakis (pentafluorophenyl) aluminate;

lithium tris (nonafluorobiphenyl) fluoroaluminate;

lithium (octyloxy) tris (pentafluorophenyl) aluminate;

lithium tetrakis (3, 5-bis (trifluoromethyl) phenyl) aluminate; and

lithium methyltris (pentafluorophenyl) aluminate.

Further, any polymerizable monomer as described herein can be used. For example, the polymerizable monomer is selected from the following:

bicyclo [2.2.1] hept-2-ene (NB);

norbornenyl-2-trifluoromethyl-3, 3, 3-trifluoropropan-2-ol (HFANB);

5-hexylbicyclo- [2.2.1] hept-2-ene (HexNB);

5-octylbicyclo [2.2.1] hept-2-ene (OctNB);

5-decylbicyclo [2.2.1] hept-2-ene (DecNB);

5-perfluorobutylbicyclo [2.2.1]]Hept-2-ene (C)₄F₉NB)；

5-phenethylbicyclo [2.2.1] hept-2-ene (PENB);

5-benzylbicyclo [2.2.1] hept-2-ene (BnNB); and

2- (bicyclo [2.2.1] hept-5-en-2-yl) bicyclo [2.2.1] heptane (NBANB).

As mentioned above, the polymerization can be carried out neat (neat) (bulk polymerization) or in solution. That is, by practicing the present invention, it is now possible to make a variety of polymers containing at least one functionalized norbornene monomer (i.e., compound of formula (IV)) in the presence of a one component (i.e., compound of formula (I) or (II)) catalyst or a two component catalyst (i.e., a combination of compound of formula (III) and compound of formula (V)) as described herein. When a two-component catalyst is used, the compound of formula (III) may be generally referred to as the primary catalyst and the compound of formula (V) may be generally referred to as the activator. However, when a two-component catalyst is used, various other compounds effective as catalysts, procatalysts and/or activators may also be used in combination with the compounds of the general formulae (III) and (V).

The compounds of the invention have also been found to be highly active as one-component or two-component catalytic compositions. Therefore, it is now possible to produce a high-quality polymer by using a small amount of a catalyst. Thus, in one embodiment, addition polymerization can be effectively carried out using a molar ratio of monomer to single component catalyst of at least 100:1 based on the total moles of monomer and catalyst used. That is, 100 moles of monomer to 1 mole of single component catalyst was used. In other embodiments, the monomer to catalyst molar ratio may be 1,000,000: 1; 500,000: 1; 100,000: 1; 20,000: 1; 10,000:1, 1,000:1, 500:1, 400:1, 200:1, etc. When a two-component catalyst system is used, the molar ratio of monomer to procatalyst to activator can be at least 100:1: 1. In other embodiments, the molar ratio of monomer to procatalyst to activator may be 1,000,000:1: 1; 500,000:1: 1; 100,000:1: 1; 20,000:1: 1; 10,000:1:1, 1,000:1:1, 500:1:1, 400:1:1, 200:1:1, etc. In some embodiments, the amount of activator used exceeds the molar amount of procatalyst used, for example the molar ratio of procatalyst to activator can be from 1:1 to 1: 6.

As described above, the bulk polymerization reaction can be carried out using a catalyst and a monomer without any solvent. Advantageously, such polymerization can also be carried out in a mold at a suitable temperature to form a three-dimensional polymeric product. In general, the reaction temperature can be carried out in a range below ambient temperature, for example below 0 ℃ to the boiling point of the monomer, however, it is recommended that the components of the reaction vessel or the mould are not heated to more than one flash point of the monomer. Typically, bulk polymerization is carried out at a temperature in the range of about 10 ℃ to 300 ℃, in some other embodiments, the temperature may be in the range of about 10 ℃ to 200 ℃; or about 20 ℃ to 100 ℃.

Since the polymerization reaction is exothermic, unless cooled molds are used, the temperature in the molds is typically higher than the temperature of the feed during polymerization. Thus, the initial mold temperature may generally range from about-20 ℃ to about 300 ℃; or from about 0 ℃ to about 200 ℃; or from 20 ℃ to 100 ℃. The temperature distribution in the mold is affected by factors such as the mold geometry, the characteristics of the mold as a heat sink or heat supply device, the reactivity of the catalyst and monomer, and the like. To some extent, the selection of appropriate temperature and heat exchange conditions must be based on the experience of a given mold, feed, and catalyst system.

After the polymerization reaction is completed, the molding object may be subjected to an additional post-curing treatment at a temperature ranging from about 100 ℃ to 300 ℃ for about 15 minutes to 24 hours, or 1 hour to 2 hours. This post-cure treatment can enhance polymer properties, including glass transition temperature (T)_g) And Heat Distortion Temperature (HDT). In addition, post-curing is desirable, but not necessary, to obtain a final stable dimensional state (dimensional state) of the sample, to minimize residual odor, and to improve final physical properties.

Vinyl addition polymerization can also be carried out in solution using a one-component catalyst (i.e., a compound of formula (I) or (II)) or a two-component catalyst (i.e., a compound of formula (III) combined with a compound of formula (V)) as described herein. In this embodiment, a solution of the catalyst is suitably mixed with one or more desired solutions of the monomer (i.e., compound of formula (IV)) under conditions known in the art to form the polymer of the present invention. Suitable polymerization solvents include, without any limitation, alkane and cycloalkane solvents, such as pentane, hexane, heptane and cyclohexane; halogenated alkane solvents such as dichloromethane, chloroform, carbon tetrachloride, ethyl chloride, 1-dichloroethane, 1, 2-dichloroethane, 1-chloropropane, 2-chloropropane, 1-chlorobutane, 2-chlorobutane, 1-chloro-2-methylpropane and 1-chloropentane; ethers such as THF and diethyl ether; aromatic solvents such as benzene, xylene, toluene, mesitylene, chlorobenzene, and o-dichlorobenzene; halocarbon solvents, e.g.112, a first electrode; and mixtures of any combination thereof.

The solution polymerization temperature may be in the range of below ambient temperature, for example below 0 ℃ to the boiling point of the solvent used. Typically, the solution polymerization is conducted at a temperature in the range of about 10 ℃ to 200 ℃, in some other embodiments, the temperature may be in the range of about 10 ℃ to 150 ℃; or about 20 ℃ to 100 ℃.

The polymers formed according to the present invention generally exhibit a number average molecular weight (M) of at least about 3,000_n). In another embodiment, the polymers of the present invention have an M of at least about 5,000_n. In another embodiment, the polymers of the present invention have an M of at least about 10,000_n. In another embodiment, the polymers of the present invention have an M of at least about 20,000_n. In yet another embodiment, the polymers of the present invention have an M of at least about 50,000_n. In some other embodiments, the polymers of the present invention have an M of at least about 100,000_n. In another embodiment, the polymer of the present invention has an M of greater than 100,000_nAnd in some other embodiments, may be higher than 500,000. Number average molecular weight (M) of the Polymer_n) Can be determined by any known technique, for example, by Gel Permeation Chromatography (GPC) equipped with a suitable detector such as a differential refractometer calibrated with narrow distribution polystyrene standards and a calibration standard. As noted above, the polymers of the present invention typically exhibit a very low polydispersity index (PDI), which is the weight average molecular weight (M)_w) And number average molecular weight (M)_n) The ratio of. Generally, the polymers of the present invention have a PDI of less than 2. In some embodiments, the PDI is less than 1.5, less than 1.4, less than 1.3, less than 1.2, or less than 1.1. It should be noted, however, that in some embodiments, the PDI may be higher than 2, such as higher than 3.

Block copolymer

Advantageously, it has now also been found that various compounds of formula (I), (II) or (III) function effectively as catalysts for forming a range of block copolymers comprising more than one norbornene-type compound of formula (IV) as described herein. The block copolymers as described herein can also be prepared by any other catalyst known in the art. It has further been found that the block copolymers of the present invention provide unique advantages and are therefore useful in a variety of applications, including but not limited to forming film materials and a variety of other optical and electronic applications. Membranes formed from block copolymers are useful, for example, for separating organic matter from biomass or other organic waste materials.

Thus, there is provided a block copolymer of the general formula (VI):

(A)_m-b-(B)_n(VI)

wherein m and n are integers of at least 15, but in other embodiments m and n may range from 20 to 4000, or from 50 to 3000, or from 100 to 2000, and in other embodiments m and n may also be higher than 4000, depending on the intended use;

b represents the bond between the two blocks of homopolymers A and B;

wherein:

represents a position bonded to another repeating unit;

p is an integer of 0,1 or 2;

R₃、R₄、R₅and R₆Are identical or different and are each, independently of one another, selected from hydrogen, linear or branched (C)₁-C₁₆) Alkyl, hydroxyRadical (C)₁-C₁₆) Alkyl, perfluoro (C)₁-C₁₂) Alkyl, (C)₃-C₁₂) Cycloalkyl group, (C)₆-C₁₂) Bicycloalkyl, (C)₇-C₁₄) Tricycloalkyl group, (C)₆-C₁₀) Aryl group, (C)₆-C₁₀) Aryl radical (C)₁-C₃) Alkyl, perfluoro (C)₆-C₁₀) Aryl, perfluoro (C)₆-C₁₀) Aryl radical (C)₁-C₃) Alkyl, di (C)₁-C₂) Alkyl maleimide (C)₃-C₆) Alkyl, di (C)₁-C₂) Alkyl maleimide (C)₂-C₆) Alkoxy (C)₁-C₂) Alkyl, hydroxy, (C)₁-C₁₂) Alkoxy group, (C)₃-C₁₂) Cycloalkoxy, (C)₆-C₁₂) Bicyclic alkoxy group, (C)₇-C₁₄) Tricycloalkoxy, (C)₆-C₁₀) Aryloxy radical (C)₁-C₃) Alkyl, (C)₅-C₁₀) Heteroaryloxy (C)₁-C₃) Alkyl, (C)₆-C₁₀) Aryloxy group, (C)₅-C₁₀) Heteroaryloxy or (C)₁-C₆) Acyloxy, wherein each of the above substituents is optionally substituted with a group selected from halogen or hydroxy.

In one embodiment of the present invention, the block polymer of the present invention further comprises a third type of repeating unit represented by the general formula (VII):

(A)_m-b-(B)_n-b-(C)_o(VII)

wherein m, n and b are as defined above, and o is an integer of at least 15, but in other embodiments o may range from 20 to 4000 or, 50 to 3000, or 100 to 2000, and in other embodiments o may also be higher than 4000, depending on the intended use of the block polymer. C is the same or different from a or B and is independently selected from a repeating unit represented by formula (IVA) derived from a monomer of formula (IV) as defined herein. In other words, the block copolymer of the present invention may be present as a diblock or as a triblock. However, the multi-block copolymers of the present invention are formed by adding more than one other monomer of formula (IV), thereby enabling the formation of any number of additional blocks. For example, diblock polymers are typically formed by first polymerizing a first monomer of formula (IV) in the presence of a suitable catalyst, and then a second monomer, which is the same or a different monomer than the first monomer, can be added to the same polymerization reaction mixture to form the diblock copolymer. Generally, the polymerization is carried out in solution at a suitable polymerization temperature as described above. That is, the diblock copolymer may be formed using any solvent as described above in the presence of one or more suitable polymerization catalysts. The reaction temperature is generally about at ambient conditions, i.e., around room temperature. However, temperatures above ambient (super-ambient), i.e. about 25 ℃ to 150 ℃, or below ambient (sub-ambient), i.e. about 25 ℃ to 0 ℃, or even lower temperatures may also be used. The polymerization can also be carried out neat, i.e.bulk polymerization without solvent. Triblock polymers are also formed by polymerizing a second monomer followed by the addition of a third monomer. The multi-block polymer is formed by sequential addition of additional monomers. As described above, the block copolymer can be formed by using the same monomer or different monomers to form different blocks with different molar ratios of the monomers as needed.

Accordingly, in one embodiment a diblock copolymer is provided wherein the block molar ratio of A: B is from 1:1 to 1: 4. In another embodiment, the block molar ratio of A: B is from 1:1 to 1: 2. In yet another embodiment, the block molar ratio of A to B is 1: 1. In yet another embodiment, the block polymer is a triblock polymer wherein the block molar ratio of a: B: C is from 1:1:1 to 1:4:1 to 1:1: 4. In further embodiments, the block molar ratio of a: B: C is 1:1: 1; and in another embodiment, the block molar ratio of A: B: C is 1:2: 1. In this regard, the size of the blocks can also be controlled by the weight fraction of each block. That is, in the diblock polymer A-B-B, the weight fraction of monomer A may be in the range of 0.1 to 1,is represented by W_A. Various triblock or other multiblock polymers can likewise be prepared using different weight fractions of the respective monomers used.

In general, any of the monomers encompassed by formula (IV) can be used to form the block polymers of the present invention. For example, non-limiting examples of a repeating units may be derived from monomers selected from the group consisting of:

5-butylbicyclo [2.2.1] hept-2-ene (BuNB);

5-hexylbicyclo [2.2.1] hept-2-ene (HexNB);

5-octylbicyclo [2.2.1] hept-2-ene (OctNB);

5-Perfluoroethylbicyclo [2.2.1]Hept-2-ene (C)₂F₅NB)；

5-n-perfluorobutylbicyclo [2.2.1]Hept-2-ene (C)₄F₉NB)；

5-perfluorohexylbicyclo [ 2.2.1%]Hept-2-ene (C)₆F₁₃NB)；

Norbornenyl-2-trifluoromethyl-3, 3, 3-trifluoropropan-2-ol (HFANB);

5-phenethylbicyclo [2.2.1] hept-2-ene (PENB);

5-benzylbicyclo [2.2.1] hept-2-ene (BnNB); and

2- (bicyclo [2.2.1] hept-5-en-2-yl) bicyclo [2.2.1] heptane (NBANB).

In another embodiment, non-limiting examples of repeating unit B are derived from monomers selected from the group consisting of:

5-butylbicyclo [2.2.1] hept-2-ene (BuNB);

5-hexylbicyclo [2.2.1] hept-2-ene (HexNB);

5-octylbicyclo [2.2.1] hept-2-ene (OctNB);

5-Perfluoroethylbicyclo [2.2.1]Hept-2-ene (C)₂F₅NB)；

5-n-perfluorobutylbicyclo [2.2.1]Hept-2-ene (C)₄F₉NB)；

5-perfluorohexylbicyclo [ 2.2.1%]Hept-2-ene (C)₆F₁₃NB)；

Norbornenyl-2-trifluoromethyl-3, 3, 3-trifluoropropan-2-ol (HFANB);

5-phenethylbicyclo [2.2.1] hept-2-ene (PENB);

5-benzylbicyclo [2.2.1] hept-2-ene (BnNB); and

2- (bicyclo [2.2.1] hept-5-en-2-yl) bicyclo [2.2.1] heptane (NBANB).

Finally, non-limiting examples of repeating unit C are derived from monomers selected from the group consisting of:

5-butylbicyclo [2.2.1] hept-2-ene (BuNB);

5-hexylbicyclo [2.2.1] hept-2-ene (HexNB);

5-octylbicyclo [2.2.1] hept-2-ene (OctNB);

5-Perfluoroethylbicyclo [2.2.1]Hept-2-ene (C)₂F₅NB)；

5-n-perfluorobutylbicyclo [2.2.1]Hept-2-ene (C)₄F₉NB)；

5-perfluorohexylbicyclo [ 2.2.1%]Hept-2-ene (C)₆F₁₃NB)；

Norbornenyl-2-trifluoromethyl-3, 3, 3-trifluoropropan-2-ol (HFANB);

5-phenethylbicyclo [2.2.1] hept-2-ene (PENB);

5-benzylbicyclo [2.2.1] hept-2-ene (BnNB); and

2- (bicyclo [2.2.1] hept-5-en-2-yl) bicyclo [2.2.1] heptane (NBANB).

In another embodiment, representative examples of repeating unit a are derived from monomers selected from the group consisting of:

5-butylbicyclo [2.2.1] hept-2-ene (BuNB);

5-hexylbicyclo [2.2.1] hept-2-ene (HexNB);

5-n-perfluorobutylbicyclo [2.2.1]Hept-2-ene (C)₄F₉NB)；

Norbornenyl-2-trifluoromethyl-3, 3, 3-trifluoropropan-2-ol (HFANB);

1- (4- (bicyclo [2.2.1] hept-5-en-2-yl) butyl) -3, 4-dimethyl-1H-pyrrole-2, 5-dione (BuDMMINB); and

2- (bicyclo [2.2.1] hept-5-en-2-yl) bicyclo [2.2.1] heptane (NBANB).

In yet another embodiment, representative examples of repeat units B are derived from monomers selected from the group consisting of:

5-butylbicyclo [2.2.1] hept-2-ene (BuNB);

5-hexylbicyclo [2.2.1] hept-2-ene (HexNB);

5-n-perfluorobutylbicyclo [2.2.1]Hept-2-ene (C)₄F₉NB)；

Norbornenyl-2-trifluoromethyl-3, 3, 3-trifluoropropan-2-ol (HFANB);

2- (bicyclo [2.2.1] hept-5-en-2-yl) bicyclo [2.2.1] heptane (NBANB).

In yet another embodiment, representative examples of repeating unit C are derived from monomers selected from the group consisting of:

5-butylbicyclo [2.2.1] hept-2-ene (BuNB);

5-hexylbicyclo [2.2.1] hept-2-ene (HexNB);

5-n-perfluorobutylbicyclo [2.2.1]Hept-2-ene (C)₄F₉NB)；

Norbornenyl-2-trifluoromethyl-3, 3, 3-trifluoropropan-2-ol (HFANB);

2- (bicyclo [2.2.1] hept-5-en-2-yl) bicyclo [2.2.1] heptane (NBANB).

Non-limiting examples of block copolymers of the present invention are selected from the following:

block copolymers derived from 5-hexylbicyclo [2.2.1] hept-2-ene and norbornenyl-2-trifluoromethyl-3, 3, 3-trifluoropropan-2-ol (HexNB-b-HFANB);

block copolymers derived from 5-butylbicyclo [2.2.1] hept-2-ene and norbornenyl-2-trifluoromethyl-3, 3, 3-trifluoropropan-2-ol (BuNB-b-HFANB)

Derived from 5-benzylbicyclo [2.2.1]Hept-2-ene and 5-n-perfluorobutylbicyclo [2.2.1]Block copolymer of hept-2-ene (BnNB-b-C)₄F₉NB)；

Derived from 5-n-perfluorobutylbicyclo [2.2.1]Hept-2-ene and 1- (4- (bicyclo [2.2.1]]Block copolymer of hept-5-en-2-yl) butyl) -3, 4-dimethyl-1H-pyrrole-2, 5-dione (C)₄F₉NB-b-BuDMMINB)；

A block copolymer derived from norbornenyl-2-trifluoromethyl-3, 3, 3-trifluoropropan-2-ol and 2- (bicyclo [2.2.1] hept-5-en-2-yl) bicyclo [2.2.1] heptane (HFANB-b-NBANB); and

block copolymers derived from 5-hexylbicyclo [2.2.1] hept-2-ene and 2- (bicyclo [2.2.1] hept-5-en-2-yl) bicyclo [2.2.1] heptane (HexNB-b-NBANB).

In one embodiment, the block polymer of the present invention is selected from the following:

a block polymer derived from 5-butylbicyclo [2.2.1] hept-2-ene, norbornenyl-2-trifluoromethyl-3, 3, 3-trifluoropropan-2-ol and 5-butylbicyclo [2.2.1] hept-2-ene (BuNB-b-HFANB-b-BuNB);

block copolymers derived from 5-n-butylbicyclo [2.2.1] hept-2-ene, 5-benzylbicyclo [2.2.1] hept-2-ene and 2- (bicyclo [2.2.1] hept-5-en-2-yl) bicyclo [2.2.1] heptane (BuNB-b-bnb-NBANB); and

block polymers derived from norbornenyl-2-trifluoromethyl-3, 3, 3-trifluoropropan-2-ol, 5-butylbicyclo [2.2.1] hept-2-ene and norbornenyl-2-trifluoromethyl-3, 3, 3-trifluoropropan-2-ol (HFANB-b-BuNB-b-HFANB).

The block polymers of the present invention can be prepared by any procedure known in the art. Generally, the polymerization is carried out in solution and in the presence of a suitable metal catalyst. In some embodiments of the present invention, it has been advantageously found that metal catalysts in combination with suitable compounds that can function as co-catalysts (co-catalysts), initiators or main initiators (pro-initiators) or activators provide a method of preparing the block polymers of the present invention. However, as noted above, any other method known in the art may also be used.

Accordingly, there is provided a process for the preparation of a block copolymer of formula (VI) as described herein, comprising the steps of: any of the first monomers a of formula (IV) as described herein is reacted with a palladium compound to form a first polymer block. Then, a second monomer B of formula (IV) different from the first monomer a of formula (IV) is added to the polymerization reaction mixture to form a block copolymer containing diblock copolymers having different molar ratios of monomeric repeat units a and B.

In another embodiment, there is also provided a process for preparing a triblock polymer comprising the step of reacting a third monomer C of formula (IV) to form a block polymer of formula (VII):

(A)_m-b-(B)_n-b-(C)_o(VII)

wherein m, n, o, B, A, B and C are as defined herein. It should be noted that monomer repeat unit C may be the same or different from a or B and is independently selected from repeat units represented by formula (IVA) derived from monomers of formula (IV) as defined herein. Moreover, as mentioned above, the block polymer of formula (VII) is therefore referred to as a triblock polymer and may have various molar ratios of the recurring units of formula A, B or C as described above.

Palladium compounds that can be used in the process of the invention include all compounds of the general formulae (I), (II) and (III) as described herein.

Advantageously, it has now been found that various other palladium compounds can also be used in the process of the present invention. Such palladium compounds suitable for use in forming the block polymers of the present invention are represented by the general formula:

(allyl) Pd (P (Q)₃))(L₁) Or (methyl) Pd (P (Q)₃))(L₁)

Wherein Q may be the same or different and is independently selected from isopropyl, tert-butyl, neopentyl and cyclohexyl; and L is₁Selected from the group consisting of halogen, trifluoroacetate and trifluoromethanesulfonate (triflate). Non-limiting examples of such palladium compounds include the following:

allylpalladium (triisopropylphosphine) chloride [ Pd (allyl) (triisopropylphosphine) Cl ];

allylpalladium (tri-tert-butylphosphine) chloride [ Pd (allyl) (tri-tert-butylphosphine) Cl ];

allylpalladium (diisopropyl-tert-butylphosphine) chloride [ Pd (allyl) (diisopropyl-tert-butylphosphine) Cl ];

allylpalladium (isopropyl-di-t-butylphosphine) chloride [ Pd (allyl) (isopropyl-di-t-butylphosphine) Cl ];

allylpalladium (di-tert-butyl-cyclohexylphosphine) chloride [ Pd (allyl) (di-tert-butyl-cyclohexylphosphine) Cl ];

allylpalladium (di-tert-butyl-neopentylphosphine) chloride [ Pd (allyl) (di-tert-butyl-neopentylphosphine) Cl ];

(allyl) palladium (tricyclohexylphosphine) trifluoromethanesulfonate [ Pd (allyl) (tricyclohexylphosphine) trifluoromethanesulfonate ];

(allyl) palladium (triisopropylphosphine) trifluoromethanesulfonate [ Pd (allyl) (triisopropylphosphine) trifluoromethanesulfonate ];

(allyl) palladium (tricyclohexylphosphine) trifluoroacetate [ Pd (allyl) (tricyclohexylphosphine) trifluoroacetate ];

(allyl) palladium (triisopropylphosphine) trifluoroethyl ester [ Pd (allyl) (triisopropylphosphine) trifluoroacetate ];

methyl palladium (triisopropylphosphine) chloride [ Pd (methyl) (triisopropylphosphine) Cl ];

methyl palladium (tri-tert-butylphosphine) chloride [ Pd (methyl) (tri-tert-butylphosphine) Cl ];

methyl palladium (diisopropyl-tert-butylphosphine) chloride [ Pd (methyl) (diisopropyl-tert-butylphosphine) Cl ];

methyl palladium (isopropyl-di-t-butylphosphine) chloride [ Pd (methyl) (isopropyl-di-t-butylphosphine) Cl ];

methyl palladium (di-tert-butyl-cyclohexylphosphine) chloride [ Pd (methyl) (di-tert-butyl-cyclohexylphosphine) Cl ];

methyl Palladium (Tricyclohexylphosphine) chloride [ Pd (methyl) (Tricyclohexylphosphine) Cl]Also abbreviated as [ (Me-Pd-PCy)₃)Cl]Wherein Cy is cyclohexyl (C)₆H₁₁)；

Methyl palladium (dicyclohexyl-t-butylphosphine) chloride [ Pd (methyl) (dicyclohexyl-t-butylphosphine) Cl ];

methyl palladium (cyclohexyl-di (tert-butyl) phosphine) chloride [ Pd (methyl) (cyclohexyl-di (tert-butyl) phosphine) Cl ]; and so on.

Another class of palladium compounds can also be used to form the block polymers of the present invention and can be represented by the general formula:

wherein Rx is substituted (C)₈-C₁₆) Aryl, e.g. 2, 5-diisopropylphenyl, mesityl, etc., L₁As defined above. Non-limiting examples of such palladium compounds include the following:

allyl (palladium) (1, 3-bis (2, 6-diisopropylphenyl) -2, 3-dihydro-1H-imidazole) Cl;

allyl (palladium) (1, 3-bis (2, 6-diisopropylphenyl) imidazolidine) Cl; and

allyl (palladium) (1, 3-ditrimethylphenyl-2, 3-dihydro-1H-imidazole) Cl.

Several of the above palladium compounds are commercially available or known in the literature and can be prepared using any procedure known in the literature.

As also noted above, the palladium compounds described above are typically used in combination with another compound that functions as a co-catalyst, initiator, primary initiator, or activator. For example, any compound of formula (V) as described above can be used for this purpose. In one embodiment, a non-limiting example of such an activator compound includes lithium tetrakis (pentafluorophenyl) boronate ethyl ether (LiFeABA- [ Li (OEt)₂)_2.5][B(C₆F₅)₄]) And N, N-dimethylanilinium tetrakis (pentafluorophenyl) -borate (DANBABA), and the like.

Thus, it should be noted that the palladium-containing catalyst used to facilitate the manufacture of the block copolymers of the present invention can be prepared as a preformed single component catalyst or mixed in situ by mixing the palladium-containing procatalyst with the activator (or cocatalyst, initiator or primary initiator as described above) in the presence of the monomers to be polymerized.

Thus, a preformed catalyst can be prepared by mixing catalyst precursors such as procatalyst and activator (or cocatalyst, initiator or main initiator) in a suitable solvent, allowing the reaction to proceed under suitable temperature conditions, and isolating the reaction product, i.e., the preformed catalyst product. By procatalyst is meant a palladium-containing compound that is converted to an active catalyst by reaction with a cocatalyst, activator, initiator or main initiator compound. Further description and synthesis of representative procatalysts and activator compounds can be reviewed in U.S. Pat. No. 6,455,650, the relevant portions of which are incorporated herein by reference.

The block copolymers formed according to the present invention typically exhibit a number average molecular weight (M) of at least about 2,000 for each block formed_n). M of each block_nCan be tailored to the desired properties (property) and based on the end use of the block copolymer. Thus, in another embodiment, one of the blocks of the block copolymer of the present invention has an M of at least about 20,000_n. In yet another embodiment, one of the blocks of the block copolymer of the present invention has an M of at least about 50,000_n. In some other embodiments, one of the blocks of the block copolymers of the present invention has an M of at least about 100,000_n. In another embodiment, one of the blocks of the diblock copolymer has an M of at least 5,000_nAnd the other block has an M of at least 20,000_n. In some other embodiments, any block of the block polymers of the present invention has an M greater than 100,000, greater than 200,000, or greater than 500,000_n. As described above, the number average molecular weight (M) of the block copolymer_n) Can be determined by any known technique, for example, by Gel Permeation Chromatography (GPC) equipped with a suitable detector such as a differential Refraction (RI) detector or a multi-angle laser Light Scattering (LS) detector calibrated with narrow distribution polystyrene standards and a calibration standard. It is also noted that each of the block copolymers of the present invention typically exhibit a very low polydispersity index (PDI ═ M)_w/M_n). In general, the PDI of each block of the block copolymer of the present invention is less than 2. In some embodiments, the PDI is less than 1.5, less than 1.4, less than 1.3, less than 1.2, or less than 1.1. It should be noted, however, that in some embodiments, the PDI may be higher than 2, such as higher than 3.

In one embodiment, various diblock polymers can be formed by performing the process of the present invention. Non-limiting examples of such diblock polymers formed by the process of the present invention may be enumerated as follows:

a block copolymer derived from 5-butylbicyclo [2.2.1] hept-2-ene and norbornenyl-2-trifluoromethyl-3, 3, 3-trifluoropropan-2-ol (BuNB-b-HFANB);

derived from 5-butylbicyclo [2.2.1]Hept-2-ene and 1- (4- (bicyclo [2.2.1]]Block copolymer of hept-5-en-2-yl) butyl) -3, 4-dimethyl-1H-pyrrole-2, 5-dione (C)₄F₉NB-b-BuDMMINB)；

A block copolymer derived from norbornenyl-2-trifluoromethyl-3, 3, 3-trifluoropropan-2-ol and 2- (bicyclo [2.2.1] hept-5-en-2-yl) bicyclo [2.2.1] heptane (HFANB-b-NBANB);

a block copolymer derived from 5-hexylbicyclo [2.2.1] hept-2-ene and 2- (bicyclo [2.2.1] hept-5-en-2-yl) bicyclo [2.2.1] heptane (HexNB-b-NBANB); and

derived from 5-benzylbicyclo [2.2.1]Hept-2-ene and 5-n-perfluorobutylbicyclo [2.2.1]Block copolymer of hept-2-ene (BnNB-b-C)₄F₉NB)。

In another embodiment, various triblock polymers can be formed by practicing the process of the present invention. Non-limiting examples of such triblock polymers formed by the process of the present invention may be enumerated as follows:

block polymers derived from 5-butylbicyclo [2.2.1] hept-2-ene, 5-benzylbicyclo [2.2.1] hept-2-ene, and 2- (bicyclo [2.2.1] hept-5-en-2-yl) bicyclo [2.2.1] heptane (BuNB-bnb-b-NBANB); and

Pervaporation membrane applications

As noted above, the block polymers of the present invention exhibit several unique properties and are therefore useful in several different applications, including as membrane materials for separation, electronic and/or optoelectronic applications.

With the increasing interest in biofuels such as ethanol, butanol, etc., there is an increasing interest in developing environmentally friendly separation processes that economically separate organic materials from water. There is also an increasing demand for purification of water streams contaminated by industrial processes and for separation of organic products from aqueous fermentation broths designed to form various organic solvents by biological processes, such as phenol from a broth from a fermentation reactor or any other biologically formed broth, such as an algal broth. In addition, concerns over separating value added products from biological and industrial waste (including any biomass-derived waste) are also increasing. While it is well known to perform such separations using processes such as distillation and gas stripping, these conventional processes, particularly distillation, are often characterized by high capital and energy costs and are therefore often problematic, e.g., it is known that over 60% of the heat generation of biofuels such as butanol is wasted if conventional separation methods are used.

More importantly, organic products, especially organic solvents prepared by the above mentioned biological processes or extracted from organic waste materials, are gaining increasing industrial application. For example, about half of the n-butanol and its esters (e.g., n-butyl acetate) produced are used as solvents in the coatings industry, including as solvents for dyes such as printing inks. Other well known applications of dicarboxylic acids, phthalic anhydride and butyl acrylate include use as additives in plasticizers, rubber additives, dispersants, semi-synthetic lubricants, polishes and cleaners, such as floor cleaners and detergents, and as hydraulic fluids. Butanol and its esters are also used as solvents, including as extractants in the production of pharmaceuticals and natural products such as antibiotics, hormones, vitamins, alkaloids, and camphor. Various other uses of butanol and its esters and ethers thereof include in various other uses as solubilizers in the textile industry, for example as additives in spinning baths or as carriers for pigmented plastics, as additives in thawing solutions, as additives in gasolines for spark-ignition engines, as raw materials for the production of glycol ethers.

Therefore, an alternative process for performing such separation, known as pervaporation, has received considerable attention as a solution to the above-mentioned "waste". In a pervaporation process, a feed liquid (typically a mixture of two or more liquids, e.g. a fermentation broth) is contacted with a membrane film (membrane film) having properties that allow one component of the feed liquid to preferentially permeate the membrane. The permeate is then removed as a vapor from the downstream side of the membrane for the membrane, typically by applying a vacuum to the permeate side of the membrane. Thus, pervaporation has proven to be an alternative in the separation of liquid mixtures with similar volatility, such as azeotropic mixtures, which are difficult to separate by conventional methods. While polymers such as polyimides, polyether-polyamides, polydimethylsiloxanes, and the like have been used with some success in forming pervaporation membranes, none of the essential characteristics required of commercially viable membrane materials to date have been demonstrated. For example, pervaporation membranes such as PERVAP 1060 (made from poly (dimethylsiloxane), PDMS), PERVAP 1070 (made from zeolites, ZSM-5, filled PDMS) (Sulzer Chemtech Membrane Systems A.G., Nonoxinxing, Germany) and PEBA (block copolymer polyether-polyamide, GKSS-Forschungszen trum Geesthacht GmbH, Gaster Hahette, Germany) can be used to separate various low volatility organics from aqueous mixtures. However, there is still a need to develop membranes with better performance that can provide efficient separation of organics from aqueous mixtures at lower capital and reduced operating costs.

Embodiments in accordance with the present invention are disclosed herein, which encompass embodiments of monomers, polymer compositions, embodiments of membranes and membrane composites, and embodiments formed therefrom, that advantageously provide heretofore unachievable pervaporation membranes for separating organic matter from various mixtures, including fermentation broths, industrial wastes, and others.

Hereinafter, exemplary embodiments of the present invention will be described. Various modifications, adaptations, or variations of such exemplary embodiments are disclosed and will be apparent to those skilled in the art. It is to be understood that all such modifications, adaptations, or variations that rely upon the teachings of the present invention and which have advanced the art are deemed to be within the scope and spirit of the present invention. For example, although the exemplary embodiments described herein generally relate to separating butanol and/or phenol from an aqueous feed, this is not meant to limit the invention to only embodiments for separating butanol and/or phenol. Thus, some embodiments of the invention include the separation of any organic material from an aqueous (aquous based) feed solution, wherein a suitable pervaporation membrane can be formed from the block copolymer of the invention. For example, some embodiments include separating hydrophobic organic materials from hydrophilic feed liquids using suitable pervaporation membranes disclosed herein. Yet other embodiments of the present invention include the separation of non-polar and polar organic materials. Examples of such separations include, but are not limited to, separation of aromatics such as benzene or toluene from water soluble alcohols such as methanol or ethanol, and separation of non-polar hydrocarbyl-based materials such as hexane and heptane from polar heterocarbyl-based materials. Various other organics also include volatile organic solvents such as Tetrahydrofuran (THF), Ethyl Acetate (EA), acetone, Methyl Ethyl Ketone (MEK), methyl isobutyl ketone (MIBK), and the like, all of which can be present in fermentation broths or industrial wastes.

The expected behavior (extruded behavior) of pervaporation membranes made from hydrophobic polymers becomes plasticized and/or swollen with increasing organic concentration. Plasticized and/or swollen membranes generally result in an undesirable increase in the permeability of both organic and water, which is generally relatively greater than the permeability of organic, thus resulting in a reduction in the separation factor. Unexpectedly, pervaporation membranes made from the block polymers of the present invention, which are generally hydrophobic, exhibit behavior that is contrary to what is normally expected. Pervaporation membranes as described herein have a separation factor that increases dramatically with increasing feed concentration (i.e., increasing organic concentration of the feed stream).

Typically in pervaporation, a multi-component liquid stream passes through a pervaporation membrane that preferentially permeates more than one component. As the multi-component liquid stream flows across the surface of the pervaporation membrane, the preferentially permeated component passes through the pervaporation membrane and is removed as a permeate vapor. Transport across the pervaporation membrane is induced by maintaining the vapor pressure on the permeate side of the pervaporation membrane below that of the multi-component liquid stream. For example, the vapor pressure differential can be achieved by maintaining the multi-component liquid stream at a temperature higher than the permeate stream. In this example, the latent heat of vaporization of the permeate component is supplied to the multi-component liquid stream to maintain the feed temperature and to allow the pervaporation process to continue. Alternatively, the vapor pressure differential is typically achieved by operating at sub-atmospheric pressure on the permeate side of the pervaporation module. The partial vacuum on the permeate side of the polynorbornene pervaporation membrane can be achieved by either: by means of a pressure drop due to cooling and condensation taking place in the condenser unit, and/or by using a vacuum pump. An optional sweep gas (sweep gas) on the permeate side can facilitate the pervaporation process by reducing the concentration of the permeate component. The vapor pressure of the feed liquid can be arbitrarily increased by heating the fermentation broth. Polynorbornene pervaporation membranes have been disclosed in U.S. patent No. 8,215,496, the relevant disclosure of which is incorporated herein by reference, and where such membranes have been successful to some extent, the block copolymer pervaporation membranes disclosed and claimed herein provide significant improvements over previously disclosed membranes, as will be apparent from the following disclosure.

Accordingly, a pervaporation membrane is provided comprising a block polymer of formula (VI) or (VII) as disclosed above. That is, any diblock or triblock polymer of the present invention can be used to form a pervaporation membrane of the present invention. In one embodiment of the present invention, the pervaporation membrane of the present invention comprises the diblock copolymer of formula (VI) of the present invention. In another embodiment, the pervaporation membrane according to the invention comprises a triblock polymer according to formula (VII) according to the invention.

In another embodiment, the pervaporation membrane of the present invention is made of a diblock copolymer selected from:

In another embodiment, the pervaporation membrane of the present invention is made of a triblock polymer selected from the group consisting of:

a block copolymer derived from 5-butylbicyclo [2.2.1] hept-2-ene, norbornenyl-2-trifluoromethyl-3, 3, 3-trifluoropropan-2-ol and 5-butylbicyclo [2.2.1] hept-2-ene (BuNB-b-HFANB-b-BuNB); and

block copolymers derived from norbornenyl-2-trifluoromethyl-3, 3, 3-trifluoropropan-2-ol, 5-butylbicyclo [2.2.1] hept-2-ene and norbornenyl-2-trifluoromethyl-3, 3, 3-trifluoropropan-2-ol (HFANB-b-BuNB-b-HFANB).

Pervaporation membranes of the present invention can be readily formed by any technique known in the art. For example, a suitable diblock or triblock polymer of formula (VI) or (VII) of the present invention comprising the desired repeat units of the polycycloalkyl norbornene-type monomer of formula (IVA) is typically dissolved in a suitable organic solvent to form a solution. The polymer solution is then typically filtered through a suitable filter to remove any residual contaminants. After filtration, trapped gas (trapped gas) can be removed. The polymer solution can then be formed into a film by any method known in the art. For example, a polymer solution is poured onto a substrate and stretched to form a film. The film is then dried and removed from the substrate for use (if necessary). The film formed in this manner is generally considered to be a single thickness film, and specific examples of this embodiment are described further below, and in some embodiments, the film is cast as a double thickness film by forming a second film on a first formed film. In some other embodiments, the polymer solution is applied to the polymer web to form a reinforced film, i.e., to the sheet to form a supported film, or to the substrate sheet to form an unsupported film. In other embodiments, the polymer solution can be suitably cast into a tubular composite or hollow fiber. Accordingly, in one embodiment, the pervaporation membrane of the present invention is in the form of a tubular composite, a hollow fiber, a flat sheet of dense membrane, or a thin film composite.

The pervaporation membrane of the present invention may be in any suitable form to achieve separation of the desired substance, e.g. butanol, from the fermentation broth. Examples include spiral wound (spiral wound) modules, fibre membranes including hollow fibre membranes, tubular membranes and flat sheet membranes such as plate and frame structures, supported or unsupported dense membranes or thin film composites.

When the block polymer pervaporation membrane is in the form of an unsupported dense membrane, the thickness of the dense membrane is from about 1 micron to about 500 microns. In another embodiment, the dense film has a thickness of about 5 microns to about 100 microns.

When the pervaporation membrane is in the form of a thin film composite, such membrane may be thinner than the unsupported membrane, e.g., as thin as about 0.1 microns. In addition, the film contains at least one layer of a block polymer and at least one layer of a non-block polymer component. Such composites may contain a multi-layer block polymer film and a multi-layer non-block polymer component. Examples of non-block polymeric components include various other polymers and inorganic materials. Examples of such polymers include polyethylene, which includesPolypropylene, polyester, polyimide, polycarbonate, polytetrafluoroethylene, poly (vinylidene fluoride) (PVDF), poly (methyl methacrylate) (PMMA), Polyacrylonitrile (PAN), mixed copolymers and terpolymers thereof, and the like. Examples of the inorganic substance include zeolite, glass frit (glass frit), carbon powder, metal screens (metal screens), metal gauze (metal screen), metal glass frit (metal frit), and the like.

A schematic of the pervaporation process is shown in fig. 1. As shown, a feed containing a plurality of species is loaded into pervaporation module 100 and into liquid chamber 102 on the feed side thereof. The vapor chamber 104 on the permeate side is separated from the liquid chamber 102 by a pervaporation membrane 106. The vapor phase is extracted from the feed liquid through a pervaporation membrane 106 selective for a given permeate and permeate vapor enriched in the given permeate relative to the feed liquid is removed from the pervaporation module 100, typically by condensation thereof.

Using a block polymer pervaporation membrane, pervaporation can be used to treat a fermentation broth containing, for example, biobutanol, ethanol, or phenol and one or more other miscible components. More specifically, fermentation broth may be added to liquid chamber 102, whereby a vacuum or gas purge is applied to vapor chamber 104 and placed in contact with one side of pervaporation membrane 106. The fermentation broth may be heated or unheated. The components of the fermentation broth adsorb in and/or on the pervaporation membrane 106, permeate and evaporate into the vapor phase. The resulting vapor or permeate, such as butanol (or phenol), is then condensed and collected. Even very low concentrations of components in the feed can be highly enriched in the permeate due to the different affinities of the different species in the broth for the pervaporation membrane and the different diffusion rates through the membrane. Accordingly, in one embodiment of the present invention, a pervaporation membrane is provided that is capable of having preferential permeability to volatile organic compounds over water. The permeability of the volatile organic compounds across the pervaporation membrane of the present invention generally increases as the organic concentration of the feed stream increases. In another embodiment, such volatile organics include, without limitation, butanol, phenol, and the like.

Fig. 2 depicts an exemplary pervaporation system 200 that can be used to separate butanol or other desired substances from a crude fermentation broth (or aqueous industrial waste or other waste containing biomass waste) containing valuable organic compounds such as biobutanol or phenol. Crude fermentation broth (or other waste material including industrial and/or biomass) from feed tank 205 is pumped via pump 215 through heater 220 as feed stream 210 to raise its temperature. The fermentation broth is then loaded under pressure into pervaporation module 225 comprising a pervaporation membrane. A permeate vapor 230 containing butanol (or phenol) is obtained from pervaporation module 225 by applying a vacuum (using vacuum pump 245), wherein the butanol vapor (or phenol vapor) is condensed in condenser 235 and collected in collector 240. Residual fermentation or retentate stream 250 that cannot pass through the polynorbornene pervaporation membrane can be discharged 255 from system 200 or directed to recycle stream 260 and returned to feed tank 205.

Complementary methods to perfect the pervaporation process include removing solids from the fermentation broth by centrifugation, filtration, decantation, fractional condensation (dephlegmation), etc.; adsorption, distillation, liquid-liquid extraction or the like is used to increase the butanol concentration in the permeate.

Butanol from biomass is often referred to as biobutanol. Biobutanol can be produced by fermenting biomass using an acetone-butanol-ethanol fermentation (a.b.e.) process. See, e.g., S-Y Li, et al, Biotechnol. prog.2011, vol.27(1), 111-120. The process uses Clostridium bacteria, such as Clostridium acetobutylicum (Clostridium), but may also be used including Saccharomyces cerevisiae (Saccharomyces cerevisiae), Zymomonas mobilis (Zymomonas mobilis), Clostridium thermohydrosulfuricum (Clostridium thermohydrosulfuricum), Escherichia coli (Escherichia coli), Candida pseudotropical (Candida pseudotropicalis) and Clostridium beijerinckii (Clostridium beijerinckii). Biobutanol can also be produced from cellulosic material using transgenic yeast for biobutanol production. The crude fermentation broth containing biobutanol may advantageously be treated by a pervaporation membrane as shown in fig. 1 and/or a pervaporation system as shown in fig. 2 to provide butanol concentrated compared to the concentration in the crude broth. It should also be noted that the pervaporation membranes of the present invention can also be used to separate various alcohols other than butanol, including ethanol and phenol, from the respective fermentation broths or industrial or biomass wastes.

The fermentation broth typically contains various carbon substrates. In addition to the carbon source, the fermentation broth may contain suitable minerals, salts, cofactors, buffers and other components of the enzymatic pathway known to those skilled in the art to be suitable for growth of the culture and necessary for promoting butanol production. Examples of commercially available fermentation broths include Luria Bertani (LB) broth, Sabouraud Dextrose (SD) broth, or Yeast Medium (YM) broth. Any of these known fermentation broths can be used in the present invention to separate volatile organics from such broths.

Likewise, it should be noted that various other organic products are selectively formed from the fermentation process. For example, phenol, commonly referred to as "green phenol", can be formed from suitable waste materials, including biological or industrial waste materials, and fermentation is accomplished by using suitable biological organisms to selectively form phenol. Phenol has been reported to be selectively produced by recombinant strains of the solvent-tolerant bacterium Pseudomonas putida S12, see, e.g., L.Heerema, et al.Desalination,200(2006), pp 485-487. Various other yeast strains have also been reported to also produce phenol, all of which use Saccharomyces bacteria, such as Saccharomyces cerevisiae (Saccharomyces cerevisiae) r.f. bayanus, EP 171 Lalvin; yeast (Saccharomyces bayanus), Ever; oval yeast (Saccharomyces cerevisiae), Ceppo20 Castelli; oval yeast (Saccharomyces oviformis), Ceppo 838 Castelli; saccharomyces cerevisiae (Saccharomyces cerevisiae) r.f. Saccharomyces cerevisiae, K1 Lalvin; and Saccharomyces cerevisiae (Saccharomyces cerevisiae), D254 Lalvin. These organisms can produce varying amounts of phenolics from synthetic and/or natural organic sources, where the primary carbon source is glucose. See M.Giaccio, J.Commodity Science (1999),38(4), 189-. Generally, as used herein, "green phenol" generally refers to phenol produced using a fermentation broth, which contains from about 0.1% to about 6% phenol. In other embodiments, the fermentation broth contains from about 0.5% to about 3% phenol.

As used herein, "butanol" generally refers to n-butanol and its isomers. In some embodiments according to the invention, the fermentation broth comprises from about 0.1% to about 10% butanol. In other embodiments, the fermentation broth contains from about 0.5% to about 6% butanol. In some other embodiments, the fermentation broth contains from about 1% to about 3% butanol. In general, the pervaporation membranes described herein are effective in separating volatile organics, such as butanol, ethanol, or phenol, from fermentation broths containing relatively low to high levels of volatile organics, and in some embodiments, fermentation broths containing at least about 1% volatile organics.

It should also be noted that certain "green phenol" feedstocks can also be produced using phenolic resins such as novolac resins and the like. Such feed streams may also be used in the pervaporation process of the present invention where phenol can be separated and/or enriched from the waste stream. In addition, various such phenol streams also contain certain inorganic and organic salts as impurities. As a result, it is difficult to remove such inorganic salts from the feed stream and to obtain phenol in a purely enriched form. Surprisingly, however, it has now been found that the pervaporation membrane of the present invention is capable of separating such inorganic and organic salts. Representative examples of inorganic salts include, without limitation, salts of lithium, sodium, potassium, magnesium, calcium, barium, and the like. Any counter anion with salts of these metals can be used in the present invention. Such non-limiting examples of anions include phosphates, sulfates, acetates, benzoates, and the like. However, other anions such as methane sulfonate (methanesulfonate), trifluoromethane sulfonate (trifluoromethanesulfonate), p-toluenesulfonate (toluenesulfonate) and halides such as fluoride, chloride, bromide and iodide can also be separated from the feed stream.

In one embodiment, a process is provided for separating an organic product, such as butanol, ethanol, phenol, THF, ethyl acetate, acetone, toluene, MEK, MIBK, or the like, from a feedstock selected from a fermentation broth or industrial waste containing the organic product. In some embodiments, the fermentation broth is charged to a pervaporation module comprising a pervaporation membrane formed from any of the block polymers described herein. The permeate vapor containing the organic product is then collected from the pervaporation module. In this process, it may be advantageous to heat the crude fermentation broth to a temperature that promotes passage of the organic product through the pervaporation membrane of the present invention. In an embodiment, the crude fermentation broth feed is heated to a temperature of about 30 ℃ to about 110 ℃. In another embodiment, the crude fermentation broth feed is heated to a temperature of about 40 ℃ to about 90 ℃. In yet another embodiment, the crude fermentation broth feed is heated to a temperature of about 50 ℃ to about 70 ℃. It should be noted that the desired temperature may depend on the type of organic matter being separated. For example, relatively low temperatures are used in the separation of butanol, while slightly higher temperatures are required in the separation of phenol. Thus, in one embodiment of the invention, the fermentation broth containing the butanol feed is heated to a temperature in the range of about 30 ℃ to about 90 ℃. In another embodiment, the fermentation broth containing the phenol feed is heated to a temperature in the range of from about 40 ℃ to about 110 ℃.

To facilitate pervaporation, a suitable vacuum may be applied to the vapor chamber of the pervaporation module. In one embodiment, the vacuum applied is from about 0.1in Hg to about 25in Hg. In another embodiment, the vacuum applied is from about 0.15 to about 5in Hg. In another embodiment, the vacuum applied is from about 0.2in Hg to about 4in Hg.

Other processes include methods that increase the separation factor of organic products, such as butanol, phenol, or ethanol, as the concentration of the organic products in the pervaporation feed stream increases. This process involves the use of pervaporation membranes to separate organic products from a pervaporation feed stream.

As used herein, "SF" is a separation factor, which is a measure of the quality of separation of a first species relative to a second species, defined as the ratio of the permeate composition to the ratio of the feed composition.

As used herein, flux is the amount of flow through a unit area of membrane per unit time.

The flux and SF can also be described by the following equations:

flux (J) ═ mass/(area, time)

Separation Factor (SF)

y is permeate concentration and x is feed liquid concentration

Thus, the efficiency of a pervaporation membrane, the separation factor (the enrichment ratio obtained when a liquid mixture permeates through the membrane) and the flux of permeation of the liquid mixture through a polymer membrane can be evaluated in at least two aspects. Thus, the higher the separation factor and flux of a membrane, the higher the separation efficiency of such a membrane. This is of course a very simplified analysis as low separation factors can often be overcome by using a multistage membrane process and such membranes, which often form high surface areas, can overcome low fluxes when the flux of the membrane is low. Thus, while the separation factor and flux factor are important considerations, other factors, such as membrane strength, elasticity, resistance to fouling during use, thermal stability, free volume, etc., are also important considerations in selecting the optimum polymer for forming the pervaporation membrane.

It has now been found that the pervaporation membranes of the present invention have a suitable Separation Factor (SF) for volatile organics such as butanol, phenol or ethanol to provide an effective means of removing volatile organics such as butanol, phenol or ethanol from fermentation broth or from other waste materials as described herein. In one embodiment, the pervaporation membrane has an SF of at least about 5 for volatile organics such as butanol, phenol, or ethanol. In another embodiment, the pervaporation membrane has an SF of at least about 10 for volatile organics such as butanol, phenol or ethanol. In yet another embodiment, the pervaporation membrane has an SF of at least about 15 for volatile organics such as butanol, phenol, or ethanol. In yet other embodiments, the pervaporation membrane has an SF of at least about 20, at least about 25, or at least about 30 for volatile organics such as butanol, phenol, or ethanol. Moreover, any of the aforementioned SFs can be achieved when the concentration of volatile organics in the feed stream, such as butanol, phenol, or ethanol, is 0.5% or higher, 1% or higher, 2% or higher, 3% or higher, 4% or higher, 5% or higher, 6% or higher.

Using the block polynorbornene pervaporation membranes of the present invention, suitable flux to volatile organics such as butanol, phenol, or ethanol can be achieved to provide an effective means of removing volatile organics such as butanol, phenol, or ethanol from the fermentation broth. In one embodiment, at least about 100g/m of volatile organic compounds such as butanol, phenol, or ethanol can be achieved using such block polynorbornene pervaporation membranes²A throughput of/hr. In another embodiment, at least about 150g/m of volatile organics such as butanol, phenol or ethanol can be achieved²A flux per hr; in yet another embodiment, the control of volatile organic compounds such as butanol, phenol or ethyl acetate can be achievedAt least about 200g/m of alcohol²A flux per hr, and in another embodiment, at least about 250g/m of volatile organics such as butanol, phenol or ethanol can be achieved using such polynorbornene pervaporation membranes²A throughput of/hr. Further, unlike conventionally found pervaporation membranes that use previously known non-polynorbornene, any of the aforementioned fluxes can be achieved when the concentration of volatile organics in the feed stream, such as butanol, phenol, or ethanol, is 0.5% or higher, 1% or higher, 2% or higher, 3% or higher, 4% or higher, 5% or higher, 6% or higher.

Surprisingly, it has been found that various block polymers as described herein are suitable for use in forming pervaporation membranes. It has further been observed that suitable combinations of diblock copolymers or triblock terpolymers, as described herein, are also suitable for adjusting the physical properties (e.g., glass transition temperature (T) of the resulting polymers_g) Modulus, free volume, hydrophobicity, hydrolytic stability, etc.) and pervaporation characteristics (e.g., SF and flux). It should also be noted that the block polymers of the present invention can be tailored to exhibit relatively high glass transition temperatures, and that the block polymers of the present invention may be capable of providing the ability to operate as pervaporation membranes at temperatures higher than those possible with currently known membranes.

Advantageously, it has now been found that the combination of different types of blocks comprising different polynorbornene repeat units provides membranes having desirable flux and separation factors. Thus, for example, the use of a diblock polymer having a combination of a relatively lipophilic block comprising monomer repeat units derived from a monomer such as HFANB and a relatively hydrophobic block comprising monomer repeat units such as BuNB provides HFANB-b-BuNB with surprising properties. The manufacture of such block polymers enables the formation of microphase separated membranes characterized by unique properties when separating organic products from the starting materials as described above and below. More specifically, by increasing the molar ratio (i.e., weight fraction) of the alcohol-philic block (e.g., HFANB), it is now possible to control the properties of the resulting membrane. For example, it is now knownIt was found that an increase in the weight fraction of the pro-alcoholic block generally increases the flux as well as the separation factor. Thus, in one embodiment, the weight fraction of the lipophilic block, e.g., the weight fraction W of HFANB_HFANB0.5 to 0.95 in the diblock polymer HFANB-b-BuNB; in other embodiments, it is from about 0.6 to 0.85; and in other embodiments, from 0.7 to 0.8. In some embodiments, the weight fraction of the lipophilic block, e.g., the weight fraction W of HFANB_HFANBIn the diblock polymer HFANB-b-BuNB was 0.5.

Likewise, the triblock polymer may have various combinations of an amphiphilic block and a hydrophobic block, such as an amphiphilic block-hydrophobic block-amphiphilic block; hydrophobic block-lipophilic block-hydrophobic block; hydrophobic block-lipophilic block; an alcohol-philic block-a hydrophobic block; and the like.

Accordingly, in one embodiment of the present invention, there is provided a process for separating an organic product from a feedstock selected from a fermentation broth or waste material containing the organic product, the process comprising the steps of:

charging a feedstock into a pervaporation module comprising a pervaporation membrane formed from a polymer according to claim 1; and

the permeate vapor containing the organic product is collected from the pervaporation module.

As previously mentioned, pervaporation can be carried out at any desired temperature. Thus, in one embodiment, pervaporation is performed while the fermentation broth is loaded into the pervaporation module at a temperature of about 30 ℃ to about 110 ℃. In this embodiment, the vacuum applied to the pervaporation module may range from about 0.1in Hg to about 25in Hg.

In this aspect of the method of the present invention, the pervaporation membrane is formed from a polymer selected from the group consisting of:

In another embodiment, the method of this aspect of the invention comprises a pervaporation membrane formed from a polymer selected from the group consisting of:

a block terpolymer derived from 5-butylbicyclo [2.2.1] hept-2-ene, norbornenyl-2-trifluoromethyl-3, 3, 3-trifluoropropan-2-ol and 5-butylbicyclo [2.2.1] hept-2-ene (BuNB-b-HFANB-b-BuNB); and

block terpolymers derived from norbornenyl-2-trifluoromethyl-3, 3, 3-trifluoropropan-2-ol, 5-butylbicyclo [2.2.1] hept-2-ene and norbornenyl-2-trifluoromethyl-3, 3, 3-trifluoropropan-2-ol (HFANB-b-BuNB-b-HFANB).

In this aspect of the process of the invention, the organic product separated from the biomass or organic waste material is butanol, ethanol or phenol.

In another aspect of the invention, there is also provided a method for separating a volatile organic product, such as butanol or phenol, from a feedstock selected from a fermentation broth or waste material containing such as butanol or phenol. The method comprises the following steps:

charging a feedstock into a pervaporation module comprising a pervaporation membrane, said pervaporation membrane being formed from a polymer selected from the group consisting of:

a block copolymer derived from 5-hexylbicyclo [2.2.1] hept-2-ene and 2- (bicyclo [2.2.1] hept-5-en-2-yl) bicyclo [2.2.1] heptane (HexNB-b-NBANB);

a block terpolymer derived from norbornenyl-2-trifluoromethyl-3, 3, 3-trifluoropropan-2-ol, 5-butylbicyclo [2.2.1] hept-2-ene and norbornenyl-2-trifluoromethyl-3, 3, 3-trifluoropropan-2-ol (HFANB-b-BuNB-b-HFANB); and

permeate vapors containing butanol or phenol are collected from the pervaporation module.

In a further aspect of the present invention, there is also provided a film forming method comprising the steps of: a solution of a block polymer of formula (VI) or (VII) as described herein is poured onto a suitable substrate and the substrate is dried at a suitable temperature to form a film. As mentioned above, the drying of the film so formed can be carried out at any temperature to achieve the desired results. Typically, the drying is carried out at a temperature in the range of about 30 ℃ to about 120 ℃, in some other embodiments the drying temperature is about 50 ℃ to 100 ℃, or 70 ℃ to 90 ℃. The time required to dry the film may range from about 10 minutes to 1 day, or from 30 minutes to 20 hours, or from 1 hour to 16 hours.

Any of the block polymers of the present invention as described herein can be used to form the membrane in this aspect of the present invention. Non-limiting examples of such diblock copolymers may be listed as follows:

In another embodiment of the method of the present invention, non-limiting examples of such triblock polymers that can be used to form the film of the present invention may be enumerated as follows:

Surprisingly, it has now been found that forming a solution of the block polymer in a suitable solvent or solvent mixture and drying results in phase separation, which may be due to some of the superior properties observed in the selective separation of organic volatiles from biomass or organic waste. It has now been observed that the selection of a suitable solvent or mixture of solvents for dissolving the block polymer results in the phase separation observed by the different surface morphologies. Examples of suitable solvents for dissolving the block polymer include hydrocarbon solvents such as toluene, and other ether solvents such as Tetrahydrofuran (THF). Surprisingly, it has now been found that the use of a mixture of solvents, for example hydrocarbon solvents and ethers such as toluene and THF, results in a significant change in the surface morphology of the films formed therefrom.

This aspect is illustrated by fig. 3 and 4, which respectively show the weight fraction W of HFANB_HFANBAtomic force micrograph of film formed from diblock copolymer of BuNB-HFANB at a (1:2) molar ratio of 0.78 (fig. 3) and weight fraction W of HFANB_HFANBAtomic force micrograph of film formed from diblock copolymer of BuNB-HFANB at a (2:1) molar ratio of 0.48 (fig. 4). A film of the diblock copolymer containing BuNB-HFANB in a (1:2) molar ratio was formed using toluene as the solvent. A membrane containing a diblock copolymer of BuNB-HFANB in a (2:1) molar ratio was formed using THF as the solvent. As can be seen from fig. 3 and 4, both films do not show any nanoscale structure, i.e. do not show any observable phase separation of the blocks. However, FIG. 5 shows an atomic force micrograph of a membrane formed from a (1:1:1) molar ratio of the triblock polymer of HFANB-BuNB-HFANB. The membrane was formed using a mixture of toluene and THF. Clearly, the membrane clearly shows a nanoscale structure demonstrating phase separation. As described further below, pervaporation in the present inventionIn the process, by using the membrane as shown in fig. 5, a higher flux can now be obtained than the membranes of fig. 3 and 4 (see table 4). This clearly illustrates at least one of the surprising beneficial effects that can be obtained from the practice of the present invention.

The microphase-separated morphology of the membrane can also be obtained by using a mixture of solvents with improved procedures. Therefore, in another embodiment of the present invention, the block polymer of the present invention is dissolved in a mixture of a nonpolar solvent and a polar solvent, and the resulting solution is cast on a suitable support to form a membrane, and then the solvent mixture is evaporated to form a microphase-separated form. Examples of the nonpolar solvent include any hydrocarbon solvent such as hexane, heptane, toluene, trifluorotoluene (TFT), and mixtures thereof. Examples of the polar solvent include ether solvents such as Tetrahydrofuran (THF) and diethyl ether; alcohols, e.g. butanol, pentanol, hexanol or heptanol (or C)₈-C₁₂Alcohols), and mixtures thereof. Typically, in this aspect of the invention, the film is made by a solution casting process as described herein. That is, typically the block polymer is dissolved in a mixture of solvents such as toluene, TFT and THF, and the solution thus formed is coated on a Polyacrylonitrile (PAN) film, followed by THF vapor annealing. Annealing can be performed by any method known in the art, such as exposing the film in a THF chamber at the desired temperature. Typically, membranes formed in this manner contain a uniform dense layer of block polymer on a porous PAN supported membrane and function as a selective layer for pervaporation separation of organic products in aqueous solution, such as biobutanol.

The following examples describe in detail the methods of making and using certain compounds/monomers, polymers and compositions of the present invention. The detailed preparation falls within the scope of the more broadly described preparation method described above and is intended to be illustrative. The examples are provided for illustrative purposes only and are not intended to limit the scope of the present invention. As used in the examples and throughout the specification, the monomer to catalyst ratio is based on mol to mol.

Examples

The following abbreviations are used above and below to describe some of the compounds, apparatuses and/or methods used to illustrate certain embodiments of the present invention.

HFANB: norbornenyl-2-trifluoromethyl-3, 3, 3-trifluoropropan-2-ol; HexNB: 5-hexylbicyclo- [2.2.1]Hept-2-ene; c₄F₉NB: 5-perfluorobutylbicyclo [2.2.1]]Hept-2-ene; BuDMMINB: 1- (4- (bicyclo [2.2.1]]Hept-5-en-2-yl) butyl) -3, 4-dimethyl-1H-pyrrole-2, 5-dione, PGMEA propylene glycol methyl ether acetate, PTFE polytetrafluoroethylene, TFT α -trifluorotoluene, THF tetrahydrofuran, R.T. -room temperature.

The reaction is usually carried out under nitrogen atmosphere, if desired in a dry box or using standard schlenk tube/airless transfer (airless transfer) techniques. Generally, the solvent is dried over molecular sieves or magnesium sulfate, or distilled from a desiccant and purged with nitrogen before use. Various other known techniques for drying the solvent may also be used.

The following examples describe procedures for preparing the various compounds disclosed herein, including certain starting materials for preparing the compounds of the present invention. It should be noted, however, that these examples are intended to illustrate the disclosure of the present invention and not to limit its scope.

Example 1

Bis (isopropoxy-dicyclopentadienyl) dichloropalladium [ Pd (i-PrO-DCPD) Cl]₂

The title compound was prepared using a slightly modified procedure as described in Chatt et al, j.chem.soc. (1957) 3413. Under nitrogen atmosphere, sodium chloropalladite [ Na ]₂PdCl₄](3g, 10.2mmol) was suspended in anhydrous isopropanol (15ml) and stirred at ambient temperature. To the suspension dicyclopentadiene (2.7g, 20.4mmol) was added and the mixture was stirred at ambient temperature for an additional 5 days. The resulting mixture was filtered, washed with heptane (three times with 5ml) and dried to yield 3.8g of a yellow powder.

Under ambient conditions (ambient condition), 1g of the yellow powder obtained above was suspended in heptane (15ml), isopropanol (15ml) was added to the suspension with stirring, and the mixture was stirred at ambient temperature for an additional 2 days. The mixture was then filtered and the solid was washed with heptane to yield 1.1g of the title compound as a slightly whitish yellow powder. By passing¹H NMR was characterized and the title compound was found to be substantially pure:¹H NMR(CD₂Cl₂δ ppm)6.46(1H), 5.88(1H), 3.72(2H), 3.18(1H), 3(1H), 2.8(1H), 2.6(1H), 2.5(1H), 2.17(2H), 1.61(1H), 1.17(1H) and 1.12 (6H).

Example 2

Bis (acetoxy-dicyclopentadienyl) dichloropalladium [ Pd (AcO-DCPD) Cl]₂

Toluene (20ml) was added to [ Pd (DCPD) Cl with stirring under atmospheric conditions]₂(0.5g, 1.6mmol) and silver acetate (AgOAc) (0.27g, 1.6 mmol). The resulting yellow suspension was stirred at ambient temperature for 1 hour. The resulting brown solution was filtered and the filtrate evaporated to dryness to give an orange oil which was washed with 30ml of ether and filtered to give the title compound as a yellowish pink colour. By passing¹H NMR was characterized and the title compound was found to be substantially pure:¹H NMR(CD₂Cl₂，δppm)，6.51(1H)，5.93(1H)，4.87(1H)，3.1(2H)2.85(1H), 2.68(3H), 2.33(1H), 2.22(2H) and 1.96 (3H).

Example 3

Bis (n-propoxy-dicyclopentadienyl) dichloropalladium [ Pd (n-PrO-DCPD) Cl]₂

Under a nitrogen atmosphere, n-propanol (25ml) was added to [ Na ] through a cannula with stirring₂PdCl₄](1g, 3.4mmol) with dicyclopentadiene (0.9g, 6.8 mmol). The resulting reddish brown suspension was stirred at ambient temperature for one day. The resulting pale beige suspension was filtered, washed three times with hexane (5ml each) and dried under vacuum to yield 1.5g of the title compound. By passing¹H NMR was characterized and the title compound was found to be substantially pure:¹HNMR(CD₂Cl₂，δppm)，6.48(1H)，5.87(1H)，3.59(1H)，3.45(1H)，3.3(1H)，3.21(1H)，3.02(1H)，2.83(1H)，2.63(1H)，2.56(1H)，2.25(1H)，2.18(1H)，1.6(1H)，1.58(4H)，1.06(1H)，0.88(3H)。

example 4

(Isopropoxy-dicyclopentadienyl) palladium (triisopropyl) phosphine [ Pd (i-PrO-DCPD) Cl (P-i-Pr)₃)]

The compound of example 1[ Pd (i-PrO-DCPD) Cl was reacted under a nitrogen atmosphere]₂(1g, 1.5mmol) was suspended in tetrahydrofuran (30ml) and stirred. To the suspension was added dropwise a solution of triisopropylphosphine (0.48g, 3mmol) in tetrahydrofuran (10ml) through a cannula. At the end of this addition the suspension became clear, the solution was stirred for a further 15 minutes and then concentrated to 10ml and filtered. The resulting yellow filtrate was stirred overnight and concentrated to dryness to obtain 1.25g of the title compound as a yellow solid. By passing¹H NMR and³¹p NMR, and the title compound was found to be substantially pure:¹h NMR (toluene-d)₈，δppm)，7.59(1H)，7.15(1H)，3.71(1H)，3.47(1H)，2.76(1H)，2.53(4H)，2.28(2H)，2.1(2H)，1.81(1H)，1.63(1H)，1.4(1H)，1.24(18H)，1.05(6H)；³¹P NMR (toluene-d)₈，δppm)50.93。

Example 5

(Isopropoxy-dicyclopentadienyl) palladium (triphenylphosphine) [ Pd (i-PrO-DCPD) Cl

(PPh₃)]

Under a nitrogen atmosphere, light petroleum ether (230ml) was added to [ Pd (i-PrO-DCPD) Cl ] of example 1]₂(3g, 4.5mmol) with triphenylphosphine (2.6g, 9.9 mmol). The resulting brown suspension was stirred at ambient temperature for 24 hours, filtered, washed with ether and then dried to yield 4.1g of the title compound as a brown powder. By passing¹H NMR and³¹p NMR, and the title compound was found to be substantially pure:¹H NMR(CD₂Cl₂，δppm)，7.67(6H)，7.48(9H)，6.89(1H)，3.88(1H)，3.33(1H)，2.93(1H)，2.83(1H)，2.67(2H)，2.33(1H)，2.21(1H)，1.92(1H)，1.54(1H)，1.27(1H)，1.09(1H)，0.99(3H)，0.79(3H)；³¹P NMR(CD₂Cl₂，δppm)30.76。

example 6

(n-propoxy-dicyclopentadienyl) palladium (triisopropyl) phosphine [ Pd (n-PrO-DCPD) Cl (P-i-Pr)₃)]

The compound of example 3 [ Pd (n-PrO-DCPD) Cl was reacted under a nitrogen atmosphere]₂(0.5g, 1.5mmol) was suspended in tetrahydrofuran (15ml) and stirred. To the suspension was added dropwise a solution of triisopropylphosphine (0.24g, 1.5mmol) in tetrahydrofuran (5ml) through a cannula. At the end of this addition the suspension became clear, the solution was stirred overnight and filtered using a 0.45mm Polytetrafluoroethylene (PTFE) syringe filter. The filtrate was concentrated to dryness to give a yellow oil which was taken up in petroleum ether (3ml) and sonicated (sonicate) for 3 minutes to precipitate the title compound as a solid. Then, the title compound was filtered and dried in vacuo (0.26 g was obtained). By passing¹H NMR and³¹p NMR, and the title compound was found to be substantially pure:¹H NMR(CD₂Cl₂，δppm)，7.05(1H)，6.78(1H)，3.61(1H)，3.36(1H)，3.18(1H)，2.89(2H)，2.64(5H)，2.35(1H)，2.24(1H)，2.09(1H)，1.55(4H)，1.47(3H)，1.34(18H)；³¹P NMR(CD₂Cl₂，δppm)50.16。

example 7

(Isopropoxy-dicyclopentadienyl) (triisopropyl) phosphine palladium trifluoromethanesulfonate

[Pd(i-PrO-DCPD)(P-i-Pr₃)(OTf)]

Example 4 was converted to the solid phase in a dry box under an inert atmosphere of nitrogenCompound [ Pd (i-PrO-DCPD) Cl (P-i-Pr)₃)](0.25g, 0.5mmol) was dissolved in dichloromethane (3ml) and stirred. To this stirred solution was added a suspension of silver triflate AgOTf (0.13mg, 5mmol) in dichloromethane (2ml), followed by a suspension of silver triflate AgOTf (0.13mg, 5mmol) in tetrahydrofuran (2ml), resulting in a milky pale yellow suspension. The mixture was stirred for 10 minutes and filtered through a 0.45mm Polytetrafluoroethylene (PTFE) syringe filter. The yellow filtrate thus obtained was concentrated to dryness to give an oily residue, which was dissolved in diethyl ether (2ml) and dried in vacuo to obtain 0.14g of the title compound as an off-white foamy solid. By passing¹H,³¹P and¹⁹f NMR, and the title compound was found to be substantially pure:¹h NMR (toluene-d)₈，δppm)，7.3(1H)，6.8(1H)，3.55(1H)，3.41(1H)，2.62(1H)，2.45(1H)，2.27(6H)，2.03(1H)，1.8(1H)，1.5(1H)，1.16(9H)，1.06(9H)，0.98(6H)，0.86(1H)；³¹P NMR (toluene-d)₈，δppm)，50；¹⁹F NMR (toluene-d)₈，δppm)，-77.3。

Example 8

(Isopropoxy-dicyclopentadienyl) (triisopropyl) phosphine (acetonitrile) tetrakis (pentafluorophenyl) boracic acid palladium

[Pd(i-PrO-DCPD)(P-i-Pr₃)(CH₃CN)]FABA

The compound of example 4 [ Pd (i-PrO-DCPD) Cl (P-i-Pr) was reacted under a nitrogen atmosphere₃)](5.1g, 10.2mmol) was dissolved in toluene (25ml) with stirring. To this solution was added a solution of lithium tetrakis (pentafluorophenyl) borate (LiFeABA) (8.92g, 10.2mmol) in acetonitrile (25ml) through a cannula. The clear yellow solution became cloudy, stirred overnight and run through celiteAnd (5) filtering. The filtrate was concentrated to give a thick mass (thick syrup mass). To the syrup was added pentane (50ml) and ether (50ml) to give a yellow solid which was filtered, washed with pentane (25ml) and dried in vacuo to give 9.9g (82% yield) of the title compound. By passing¹H and³¹p NMR, and the title compound was found to be substantially pure:¹h NMR (acetone-d)₆，δppm)，7.17(1H)，6.76(1H)，3.85(1H)，3.72(1H)，3.5(2H)，2.94(2H)，2.7(5H)，2.4(1H)，2.32(2H)，2.1(1H)，1.56(1H)，1.42(18H)，1.18(1H)，1.09(6H)；³¹P NMR (acetone-d)₆，δppm)，52.19。

Example 9

(Isopropoxy-dicyclopentadienyl) (triisopropyl) phosphine (pyridine) tetrakis (pentafluorophenyl) borate palladium

[Pd(i-PrO-DCPD)(P-i-Pr₃)(p)]FABA

The compound of example 8 [ Pd (i-PrO-DCPD) (P-i-Pr) was reacted under a nitrogen atmosphere₃)(CH₃CN)]FABA (0.25g, 0.212mmol) was dissolved in toluene (5ml) and stirred. Pyridine (90ml) was added to the solution by syringe, resulting in a pale yellow solution. The solution was concentrated to dryness to give a yellow oil, which was dissolved in diethyl ether (1ml) and evaporated to dryness to give 0.18g of the title compound as a white foamy solid. By passing¹H and³¹p NMR, and the title compound was found to be substantially pure:¹H NMR(CD₂Cl₂，δppm)，8.54(2H)，7.92(1H)，7.54(2H)，7.08(1H)，5.41(1H)，3.82(1H)，3.72(1H)，3.06(2H)，2.75(1H)，2.65(1H)，2.46(1H)，2.34(6H)，1.65(1H)，1.39(18H)，1.18(6H)；³¹P NMR(CD₂Cl₂，δppm)，50.35。

example 10

(Isopropoxy-dicyclopentadienyl) (triisopropyl) phosphine (acetonitrile) palladium tetrafluoroborate

[Pd(i-PrO-DCPD)(P-i-Pr₃)(CH₃CN)]BF₄

In a dry box, under an inert atmosphere of nitrogen, the compound of example 4 [ Pd (i-PrO-DCPD) Cl (P-i-Pr)₃)](1g, 2mmol) was suspended in toluene (10ml) with stirring. To this suspension was added silver tetrafluoroborate AgBF in acetonitrile (5ml) via a pipette₄(0.4g, 2mmol) of the resulting solution. The suspension quickly became clear and a grey solid precipitated, which was stirred for an additional 5 minutes and then filtered through a 0.45mm Polytetrafluoroethylene (PTFE) syringe filter. The filtrate was concentrated to dryness to give a yellow oily residue which was washed twice with pentane (5ml) and then taken up in diethyl ether (5 ml). The resulting solution was concentrated to dryness to obtain 820mg of the title compound as a light pearl-colored foamy solid. By passing¹H NMR and³¹p NMR, and the title compound was found to be substantially pure:¹H NMR(CDCl₃，δppm)，7.21(1H)，6.51(1H)，3.77(1H)，3.67(1H)，2.96(2H)，2.71(2H)，2.46(7H)，2.21(2H)，1.58(26H)；³¹P NMR(CD₂Cl₂，δppm)，52.49。

example 11

Homopolymers of norbornenyl-2-trifluoromethyl-3, 3, 3-trifluoropropan-2-ol (HFANB)

Example 11 illustrates that the compounds of the present invention have high catalytic activity compared to palladium catalysts reported in the literature, and some comparative examples are provided below as comparative examples 1 and 2, all of which are performed under substantially the same conditions to show the difference in catalytic activity of each of the compounds used therein.

To a suitable reaction vessel were added HFANB (1g, 3.7mmol) and toluene (3g), and sparged with nitrogen for 30 minutes, then heated to 80 ℃. To this solution was added a solution of the compound from example 8 (0.022g, 0.018mmol) in toluene (1 ml). The mixture was stirred for 30 minutes and then cooled to room temperature. The polymerization was stopped by adding a solution of ((phenylphosphonediyl) bis (ethane-2, 1-diyl)) bis (diphenylphosphinane), triphosphon (0.04g, 0.06mmol) in dichloromethane (0.3 ml). Then, the polymer was precipitated by pouring the mixture into an excess of ethanol (10mL), and 1g of polymer was obtained (100% conversion). Characterization of the polymer by GPC: m_w＝60,600；M_n＝16,700；PDI＝3.6。

Examples 12 to 15

Homopolymerization with the Compound of example 4

Example 11 was substantially repeated in these examples 12 to 15, except that various monomers as listed in table 1 were used as polymerization catalysts in a molar ratio of monomer: catalyst: LiFABA of 100:1:1 with the compound of example 4 and lithium tetrakis (pentafluoroborate) LiFABA. At the end of the indicated reaction time, the reaction was stopped and the solvent was evaporated. The remaining material was dissolved in THF and filtered. Then, the polymer is precipitated by pouring the polymer solution into water or acetone. Then, the powdery polymer thus obtained was collected and precipitated again twice by dissolving in THF and pouring the solution into water or acetone.

The monomers used, the solvents used, the polymerization temperature, the reaction time, the conversion and the GPC data of the polymers obtained in these examples 12 to 15, respectively, are summarized in Table 1.

TABLE 1

R.t. -room temperature; TFT-trifluorotoluene;

examples 15A to E

Examples 15A-E below provide procedures for making various methyl (palladium) phosphine compounds used in the manufacture of the living polymers of the present invention.

Example 15A

[(CH₃)Pd(P^tBu₃)(Cl)]

The title compound was prepared using a slightly modified procedure as described in k.nozaki et al, Organometallics,2006,4588. Under nitrogen atmosphere, [ (1, 5-cyclooctadiene) Pd (CH)₃)(Cl)](2.5g, 9.43mmol) was dissolved in anhydrous dichloromethane (2.5ml) and stirred at-78 ℃. To this solution was added a solution of tri-tert-butylphosphine (1.91g, 9.43mmol) in dichloromethane (2mL) and the mixture was stirred at-78 deg.C for an additional 5 minutes. The mixture solution was then warmed (arm up) to ambient temperature and stirring was continued for 15 minutes. The resulting mixture was filtered, washed with n-pentane (three times with 10ml) and dried to yield 2.73g of the title compound as a yellow powder.

By passing¹H NMR and³¹P-NMRCharacterisation, the title compound was found to be substantially pure:¹H NMR(CD₂Cl₂，δppm)1.75(s，3H)，1.52(d，12Hz，27H)。31P-NMR(CD₂Cl₂，δppm)69.5

example 15B

[(CH₃)Pd(P(^tBu)₂(Cy))(Cl)]

Using [ (1, 5-cyclooctadiene) Pd (CH)₃)(Cl)](300mg, 1.1mmol) and di-tert-butyl-cyclohexylphosphine (260mg, 1.1mmol) except for substantially following the procedure of example 15A to give 280mg of the title compound as a pale yellow powder.

By passing¹H NMR and³¹P-NMR, and the title compound was found to be substantially pure:¹H NMR(CD₂Cl₂，δppm)2.35(m，2H)，1.75(m，5H)，1.52(m，18H)，1.30(m，4H)，0.82(s，3H)。³¹P-NMR(CD₂Cl₂，δppm)71.5

example 15C

[(CH₃)Pd(P(^tBu)₂(ⁱPr))(Cl)]

Using [ (1, 5-cyclooctadiene) Pd (CH)₃)(Cl)](430mg, 1.62mmol) and di-tert-butyl-isopropylphosphine (320mg, 1.7mmol) except for substantially following the procedure of example 15A to give 380mg of the title compound as a pale yellow powder.

By passing¹H NMR and³¹P-NMR, and the title compound was found to be substantially pure:¹H NMR(CDCl₃，δppm)2.8(m，1H)，1.54(m，24H)，0.79(s，3H)。³¹P-NMR(CDCl₃，δppm)71.5。

example 15D

[(CH₃)Pd(P(Cy)₃)(Cl)]

Using [ (1, 5-cyclooctadiene) Pd (CH)₃)(Cl)](600mg, 2.3mmol) and tris-cyclohexylphosphine (630mg, 2.3mmol) except for substantially following the procedure of example 15A to give 350mg of the title compound as a pale yellow powder.

By passing¹H NMR and³¹P-NMR, and the title compound was found to be substantially pure:¹H NMR(CDCl₃，δppm)1.8(m，23H)，1.32(m，10H)，0.79(s，3H)。³¹P-NMR(CDCl₃，δppm)47。

example 15E

[(CH₃)Pd(P(ⁱPr)₃)(Cl)]

Using [ (1, 5-cyclooctadiene) Pd (CH)₃)(Cl)](210mg, 0.8mmol) and triisopropylphosphine (130mg, 0.8mmol) except for substantially following the procedure of example 15A to give 180mg of the title compound as a pale yellow powder.

By passing¹H NMR and³¹P-NMR, and the title compound was found to be substantially pure:¹H NMR(CD₂Cl₂，δppm)2.40(m，3H)，1.42(m，18H)0.72(s，3H)。³¹P-NMR(CD₂Cl₂，δppm，50℃)56.6。

example 15F

[(CH₃)Pd(P(ⁱPr)₂(^tBu))(Cl)]

Using [ (1, 5-cyclooctadiene) Pd (CH)₃)(Cl)](500mg, 1.9mmol) and diisopropyl-tert-butylphosphine (330mg, 1.9mmol) except for substantially following the procedure of example 15A to give 510mg of the title compound as a pale yellow powder.

By passing¹H NMR and³¹P-NMR, and the title compound was found to be substantially pure:¹H NMR(CD₂Cl₂，δppm)2.55(m，2H)，1.52(m，21H)0.80(s，3H)。³¹P-NMR(CD₂Cl₂，δppm，RT)66.5。

example 15AA-AI

Examples 15AA-AI below provide procedures for making various allylic (palladium) phosphine and imidazole compounds used in the manufacture of the living polymers of the invention.

Example 15AA

[(η³Allyl group Pd (P: (C))ⁱPr)₃)(Cl)]

Under nitrogen atmosphere [ (η)³Allyl group Pd (Cl)]₂(4g, 10.9mmol) was dissolved in dry toluene (100ml) and stirred at-78 ℃. To this solution was added triisopropylphosphine (3.68g, 23mmol) in toluene solution (50mL), and the mixture was stirred at-78 ℃ for an additional 5 minutes. The mixture was then warmed to ambient temperature and stirring was continued for 2 days. The resulting mixture was evaporated to dryness and the resulting solid was dissolved in THF (48 ml). After stirring for 5 hours, the solution was filtered to remove any metals and then evaporated to dryness. The resulting solid was washed with diethyl ether (three times with 20ml) and dried to give 5.7g of the title compound as a pale yellow powder.

By passing¹H NMR and³¹P-NMR, and the title compound was found to be substantially pure:¹H NMR(CDCl₃，δppm)5.42(m，1H)，4.73(m，1H)，3.75(m，1H)，3.62(m，1H)，2.75(m，1H)，2.53(m，3H)，1.30(m，18H)。³¹P-NMR(CDCl₃，δppm)53。

example 15AB

[(η³Allyl group Pd (P: (C))^tBu)₃)(Cl)]

The procedure of example 15AA was essentially followed except for using tri-tert-butylphosphine (420mg, 2.08mmol) in toluene solution (15mL) to obtain 310mg of the title compound as a yellow powder.

By passing¹H NMR and³¹P-NMR, and the title compound was found to be substantially pure:¹H NMR(CD₂Cl₂，δppm)5.48(m，1H)，4.65(m，1H)，4.23(m，1H)，3.78(m，1H)，2.75(m，1H)，1.60(m，27H)。³¹P-NMR(CD₂Cl₂，δppm)88。

example 15AC

[(η³Allyl group (Pd (P) (Cy)) (^tBu)₂)(Cl)]

The procedure of example 15AA was essentially followed except for using di-tert-butylcyclohexylphosphine (620mg, 2.73mmol) in toluene solution (15mL) to give 350mg of the title compound as a pale yellow powder.

By passing¹H NMR and³¹P-NMR was carried out and the title compound was found to be substantially pure.¹H NMR(CD₂Cl₂，δppm)5.48(m，1H)，4.65(m，1H)，4.23(m，1H)，3.78(m，1H)，2.75(m，1H)，1.80-1.40(m，29H)。³¹P-NMR(CD₂Cl₂，δppm)72。

Example 15AD

[(η³Allyl group Pd (P: (C))ⁱPr)(^tBu)₂)(Cl)]

The procedure of example 15AA was essentially followed except for using di-tert-butyl-isopropylphosphine (510mg, 2.73mmol) in toluene solution (10mL) to obtain 480mg of the title compound as a pale yellow powder.

By passing¹H NMR and³¹P-NMR, and the title compound was found to be substantially pure:¹H NMR(CDCl₃，δppm)5.40(m，1H)，4.73(m，1H)，3.82(m，1H)，3.70(m，1H)，3.25(m，1H)，2.75(m，1H)，1.63(m，24H)。³¹P-NMR(CDCl₃，δppm)71.8。

example 15AE

[(η³Allyl group Pd (P: (C))ⁱPr)₂(^tBu))(Cl)]

The procedure of example 15AE was essentially followed, except for using tert-butyl-diisopropylphosphine (480mg, 2.73mmol) in toluene solution (10mL), to give 490mg of the title compound as a pale yellow powder.

By passing¹H NMR and³¹P-NMR, and the title compound was found to be substantially pure:¹H NMR(CDCl₃，δppm)5.40(m，1H)，4.73(m，1H)，3.82(m，1H)，3.70(m，1H)，3.25(m，1H)，2.75(m，3H)，1.45(m，21H)。³¹P-NMR(CDCl₃，δppm)63.2。

the following palladium compounds were purchased from Johnson Matthey and used as received:

example 15AF

Example 15AG

Practice ofExample 15AH

Example 15AI

Example 16A

Homopolymers of 5-butyl-2-norbornene (BuNB)

To a suitable reaction vessel were added BuNB (1.2g, 7.98mmol) purged with nitrogen, toluene (22.32g) and α -trifluorotoluene (TFT) (0.48g) to this solution was added a solution of the compound of example 15A (30mg, 0.79mmol) and lithium tetrakis (pentafluorophenyl) boride LiFeABA (70mg, 0.79 mmol). after 20 minutes of polymerization, the reaction solution was sampled and washed with toluene/CH₃The CN solution deactivated the enzyme. Characterization of the polymer by GPC: m_w＝34,509；M_n＝30,752；PDI＝1.1。

Examples 16B to 16R

Homopolymerization of functionalized norbornene Using Compounds of examples 15A-15E

Homopolymerization with various norbornene monomers and the palladium compounds of examples 15A to 15E was carried out using substantially the same procedure as described in example 16A. The norbornenes used in these examples 16B to 16R, respectively, the solvents used, the reaction times, the conversions and the GPC data of the polymers obtained are summarized in Table 1A. In each of these examples, the molar ratio of Pd compound, LiFABA, and norbornene monomer was 1/1/100.

TABLE 1A

Example 16AA

Homopolymers of 5-butyl-2-norbornene (BuNB)

To a suitable reaction vessel were added BuNB (1.2g, 7.98mmol) purged with nitrogen, toluene (22.32g) and α -trifluorotoluene (TFT) (0.48g) to this solution was added a solution of the compound of example 15AA (31mg, 0.079mmol) and lithium tetrakis (pentafluorophenyl) boride LiFeABA (70mg, 0.079 mmol). after 20 minutes, the reaction solution was sampled and washed with toluene/CH₃The CN solution deactivated the enzyme. The polymer was isolated and characterized by GPC: m_w＝25,239，M_n＝22,243，PDI＝1.1。

Example 16AB-AS

Homopolymerization with the Compounds of example 15AA-AI

Homopolymerization with various norbornene monomers and the palladium compounds of examples 15AA to 15AI was carried out using substantially the same procedure as described in example 16A. The norbornenes used in each of these examples 16AB-16AS, the solvents used, the reaction times, the conversions and the GPC data of the polymers obtained are summarized in Table 1B. In each of these examples, the molar ratio of the Pd compound, LiFABA, and norbornene monomer (Pd compound/LiFABA/NB monomer) was 1/1/100.

TABLE 1B

Not determined ND

It is clear from the above data that, as summarized in tables 1A and 1B above, the allyl-palladium phosphine compounds of examples 15AA-AI generally exhibit higher reactivity and more activity characteristics than the corresponding methyl-palladium phosphine compounds of example 15 AE.

Examples 16 to 20

Diblock polymers

Example 11 was substantially repeated in these examples 16 to 20, except that various different monomers as listed in table 2 were used to form the diblock polymer. In all of these examples, a first monomer is polymerized and then a second monomer is added to the resulting polymer mixture to obtain a diblock polymer. In example 19, the polymerization catalysts used in these examples 16 to 20 were lithium tetrakis (pentafluorophenyl) boride LiFABA and allylpalladium (triisopropylphosphine) chloride [ Pd (allyl) (triisopropylphosphine) Cl ] in a molar ratio of monomer 1: monomer 2: catalyst: LiFABA of 100:100:1:1, except that the molar ratio of monomer 1: monomer 2: catalyst: LiFABA was 250:250:1: 1. A50: 50(v/v) mixture of toluene and trifluorotoluene was used in example 20, except that the solvent used in each of these examples was toluene and polymerization was carried out at room temperature. The resulting residual substance was reprecipitated by dissolving in THF and filtering the solution and then reprecipitating in water or acetone as described in examples 12 to 15.

The monomers used, the monomer ratios in the resulting polymers, the reaction times, the conversions and the GPC data of the resulting polymers in each of these examples 16 to 20 are summarized in table 2.

TABLE 2

Precipitating the polymer from the reaction solution; n.m. -not determined

Examples 21 to 24

Diblock polymers

Example 11 was substantially repeated in these examples 21 to 24, except that various monomers as listed in table 3 were used to form the diblock polymer. In all of these examples, a first monomer is polymerized and then a second monomer is added to the resulting polymer mixture to obtain a diblock polymer. In example 23, the polymerization catalysts used in these examples 21 to 24 were lithium tetrakis (pentafluorophenyl) boride LiFABA and methyl palladium (triisopropylphosphine) chloride, [ Pd (methyl) (tri-tert-butylphosphine) Cl ] in a molar ratio of monomer 1: monomer 2: catalyst: LiFABA of 500:500:1:1, except that the molar ratio of monomer 1: monomer 2: catalyst: LiFABA was 100:100:1: 1. Polymerization was carried out at room temperature in example 24, except that trifluorotoluene was used in example 24 and the solvent used in each of these examples was toluene and polymerization was carried out at 45 ℃. At the end of the specified reaction time, the polymerization was stopped and the polymer isolated by evaporation of the solvent, as in examples 12-15. The resulting residual substance was reprecipitated by dissolving in THF and filtering the solvent, followed by reprecipitation in water or acetone as described in examples 12 to 15.

The monomers used in each of these examples 21 to 24, the monomer ratio in the resulting polymer, the time, the conversion and the GPC data of the resulting polymer are summarized in table 3.

TABLE 3

Example 25

Diblock polymers of HFANB and BuNB (HFANB-b-BuNB)

Example 11 was substantially repeated in this example 25, except that the polymerization catalyst used in this example was lithium tetrakis (pentafluorophenyl) boride LiFABA and the compound of example 4in a molar ratio of monomer 1: monomer 2: catalyst: LiFABA of 100:100:1: 1. The polymerization was carried out in a 50:50(v/v) mixture of toluene and trifluorotoluene and was carried out at room temperature. First, monomer 1HFANB was polymerized at room temperature for 60 minutes, at which time a polymer sample was analyzed by GPC and the number average molecular weight M was determined_n49,000, PDI 1.2, and 89% conversion. Monomer 2BuNB was then added to the reaction mixture and polymerization was continued for 15 minutes at 100% monomer conversion. At this point the procedure was essentially as described in examples 12-15 to stop the polymerization. The resulting diblock polymer HFANB-b-BuNB showed 102,000M by GPC_nAnd a PDI of 1.2.

Example 26

Triblock Polymer-BuNB-b-HFANB-b-BuNB (1:1:1 Block ratio)

Example 11 was substantially repeated in this example 26, except that BuNB and HFANB monomers were used to form the title triblock polymer. First, monomer 1BuNB was polymerized, then monomer 2HFANB was added to the resulting polymer mixture to form a diblock polymer, and in the last step monomer 3 BuNB was added to form the title triblock polymer. The polymerization catalyst used in this example 26 was lithium tetrakis (pentafluorophenyl) boride LiF ABA, in a molar ratio of monomer 1: monomer 2: monomer 3: catalyst LiFABA of 100:100:100:1:1,And allylpalladium (triisopropylphosphine) chloride [ Pd (allyl) (triisopropylphosphine) Cl]. The solvent used was toluene, and the polymerization was carried out at room temperature. The first polymerization with BuNB was carried out for 9 minutes with a conversion of 97%, M_n35,000, PDI 1.1; second polymerization with HFANB for 60 min at 95% conversion, M_n80,000, PDI 1.1; final polymerization with BuNB was carried out for 3 minutes at 97% conversion, M_n108,000, PDI 1.2.

Examples 26A to C

Various other diblock and triblock polymers

In these examples 26A-C, diblock and triblock polymers were synthesized by sequentially adding the respective norbornene monomers at room temperature under a nitrogen atmosphere. The total monomer concentration was 4 wt%. A representative procedure for the preparation of BuNB-b-HFANB example 26A includes the following. Will be (t-Bu)₃P) PdMeCl (12mg, 0.033mmol), LiFeABA (29mg, 0.033mmol), toluene (6g) and TFT (6g) were added to a 250mL round bottom flask equipped with a magnetic stir bar and the mixture was stirred for 5 minutes. BuNB (0.5g, 3.3mmol) was injected into the flask in one portion with vigorous stirring. After complete consumption of BuNB (30 min), a small amount of the reaction mixture was removed and quenched with acetonitrile for GPC analysis of the poly (BuNB) block. Then, HFANB (1.8g, 6.6mmol) in toluene/TFT (44g, 50/50 wt%) was added to the reaction flask. HFANB was polymerized for 2 days. By repeated precipitation to methanol/H₂O (50/50 vol%) and recovering the block copolymer. The resulting polymer was dissolved in THF and the solution was stirred on activated carbon, followed by removal of the remaining Pd catalyst by alumina plug (alumina plug). Precipitating the filtrate to methanol/H₂O (50/50 vol%), followed by drying at 60 ℃ under vacuum. The ratio of the monomers, the solvent, the reaction time,% conversion, M_nAnd PDI are summarized in Table 3A, except that two other block polymers BnNB-b-C were prepared using the same procedure₄F₉NB (example 26B) and BuNB-B-BnNB-B-NBANB (example)Example 26C).

TABLE 3A

^a4% by weight of each monomer in the respective solvent;^btol ═ toluene;^cTFT ═ α, -trifluorotoluene;^ddetermination by NMR;^edetermination by GPC Using a differential Refractometry (RI) detector calibrated with narrow distribution polystyrene standards (THF)

Examples 26D to G

Block copolymers of HFANB-b-BuNB (different monomer ratios)

These examples 26D-G further illustrate the use (η)³Allyl) Pd (i-Pr)₃P) Cl prepared diblock polymers with different monomer ratios (i.e., molar ratios) of HFANB to BuNB.

A representative procedure for the preparation of BuNB-b-HFANB example 26D included the following addition of BuNB (0.99g, 6.6mmol) and toluene/TFT (19g, 50/50 wt%) to a suitable reaction vessel equipped with a magnetic stirrer, stirring the mixture for 5 minutes prior to injection of the initiator solution, addition of (η) from TFT (39mg, 0.12mmol) to a vial equipped with a magnetic stir bar³Allyl) Pd (i-Pr)₃0.23mL of 0.50M solution of P) Cl and 0.23mL of 0.50M solution of LiFeABA in TFT (100mg, 0.12mmol) and stirring for 20 min to activate the Pd main initiator 0.30mL (η)³Allyl) Pd (i-Pr)₃P)Cl/Li[FABA]Solution (pair (η)³Allyl) Pd (i-Pr)₃P) Cl and Li [ FABA ]]0.075mmol each) was injected in one portion into the flask containing the BuNB solution with vigorous stirring. After complete consumption of BuNB (15 min), a small amount of the reaction mixture was removed and quenched with acetonitrile for GPC analysis of the first polybunb block. Then, toluene/HFAN in TFT (83g, 50/50 wt.%) was addedB (4.4g, 16mmol) was added to the reaction flask. HFANB was polymerized for 3 hours. By repeating the precipitation to MeOH/H₂O (50/50 vol%) and recovering the block copolymer. The polymer thus obtained was dissolved in THF and the solution was stirred on activated carbon, followed by removal of the remaining Pd catalyst by alumina plug. The resulting filtrate was precipitated into MeOH/H₂O (50/50 vol%), followed by drying at 60 ℃ under vacuum. Changing the weight fraction W of the monomer feed composition, HFANB, as summarized in Table 3B_HFANBEssentially the same procedure was used to prepare other block copolymers of BuNB-b-HFANB. Also summarized in Table 3B are the molar ratio of block polymers, the degree of polymerization, DP, and the number average molecular weight M by GPC using a multi-angle laser Light Scattering (LS) detector (THF)_nAnd a polydispersity PDI determined by GPC using a differential Refractometry (RI) detector calibrated with narrow distribution polystyrene standards (THF).

TABLE 3B

These results are again demonstrated (η)³Allyl) Pd (i-Pr)₃P) Cl is a more reactive initiator leading to higher molecular weight polymers as summarized in table 3B. All polymers of examples 26D-26G were also characterized by Differential Scanning Calorimetry (DSC). In any of the polymers of examples 26D to 26G, no glass transition was detected from DSC to 200 ℃.

Example 27

Preparation of the film

Single Thickness Film (Single thick Film) or Thin Film Composite (TFC) Film: a polymer formed according to the present invention, as specifically disclosed in any one of examples 16 to 26, for example, was dissolved in an organic solvent to form a solution, which was then filtered. After filtration, the trapped gas was removed. The polymer is poured onto a substrate and stretched to form a film, dried and ready for use. In some cases, the film is dried and can be removed from the substrate to serve as an unsupported film.

Specifically, the polymer (10g) formed in example 16 was dissolved in THF (100g) to prepare a solution, which was filtered through a 5 μm nylon filter. After filtration, the solution was rolled over a jar roller (jar roller) overnight to remove trapped gases introduced during filtration. The polymer solution was poured onto a PAN ultrafiltration substrate and stretched using a Gardner Film Casting Knife (Gardner Film Casting Knife) to form a Film with a substantially uniform thickness. The membrane was allowed to air dry for one hour, followed by annealing at 60 ℃ for 10 minutes to form a TFC membrane. Meanwhile, the film was coated on a glass substrate, and the thickness was measured using a Dektak profilometer.

Double Thickness Film (Double Thickness Film): a dual thickness film is prepared in a similar manner to the single film except that a second layer of solution is provided on the first film before the first film is removed from the substrate and the second film is then stretched. After the second pass, the bilayer was dried and then removed from the substrate and ready for use.

For example, the single thickness film example described above was conducted except that after about 5 hours from the first film casting, a second aliquot of the polymer solution was poured onto the first film, which was stretched as performed with the Gardner film casting knife above to provide the second layer. After the second pass, the film was dried in air overnight.

Example 27A

Films of the polymers of examples 26D-G

A thin film composite membrane having a dense polymer coating of the block polymers of examples 26D-G on the upper surface was prepared by a simple blade coating (simple blade coating) method using a PAN membrane as a support. The block polymers of examples 26D-G were dissolved in toluene/TFT/THF mixture (40/40/20 wt%) to prepare a 10 wt% solution and filtered through a 0.45 μm fine pore PTFE filter. Each polymer solution thus formed was poured onto a PAN film supported by a glass sheet and stretched with a film casting knife (gap height of 25 μm) to form a film having a uniform thickness. The coating was dried slowly and annealed in a THF chamber for 2 hours to microphase separate the block copolymer. After drying the film on a hot plate at 60 ℃ for 1 hour, the film was then dried in vacuo overnight at 60 ℃.

Example 28

Pervaporation test

To place the membrane in the capsule, the membrane was cut into 2 inch diameter circles and then placed in the pervaporation test unit. The feed solution in the test unit was heated to the desired temperature for circulation in the bypass mode and then circulated through the membrane housing in the continuous mode at 450mL/min to check for leaks. After the end of the inspection, a vacuum was pulled on the dry side of the membrane and all permeate was collected into a cold trap (cooled with liquid nitrogen). The system was run for three hours and the collected permeate was warmed to room temperature and evaluated.

Evaluation of permeate

The room temperature permeate collected as described above was separated into two phase liquids. MeOH was added to the permeate to make the phases miscible, thereby providing a single phase permeate. The single phase permeate (1g) was added to a GC sampling vial containing 0.02g PGMEA and mixed well. The samples from the vials were then injected into a gas chromatograph where% butanol or% phenol was determined by evaluating the peak area of butanol or phenol against PGMEA standards.

In addition to forming flat sheet membranes supported on PAN ultrafiltration substrates, the possibility of forming hollow fibers comprising block polymer embodiments of the present invention can also be evaluated. The following procedure was used to successfully form hollow fibers for further evaluation.

Example 29

Manufacture of hollow fiber membranes

The block polymer formed according to the present invention as specifically disclosed in any one of examples 16 to 26 was dissolved in an organic solvent, and filtered to remove particles. The solution is then pressure transferred by passing it through the outer holes of the spinneret, while the mixture of solvent and salt is pressure transferred by passing it through the inner holes of the spinneret. These pressure-transferred materials are directed into a precipitation bath to provide hollow fibers. The size of the hollow fibers can be controlled by the size of the internal and external pores and the pressure of solvent transfer.

For example, the block copolymer of example 18, BuNB-b-HFANB (1:1), was dissolved in 10 wt.% THF and filtered through a 100 micron filter to remove particles. The solution was then pressure transferred through the outer orifice of a two-orifice spinneret having an outer diameter of 1.0mm and an inner diameter of 0.5mm, while a mixture of 20/80MeOH/5 wt.% LiCl (aq.) solution was pressure transferred through the inner orifice of the spinneret. These pressure-transferred materials were directed to a precipitation bath (20/80 MeOH/water) where hollow fibers were observed and evaluated. The size of the hollow fibers taken out of the bath can be confirmed by SEM.

Example 30

Formation of thin film composite hollow fibers

Generally, the polymers formed according to the present invention specifically disclosed in any one of examples 16 to 26 were dissolved in a suitable solvent (e.g., THF) at a suitable concentration (e.g., 10 wt.%) and the particles were removed by filtration through a 100 micron filter. Hollow fiber microfiltration or ultrafiltration membranes (e.g., 0.1 micron PVDF or 3000MWCO polysulfone) with blocked lumens are dipped into the block polymer solution and then pulled out of solution. The solvent is removed by drying the fibers under suitable conditions (e.g., drying at 23-60 ℃ for 0.5-12 hours). The size of the empty fibers removed from the bath can be confirmed by SEM.

Example 31

Comparative operability of Single thickness films made from the different Block Polymer compositions of the present invention and other polymers

A comparison of the block polymer and random polymer compositions of the present invention was made to observe the selective separation performance of n-butanol in the pervaporation test. The two dependent variables examined were flux and% organics in the permeate. The feed solution concentration (1%) was varied. The feed solution was heated to 65 ℃ using a hot bath. Through heat losses, it brings about a shell temperature of about 60 ℃. To collect permeate samples, vacuum traps in liquid nitrogen were used. The vacuum was 0.4in Hg (10 Torr). The feed solution was pumped into the system through a diaphragm pump at 450 mL/min. Samples were collected using a three hour test. Several different block polymers of BuNB/HFANB prepared according to example 18 were compared to a 1:1 random copolymer of BuNB/HFANB, all of which were used as thin film composite membranes prepared according to the procedure described in example 26. The thickness of the film was varied from about 2 microns to about 4 microns. The flux numbers in table 4 were normalized to the film thickness of 3 μm. The results are summarized in table 4.

TABLE 4

Pervaporation performance of feed to 1% n-butanol

n.m. ═ unmeasured

As is clear from Table 4, the membrane sample No. 6 made from the triblock polymer of HFANB-b-BuNB-b-HFANB (1:1:1) shows superior separation performance than the membrane sample No. 1 formed from the 1:1 random copolymer of BuNB/HFANBs. Most notably, as summarized in table 4, the triblock polymer (HFANB-b-BuNB-b-HFANB) was used at the same butanol concentration in the permeate to achieve significantly higher flux when compared to a membrane of similar thickness formed from the random copolymer (BuNB/HFANB random copolymer of membrane sample No. 1). It should also be noted that the film formed only from the triblock polymer, film sample No. 6, exhibited phase separation as observed by Atomic Force Microscopy (AFM) (fig. 5), clearly showing different surface morphologies when compared with the film formed from the diblock copolymer BuNB-HFANB (2:1), sample No. 3 (fig. 4) and the film formed from BuNB-b-HFANB (1:2), and the AFM of sample No. 5 (fig. 3), both of sample No. 3 and sample No. 5 exhibiting no phase separation under the conditions under which these samples were prepared, and thus having no nano-scale structure. On the other hand, the membrane formed from the triblock polymer HFANB-b-BuNB-b-HFANB, sample No. 6, fig. 5, shows an ordered structure, which may be due to among other factors, the high flux observed.

Example 32

Pervaporation test Using the Membrane of example 27A

Tests were conducted essentially using the procedure described in example 28, except for the film formed from example 27A. The effective area of the membrane was 13.38cm². The permeation flux and separation factor were determined using a 1 wt% n-BuOH aqueous solution as feed. The feed flow rate was controlled to 450mLmin by a diaphragm pump^–1. The feed temperature is controlled by a heat exchanger connected to a temperature-adjustable water circulator. The feed was circulated without the membrane for 30 minutes to heat to the desired temperature. After circulating the feed in the presence of the membrane for 1 minute to check for leaks, the permeate was collected into a cold trap immersed in liquid nitrogen using a vacuum pump. The pressure on the permeate side of the membrane was monitored by a vacuum gauge to maintain it below 10 Torr. The cold trap was weighed to calculate the total flux (J) before and after the pervaporation experiment. By using acetone-d₆As a solvent, with¹H NMR determines the composition of the permeate; adding small amount of anhydrous ethanolAdded to the permeate to make the phases miscible, providing a single phase solution prior to NMR analysis. Three different films were prepared for each of the polymers of examples 26D to 26G, and analyzed under the same experimental conditions in order to ensure the reliability of the results. For stability testing, two cold traps were used to alternatively collect the permeate and the permeate that passed through the membrane was replenished into the feed to maintain the n-BuOH feed concentration at 1 wt%. The permeate total flux (J) and Separation Factor (SF) were calculated using the equations provided above.

The pervaporation experiments were carried out at 37 ℃ and 60 ℃. In the feed solution, higher fluxes and separation factors were obtained at higher temperatures of 60 ℃. The flux measured for each membrane sample was normalized using the equation J '═ J x (t/2), where J' is the normalized flux, J is the measured flux, and t is the thickness of the membrane. For normalized flux, the effect of different membrane thicknesses on flux was eliminated. FIG. 6(a) shows the normalized flux and Separation Factor (SF) obtained for each membrane formed from the polymers of examples 26D-26G labeled a-BCPs (vinyl addition block copolymers), where W is_HFANBThe weight fraction of HFANB in each of the polymers of examples 26D-26G was used. Also shown in FIG. 6(a) are p-homopolymers, poly-HFANB (where W is_HFANBIs 1.0) and homopolymer, poly-BuNB (where W is_HFANB0.0) of the flux and SF obtained. From this data, it can be seen that the polymer of example 26E has a W of 0.81_HFANBThe polymer of (HFANB: BuNB ═ 70:30 molar ratio) showed the highest separation factor of 21.2 at 60 ℃. Then, as shown in FIG. 6(b), the flux follows W due to the decrease in the swelling ratio_HFANBGradually decreases. The Separation Factor (SF) observed for the poly-HFANB membrane was found to be only 13.7, probably due to its relatively large swelling in 1 wt% n-BuOH aqueous solution, which increased the penetration of water molecules (fig. 6 (b)).

The following two comparative examples 1 and 2 are provided herein to illustrate that certain known catalysts in the literature exhibit inferior catalytic activity compared to that of the compounds of the present invention under similar reaction conditions.

Comparative example 1

The catalyst used is palladium (acetoxy (bis (triisopropylphosphine))) (acetonitrile) tetrakis (pentafluorophenyl) borate [ Pd (OAc)) (P-i-Pr)₃)₂(CH₃CN)]Example 11 was substantially repeated, except for FABA. The monomer conversion was found to be only 25%. The polymer was characterized by GPC: m_w＝12,000；M_n＝6,600；PDI＝3.6。

Comparative example 2

The catalyst is palladium (acetylacetone) (triisopropylphosphine) (acetonitrile) tetrakis (pentafluorophenyl) borate [ Pd (acac) (P-i-Pr)₃)(CH₃CN)]Example 11 was substantially repeated in comparative example 2, except for FABA. No polymerization occurred under these conditions.

Comparative example 3

ROMP Poly HFANB-b-poly BuNB (r-BCP81)

ROMP block copolymers of HFANB and BuNB (r-BCP81) were synthesized at room temperature by sequential addition of monomers under a nitrogen atmosphere. The block copolymer was named r-BCP81, wherein ' r ' represents 'ROMP Polymer ',' BCP 'denotes'Block copolymer Copolymer', and ' 81 ' represents the weight combination of HFANB monomer units in the polymer (81 wt%). Initial monomer concentration was 4 wt%, charged as a 4 wt% solutionA continuous HFANB monomer. BuNB (0.8g, 5.3mmol) and toluene (19g) were added to a 250mL round bottom flask equipped with a magnetic stirrer and the mixture was stirred for 5 minutes before injection of the hair agent solution. To a vial equipped with a magnetic stir bar was added bis (tricyclohexylphosphine) benzylidene ruthenium (IV) dichloride (0.034g, 0.05mmol), tricyclohexylphosphine (PCy)₃0.057g, 0.2mmol) and toluene (4mL) and stirred for 5 min. The initiator solution was injected into the flask containing the BuNB solution in one shot with vigorous stirring. After complete consumption of the BuNB (1h), a small amount of the reaction mixture was removed and capped with an excess of ethyl vinyl ether for GPC analysis of the first polyBuNB block. Then HFANB (3.4g, 12mmol) in toluene (81g) was added to the reaction flask. HFANB was polymerized for 6 hours. Capping the block copolymer with an excess of ethyl vinyl ether and reacting the resulting mixture with a catalyst at N₂The solvent was evaporated and recovered under flow. The polymer thus obtained was dissolved in 1L of a cyclohexane/THF mixture (95/5 vol%) and then charged to a 2L Parr reactor. Using supports on CaCO₃(8g) Pd (0) heterogeneous (hetereogenous) catalyst on, at 100 ℃ and 400-₂The hydrogenation was carried out for 2 days. By passing¹HNMR followed the progress of the reaction and confirmed greater than 99.9% saturation of the olefinic double bonds. After filtration of the catalyst, the resulting filtrate was concentrated and precipitated into MeOH/H₂O (50/50 vol%), followed by drying at 60 ℃ under vacuum.

Comparative example 4

Random vinyl addition copolymer of HFANB/BuNB (a-RCP81)

During polymerization at room temperature under a nitrogen atmosphere, a vinyl addition random copolymer of HFANB and BuNB (a-RCP81) was synthesized by several separations of BuNB solution and charging into the reaction flask. The random copolymer was named a-RCP81, wherein ' a ' represents ' vinyl addition polymer ', ' RCP ' represents 'Random copolymer', and ' 81 ' represents the weight combination of HFANB monomer units in the polymer (81 wt%). The initial monomer concentration was 5 wt%, and all subsequent BuNB were charged as a 5 wt% solution. Mixing HFANB (4.4g, 16 mm)ol), BuNB (0.5g, 3.3mmol) and toluene/TFT (94g, 50/50 wt%) were added to a 250mL round bottom flask equipped with a magnetic stirrer, the mixture was stirred for 5 minutes before injecting the initiator solution and the (η) in TFT (39mg, 0.12mmol) was added to a vial equipped with a magnetic stir bar³Allyl) Pd (i-Pr)₃P) 0.50M solution of Cl 0.23mL Li [ FABA ] in TFT (100mg, 0.12mmol)]0.23mL of 0.5M solution and stirred for 20 minutes to activate the Pd main initiator 0.30mL (η)³Allyl) Pd (i-Pr)₃P)Cl/Li[FABA]Solution (pair (η)³Allyl) Pd (i-Pr)₃P) Cl and Li [ FABA ]]0.075mmol each) was injected in one portion into the flask containing the monomer solution with vigorous stirring. After the initiator injection, subsequent BuNB solutions (0.2, 0.15, 0.10 and 0.05g of BuNB) were then injected into the reaction flask at 10, 30, 45 and 60 minutes, respectively. The monomers were polymerized for 3 h. Random copolymer was precipitated by repeated precipitation to MeOH/H₂O (50/50 vol%) and recovered. The polymer thus obtained was dissolved in THF, and the solution was stirred on activated carbon, followed by removal of the remaining Pd catalyst by alumina plug. The resulting filtrate was precipitated into MeOH/H₂O (50/50 vol%), followed by drying at 60 ℃ under vacuum.

Comparative example 5

Pervaporation test Using r-BCP81, a-RCP81, and a-BCP81

Using the polymers from comparative examples 3 and 4, membranes were made essentially using the procedure shown in example 27A, and then tested according to the procedure shown in example 32 in order to isolate 1 wt% n-BuOH. Fig. 7(a) shows the obtained results. As is clear from fig. 7(a), the membrane of comparative example 3 formed from the ROMP polymer r-BCP81 resulted in a very low separation factor of 5.1. This may be due to the fact that: the ROMP polymer r-BCP81 with flexible backbone structure resulted in a large amount of swelling (about 31%) in a 1 wt% n-BuOH aqueous solution as shown in FIG. 7 (b).

The flux of the membrane formed from the polymer of example 26E, i.e., a-BCP81, was found to be slightly lower than that of the membrane formed from the polymer of comparative example 4, i.e., a-RCP81 membraneFlux, but the separation factor (21.2) of a-BCP81 membrane was higher than that (18.5) of a-a-RCP81 membrane. This should be attributed to microphase separation of a-BCP81 as described herein. The phase separated polybunb domains (domains) in a-BCP81 effectively inhibited swelling of the polyhfanb domains, while the randomly distributed BuNB fragments in a-RCP81 failed to provide sufficient inhibition of polyhfanb swelling due to molecular dilution of BuNB in the polyhfanb matrix (fig. 7 (b)). Thus, it should be noted that the high T of the polymers of the invention_gThe backbone structure and the molecular architecture of block copolymers (architecture) are very important for increasing the butanol selectivity in pervaporation processes.

While the invention has been illustrated by certain of the foregoing embodiments, it is not to be construed as limited thereby but is to be understood to encompass the generic scope as hereinbefore disclosed. Various modifications and embodiments may be made without departing from the spirit and scope of the invention.

Claims

1. A block polymer of the general formula (VI):

(A)_m-b-(B)_n(VI)；

wherein m and n are integers of at least 15;

b represents a bond;

wherein:

represents a position bonded to another repeating unit;

p is an integer of 0,1 or 2;

R₃、R₄、R₅and R₆Are identical or different and are each, independently of one another, selected from hydrogen, linear or branched C_1-16Alkyl, hydroxy C_1-16Alkyl, perfluoro C_1-12Alkyl radical, C_3-12Cycloalkyl radical, C_6-12Bicycloalkyl radical, C_7-14Tricycloalkyl radical, C_6-10Aryl radical, C_6-10Aryl radical C_1-3Alkyl, perfluoro C_6-10Aryl, perfluoro C_6-10Aryl radical C_1-3Alkyl, di-C_1-2Alkyl maleimide C_3-6Alkyl, di-C_1-2Alkyl maleimide C_2-6Alkoxy radical C_1-2Alkyl, hydroxy, C_1-12Alkoxy radical, C_3-12Cycloalkoxy, C_6-12Bicyclic alkoxy radical, C_7-14Tricycloalkoxy, C_6-10Aryloxy radical C_1-3Alkyl radical, C_5-10Heteroaryloxy group C_1-3Alkyl radical, C_6-10Aryloxy radical, C_5-10Heteroaryloxy or C_1-6Acyloxy, wherein each of the above substituents is optionally substituted with a group selected from halogen or hydroxy,

wherein the block polymer of the formula (VI) has residues of initiators,

the initiator is represented by the general formula (I):

wherein:

is C_5-10Cycloalkenyl radical, C_7-12Bicycloalkenyl or C_8-12A tricycloalkenyl group;

m is palladium;

LB is a Lewis base;

is a weakly coordinating anion;

y isWherein R is independently selected from methyl, ethyl, C_3-6Alkyl, substituted or unsubstituted C_3-7Cycloalkyl radical, C_6-10Aryl radical, C_6-10Aralkyl, methoxy, ethoxy, C_3-6Alkoxy, substituted or unsubstituted C_3-7Cycloalkoxy, C_6-10Aryloxy radical or C_6-10An aralkyloxy group; and

R₁is methyl, ethyl, straight or branched C_3-6Alkyl radical, C_6-10Aryl radical, C_6-10Aralkyl or R₂CO, wherein R₂Is methyl, ethyl or C_3-6An alkyl group;

or the initiator is represented by the general formula (III):

wherein:

m is palladium;

x is halogen, triflate, mesylate or tosylate;

y isWherein R is independently selected from methyl, ethyl, C_3-6Alkyl, substituted or notSubstituted C_3-7Cycloalkyl radical, C_6-10Aryl radical, C_6-10Aralkyl, methoxy, ethoxy, C_3-6Alkoxy, substituted or unsubstituted C_3-7Cycloalkoxy, C_6-10Aryloxy radical or C_6-10An aralkyloxy group; and is

R₁Is methyl, ethyl, straight or branched C_3-6Alkyl radical, C_6-10Aryl radical, C_6-10Aralkyl or R₂CO, wherein R₂Is methyl, ethyl or C_3-6An alkyl group; and is

When R is phenyl, R₁Is not methyl.

2. The block polymer of claim 1, wherein the block polymer further comprises a third repeat unit and is represented by general formula (VII):

(A)_m-b-(B)_n-b-(C)_o(VII)；

wherein m, n and b are as defined in claim 1, and o is an integer of at least 15;

c is the same as or different from a or B and is independently selected from a repeating unit represented by the general formula (IVA) derived from a monomer of the general formula (IV) as defined in claim 1.

3. The block polymer of claim 1, wherein the block molar ratio of A: B is from 1:1 to 1: 4.

4. The block polymer of claim 1, wherein the block molar ratio of A: B is from 1:1 to 1: 2.

5. The block polymer according to claim 1, wherein the block molar ratio of A: B is 1: 1.

6. The block polymer of claim 2, wherein the block molar ratio of A: B: C is from 1:1:1 to 1:4:1 to 1:1: 4.

7. The block polymer of claim 2, wherein the block molar ratio of A: B: C is 1:1: 1.

8. The block polymer of claim 2, wherein the block molar ratio of A: B: C is 1:2: 1.

9. The block polymer of claim 1, wherein a is derived from a monomer selected from the group consisting of:

5-butylbicyclo [2.2.1] hept-2-ene (BuNB);

5-hexylbicyclo [2.2.1] hept-2-ene (HexNB);

5-octylbicyclo [2.2.1] hept-2-ene (OctNB);

5-Perfluoroethylbicyclo [2.2.1]Hept-2-ene (C)₂F₅NB)；

5-n-perfluorobutylbicyclo [2.2.1]Hept-2-ene (C)₄F₉NB)；

5-perfluorohexylbicyclo [ 2.2.1%]Hept-2-ene (C)₆F₁₃NB)；

Norbornenyl-2-trifluoromethyl-3, 3, 3-trifluoropropan-2-ol (HFANB);

5-phenethylbicyclo [2.2.1] hept-2-ene (PENB); and

2- (bicyclo [2.2.1] hept-5-en-2-yl) bicyclo [2.2.1] heptane (NBANB).

10. The block polymer of claim 1, wherein B is derived from a monomer selected from the group consisting of:

5-butylbicyclo [2.2.1] hept-2-ene (BuNB);

5-hexylbicyclo [2.2.1] hept-2-ene (HexNB);

5-octylbicyclo [2.2.1] hept-2-ene (OctNB);

5-Perfluoroethylbicyclo [2.2.1]Hept-2-ene (C)₂F₅NB)；

5-n-perfluorobutylbicyclo [2.2.1]Hept-2-ene (C)₄F₉NB)；

5-perfluorohexylbicyclo [ 2.2.1%]Hept-2-ene (C)₆F₁₃NB)

Norbornenyl-2-trifluoromethyl-3, 3, 3-trifluoropropan-2-ol (HFANB);

5-phenethylbicyclo [2.2.1] hept-2-ene (PENB); and

2- (bicyclo [2.2.1] hept-5-en-2-yl) bicyclo [2.2.1] heptane (NBANB).

11. The block polymer of claim 2, wherein C is derived from a monomer selected from the group consisting of:

5-butylbicyclo [2.2.1] hept-2-ene (BuNB);

5-hexylbicyclo [2.2.1] hept-2-ene (HexNB);

5-octylbicyclo [2.2.1] hept-2-ene (OctNB);

5-Perfluoroethylbicyclo [2.2.1]Hept-2-ene (C)₂F₅NB)；

5-n-perfluorobutylbicyclo [2.2.1]Hept-2-ene (C)₄F₉NB)；

5-perfluorohexylbicyclo [ 2.2.1%]Hept-2-ene (C)₆F₁₃NB)；

Norbornenyl-2-trifluoromethyl-3, 3, 3-trifluoropropan-2-ol (HFANB);

5-phenethylbicyclo [2.2.1] hept-2-ene (PENB); and

2- (bicyclo [2.2.1] hept-5-en-2-yl) bicyclo [2.2.1] heptane (NBANB).

12. The block polymer of claim 1, wherein a is derived from a monomer selected from the group consisting of:

5-butylbicyclo [2.2.1] hept-2-ene (BuNB);

5-hexylbicyclo [2.2.1] hept-2-ene (HexNB);

5-n-perfluorobutylbicyclo [2.2.1]Hept-2-ene (C)₄F₉NB)；

Norbornenyl-2-trifluoromethyl-3, 3, 3-trifluoropropan-2-ol (HFANB);

2- (bicyclo [2.2.1] hept-5-en-2-yl) bicyclo [2.2.1] heptane (NBANB).

13. The block polymer of claim 1, wherein B is derived from a monomer selected from the group consisting of:

5-butylbicyclo [2.2.1] hept-2-ene (BuNB);

5-hexylbicyclo [2.2.1] hept-2-ene (HexNB);

5-n-perfluorobutylbicyclo [2.2.1]Hept-2-ene (C)₄F₉NB)；

Norbornenyl-2-trifluoromethyl-3, 3, 3-trifluoropropan-2-ol (HFANB);

2- (bicyclo [2.2.1] hept-5-en-2-yl) bicyclo [2.2.1] heptane (NBANB).

14. The block polymer of claim 2, wherein C is derived from a monomer selected from the group consisting of:

5-butylbicyclo [2.2.1] hept-2-ene (BuNB);

5-hexylbicyclo [2.2.1] hept-2-ene (HexNB);

5-n-perfluorobutylbicyclo [2.2.1]Hept-2-ene (C)₄F₉NB)；

Norbornenyl-2-trifluoromethyl-3, 3, 3-trifluoropropan-2-ol (HFANB);

2- (bicyclo [2.2.1] hept-5-en-2-yl) bicyclo [2.2.1] heptane (NBANB).

15. The block polymer of claim 1, selected from the following:

block polymers derived from 5-hexylbicyclo [2.2.1] hept-2-ene and norbornenyl-2-trifluoromethyl-3, 3, 3-trifluoropropan-2-ol (HexNB-b-HFANB);

a block polymer derived from 5-butylbicyclo [2.2.1] hept-2-ene and norbornenyl-2-trifluoromethyl-3, 3, 3-trifluoropropan-2-ol (BuNB-b-HFANB);

derived from 5-butylbicyclo [2.2.1]Hept-2-ene and 1- (4- (bicyclo [2.2.1]]Block polymers of hept-5-en-2-yl) butyl) -3, 4-dimethyl-1H-pyrrole-2, 5-dione (C)₄F₉NB-b-BuDMMINB)；

A block polymer derived from norbornenyl-2-trifluoromethyl-3, 3, 3-trifluoropropan-2-ol and 2- (bicyclo [2.2.1] hept-5-en-2-yl) bicyclo [2.2.1] heptane (HFANB-b-NBANB); and

block polymers derived from 5-hexylbicyclo [2.2.1] hept-2-ene and 2- (bicyclo [2.2.1] hept-5-en-2-yl) bicyclo [2.2.1] heptane (HexNB-b-NBANB).

16. The block polymer of claim 2, selected from the following:

a block polymer derived from 5-butylbicyclo [2.2.1] hept-2-ene, norbornenyl-2-trifluoromethyl-3, 3, 3-trifluoropropan-2-ol and 5-butylbicyclo [2.2.1] hept-2-ene (BuNB-b-HFANB-b-BuNB); and

17. A process for preparing a block polymer of the general formula (VI):

(A)_m-b-(B)_n(VI)；

wherein m and n are integers of at least 15;

b represents a bond;

a and B are respectively first and second monomer repeat units that are different from each other and are each independently derived from first and second monomers of formula (IV):

wherein:

represents a position bonded to another repeating unit;

p is an integer of 0,1 or 2;

R₃、R₄、R₅and R₆Are identical or different and are each, independently of one another, selected from hydrogen, linear or branched C_1-16Alkyl, hydroxy C_1-16Alkyl, perfluoro C_1-12Alkyl radical, C_3-12Cycloalkyl radical, C_6-12Bicycloalkyl radical, C_7-14Tricycloalkyl radical, C_6-10Aryl radical, C_6-10Aryl radical C_1-3Alkyl, perfluoro C_6-10Aryl, perfluoro C_6-10Aryl radical C_1-3Alkyl, di-C_1-2Alkyl maleimide C_3-6Alkyl, di-C_1-2Alkyl maleimide C_2-6Alkoxy radical C_1-2Alkyl, hydroxy, C_1-12Alkoxy radical, C_3-12Cycloalkoxy, C_6-12Bicyclic alkoxy radical, C_7-14Tricycloalkoxy, C_6-10Aryloxy radical C_1-3Alkyl radical, C_5-10Heteroaryloxy group C_1-3Alkyl radical, C_6-10Aryloxy radical, C_5-10Heteroaryloxy or C_1-6Acyloxy, wherein each of the above substituents is optionally substituted with a group selected from halogen or hydroxy;

the process comprises the following steps:

reacting the first monomer with a palladium compound to form a first polymer block; and reacting said second monomer different from the first monomer to form a block polymer,

wherein the palladium compound is represented by the general formula (I):

wherein:

m is palladium;

LB is a Lewis base;

is a weakly coordinating anion;

or the palladium compound is represented by the general formula (III):

wherein:

m is palladium;

x is halogen, triflate, mesylate or tosylate;

y isWherein R is independently selected from methyl, ethyl, C_3-6Alkyl, substituted or unsubstituted C_3-7Cycloalkyl radical, C_6-10Aryl radical, C_6-10Aralkyl, methoxy, ethoxy, C_3-6Alkoxy, substituted or unsubstituted C_3-7Cycloalkoxy, C_6-10Aryloxy radical or C_6-10An aralkyloxy group; and is

When R is phenyl, R₁Is not methyl.

18. The process of claim 17, further comprising reacting a third monomer to form a block polymer of general formula (VII):

(A)_m-b-(B)_n-b-(C)_o(VII)；

wherein m, n and b are as defined in claim 17, and o is an integer of at least 15; and

c is the same or different from A or B and is independently selected from a repeating unit represented by the general formula (IVA):

wherein p and R₃、R₄、R₅And R₆As defined in claim 17, wherein the first and second sets of coils,

the repeating units are derived from monomers of general formula (IV) as defined in claim 17.

19. The process of claim 17, wherein the block polymer formed is selected from the following:

20. The process of claim 18, wherein the polymer formed is selected from the following: