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WO2003000750A1 - Procedes de polymerisation faisant intervenir un catalyseur hautement actif - Google Patents

Procedes de polymerisation faisant intervenir un catalyseur hautement actif Download PDF

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Publication number
WO2003000750A1
WO2003000750A1 PCT/US2002/019965 US0219965W WO03000750A1 WO 2003000750 A1 WO2003000750 A1 WO 2003000750A1 US 0219965 W US0219965 W US 0219965W WO 03000750 A1 WO03000750 A1 WO 03000750A1
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Prior art keywords
halogenated
independently
aryl
biaryl
arylene
Prior art date
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Ceased
Application number
PCT/US2002/019965
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English (en)
Inventor
Eugene Y. Chen
Debashis Chakraborty
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Colorado State University Research Foundation
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Colorado State University Research Foundation
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Filing date
Publication date
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Publication of WO2003000750A1 publication Critical patent/WO2003000750A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/04—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers only
    • C08G65/06—Cyclic ethers having no atoms other than carbon and hydrogen outside the ring
    • C08G65/08—Saturated oxiranes
    • C08G65/10—Saturated oxiranes characterised by the catalysts used
    • C08G65/12—Saturated oxiranes characterised by the catalysts used containing organo-metallic compounds or metal hydrides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
    • C08G65/2642—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds characterised by the catalyst used
    • C08G65/2645—Metals or compounds thereof, e.g. salts
    • C08G65/2654—Aluminium or boron; Compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
    • C08G65/2642—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds characterised by the catalyst used
    • C08G65/2645—Metals or compounds thereof, e.g. salts
    • C08G65/266—Metallic elements not covered by group C08G65/2648 - C08G65/2645, or compounds thereof

Definitions

  • the present invention provides a method for polymerizing epoxides and olefins.
  • Polyethers made from epoxides are well known and useful in a number of applications, such as detergent and cleaner compositions, oil well drilling fluids, inks, metal working fluids, lubricants in paper coating compositions, ceramics manufacturing, chemical intermediates for nonionic surfactants which in turn are used in cosmetics, textiles and chemical processing, cellular and noncellular polyurethanes, chemical intermediates for esters which are used in textile spin finishes, cosmetic agents, and as foam control agents for a wide variety of processes.
  • epoxides i.e., al ylene oxides
  • polymers may have no more than one oxyalkylene group in succession, or be a higher molecular weight polymer containing one or more long chains of consecutive oxyalkylene groups.
  • Polyethers of this type are commonly made through an anionic polymerization process, whereby the epoxide is combined with an initiator compound and a strongly basic catalyst such as potassium hydroxide or certain organic amines.
  • the initiator compound contains one or more oxyalkylatable groups such as hydroxyl, thiol, carboxylic acid and the like.
  • the initiator compound determines the functionality (i.e., number of hydroxyl groups/molecule of product) and in some cases may introduce some desired functional group into the product.
  • initiator compounds cannot be alkoxylated using strongly basic catalysts, because they contain base-sensitive functional groups.
  • initiators containing certain types of alkenyl or alkynyl groups undergo a side reaction in which the alkenyl or alkynyl group will "migrate" along the molecular chain, so that the unsaturation in the polyether is at a different place than it was on the initiator. This is of particular concern when terminal unsaturation is desired. Often, unsaturation that is in a terminal position on the initiator migrates to a non-terminal position during the alkoxylation reaction.
  • One aspect of the present invention provides a process for polymerizing an epoxide.
  • the process comprises contacting the epoxide with a polymerization catalyst to produce a polyether, i.e., poly(alkylene oxide) polymer.
  • the polymerization catalyst comprises (a) a metal selected from the group consisting of boron, aluminum, and gallium; and (b) a ligand selected from the group consisting of halogenated aryl, halogenated aryloxy, halogenated biaryl, halogenated biaryloxy, halogenated arylene, and a mixture thereof.
  • Another aspect of the present invention provides a process for producing a polyolefin by polymerizing an olefin in the presence of a polymerization catalyst.
  • the polymerization catalyst for production of the polyolefin comprises (a) aluminum; and (b) a ligand selected from the group consisting of halogenated aryl, halogenated aryloxy, halogenated biaryl, halogenated biaryloxy, halogenated arylene, and a mixture thereof.
  • the present invention is to effectively end-capping polyether polyols containing a secondary hydroxyl group with ethylene oxide using a catalyst of the present invention.
  • the polyether polyol is prepared using a non-finishing catalyst, such as a double metal cyanide (DMC) catalyst.
  • a non-finishing catalyst such as a double metal cyanide (DMC) catalyst.
  • the catalysts of the present invention can be used to add alkylene oxides to monomeric initiators containing two or more active hydrogen atoms, such as glycerin, sorbitol, sucrose, trimethylol propane, etc. The resulting products can be further reacted with other alkylene oxide monomers to provide higher molecular weight polyols.
  • the present inventor has found that polymerization catalysts of the present invention have a high turn-over rate. Furthermore, polymerization catalysts of the present invention produce polymers at a significantly higher yield then similar catalysts having non-halogenated ligands.
  • Figure 1 shows some of the representative polymerization catalysts of the present invention.
  • Alkyl refers to a saturated linear or branched monovalent hydrocarbon moiety having from one to twenty carbon atoms, preferably one to six carbon atoms.
  • exemplary alkyl groups include methyl, ethyl, ⁇ -propyl, 2-propyl, tert-butyl, pentyl, and the like.
  • Alkoxy refers to a moiety of the formula -OR , where R b is alkyl as defined above.
  • Aryl refers to a monovalent monocyclic or bicyclic aromatic hydrocarbon moiety of six to ten carbon ring atoms.
  • the aryl group can be optionally substituted with one or more substituents selected from alkyl, haloalkyl, and alkoxy group.
  • the term aryl includes, but is not limited to, phenyl, naphthyl, and the like.
  • Arylene refers to a divalent monocyclic or bicyclic aromatic hydrocarbon moiety of six to ten carbon ring atoms.
  • the arylene group can be optionally substituted with one or more substituents selected from alkyl, haloalkyl, and alkoxy group.
  • aryl includes, but is not limited to, phenylene, naphthylene, and the like. When one or more number is present in front of the term “arylene", the numbers indicate relative positions of the substituents.
  • 1,2-phenylene and 1,4-phenylene refer to divalent phenyl groups in which two substituents attached to the arylene are at positions 1,2- and 1,4- relative to each other, respectively.
  • Aryloxy refers to a moiety of the formula -OR a , where R a is aryl as defined above.
  • Biaryl refers to an aryl group which is substituted with another aryl group.
  • Exemplary aryl groups include biphenyl, binaphthyl, phenylnaphthyl, and the like.
  • Halogenated refers to a moiety in which one or more hydrogen has been replace with halide, such as chlorine, bromine, or preferably fluorine.
  • Perfluorinated means all of the hydrogen atoms of a moiety have been replaced with fluorine.
  • Turn-over rate refers to moles of monomers consumed per mole of a polymerization catalyst per hour. The turn-over rate is typically measured in the absence of any significant amount of solvent.
  • the terms "those defined above” and “those defined herein” when referring to a variable incorporates by reference the broad definition of the variable as well as preferred, more preferred and most preferred definitions, if any.
  • Polymerization catalysts of the present invention are useful in polymerization reactions of epoxides and olefins. Unlike conventional catalysts, present inventors have found that the catalysts of the present invention have a high turn-over rate thereby requiring only a small amount of the catalyst and/or a short polymerization reaction time. Furthermore, polymerization catalysts of the present invention produces polymers at a significantly higher yield compared to similar catalysts having non-halogenated ligands. [27] While the present invention is generally described in connection with using the polymerization catalysts described herein, methods of the present invention are not limited to this composition.
  • methods of the present invention can also include one or more initiators which are conventionally known to one skilled in the art in producing polyethers from epoxides.
  • methods of the present invention can also include other components which are typically used in polymerization reactions, such as stabilizers, surfactants, coloring agents, cross-linkers, etc.
  • Polymerization catalysts of the present invention comprise a metal and a halogenated aromatic ligand.
  • the aromatic ligand can be attached directed to the metal or it can be attached to the metal through an oxygen atom.
  • the metal is a Group III metal, e.g., boron, aluminum, gallium, indium, and thallium. More preferably, the metal is selected from the group consisting of boron, aluminum, and gallium. For polymerization of epoxides, the metal is preferably boron or aluminum. For polymerization of olefins, the metal is preferably aluminum.
  • the ligand is selected from the group consisting of halogenated aryl, halogenated aryloxy, halogenated biaryl, halogenated biaryloxy, halogenated arylene, and a mixture thereof.
  • At least one of the ligand is perhalogenated moiety described above. Still more preferably, at least one of the ligand is perfluorinated moiety described above. And most preferably, all of the ligands are perfluorinated moiety described above.
  • the polymerization catalyst is of the formula: (X) a -M-[(0) b -Ar 1 ] c
  • each Ar 1 is independently halogenated aryl or halogenated biaryl. More preferably, each Ar 1 is independently perfluorinated aryl or perfluorinated biaryl. Still more prefrably, each Ar 1 is independently pentylfluorophenyl, 2-pentafluorophenyl-3, 4,5,6- tetrafluorophenyl, or l,3,4,5,6,7,8-heptafluoronaphth-2-yl.
  • the polymerization catalyst is of the formula: [Ar 1 -(O) b ] c -M 1 -Ar 2 -M 2 -[(O) d -Ar 3 ] e ⁇
  • b, c, and Ar 1 are those defined herein; each of M 1 and M 2 is independently B, Al, or Ga; preferably M 1 and M 2 are the same; each d is independently 0 or 1; each Ar is independently aryl, halogenated aryl, biaryl, or halogenated biaryl; and Ar 2 is arylene or halogenated arylene; each e is independently an integer of at least 1, provided at least one of Ar 1 and Ar 3 is halogenated aryl or Ar 2 is halogenated arylene, and provided the sum of c+1 and the sum of e+1 are equal to the oxidation state of appropriate M, i.e., metal to which respective ligands having variable c and
  • each of Ar and Ar is independently halogenated aryl.
  • Ar and Ar are pentafluorophenyl.
  • b and d are 0.
  • Ar is 1,2-substituted phenylene, 1,2-substituted tetrafluorophenylene, 1,4-substituted phenylene, or 1,4-substituted tetrafluorophenylene.
  • the polymerization catalyst is of the formula:
  • M 1 , M 2 , b, d, Ar 1 , Ar 2 , and Ar 3 are those defined herein;
  • Ar 4 is independently arylene or halogenated arylene; provided at least one of Ar 1 or Ar 3 is halogenated aryl or one of Ar 2 or Ar 4 is halogenated arylene.
  • each of Ar 2 and Ar 4 is independently 1,2- substituted phenylene, 1,2-substituted tetrafluorophenylene, 1,4-substituted phenylene, or
  • polymerization catalysts of the present invention are useful in producing polyethers from epoxides such as, but are not limited to, ethylene oxide, propylene oxide, butylene oxide, and cyclohexene oxide.
  • polymerization catalysts of the present invention are also useful in producing polymers from olefins, such as styrene, isobutylene and vinyl ether.
  • the catalysts are also useful in capping of polyalkylene oxides and polyoxystyrene polymers with ethylene oxide (EO), examples of such polymers include polypropylene, polybutylene, polypropylene/ polybutylene polymers or a mixture thereof.
  • EO ethylene oxide
  • the catalyst is used to end-cap a polyoxypropylene polymer with EO.
  • Process conditions for end-capping with EO are well known in the art.
  • the turn-over rate of the polymerization catalysts of the present invention is at least about 500 per hour, preferably at least about 1,000, more preferably at least about 2,000, and most preferably at least about 4,000.
  • the amount of the polymerization catalyst used can be significantly less than the stoichiometric amount, i.e., less than one equivalent, of the compound.
  • the amount of polymerization catalyst used is less than about 0.1 mole% of the epoxide, preferably less than about 0.01 mole%, and more preferably less than about 0.001 mole .
  • the present invention is not limited to the above described turn-over rate and catalyst concentration.
  • the tum-over rate and the amount of catalyst used in a given reaction depends on a variety of factors, including the nature of the substrate, reaction solvent, the amount and/or the nature of any impurities that may be present in the reagents and/or the solvent, etc.
  • the preferred turn-over rate is at least about 50,000, more preferably at least about 100,000, and most preferably at least about 150,000.
  • the turn-over rate is preferably at least about 20,000, more preferably at least about 40,000, and most preferably at least about 60,000.
  • the turn-over rate is preferably at least about 2000, more preferably at least about 3,000, and most preferably at least about 4,000.
  • the catalysts are typically prepared from reaction of group El metal halides, alkyls, or alkoxides with an appropriate halogenated aromatic organic ligand in neutral form or anionic form complexed with other metals such as Li, Mg, Sn, etc. Hydrocarbon and ether solvents are commonly used for the catalyst preparation.
  • the catalysts are generally isolated and purified by recrystallization or sublimation.
  • the invention includes a process for making an epoxide polymer.
  • This process comprising polymerizing an epoxide in the present of a catalyst of the present invention.
  • Preferred epoxides are ethylene oxide propylene oxide, butylene oxides, styrene oxide, and the like, and mixtures thereof.
  • the process can be used to make random or block copolymers.
  • the epoxide polymer can be, for example, a polyether polyol derived from the polymerization of an epoxide in the presence of a hydroxyl group containing initiator. Process conditions for such polymerization reactions are well known in the art.
  • Polymers produced by a process of the present invention are useful in a variety of applications, including, but not limited to producing polyurethanes.
  • Polyurethanes can be produced by reacting a polyol which is prepared according to the process described herein with an isocyanate.
  • Processes for producing polyurethanes is well known to one of ordinary skill in the art. For example, see U.S. Patent Nos. 5,010,117, issued to Herrington et al., 3,535,307, issued to Moss et al., and 4,687,851, issued to Laughner, and EP Publication No. 0 394 487 by Takeyasu et al., which are incorporated herein by reference in their entirety.
  • Tris(perfluorophenyl)borane B(C 6 F 5 ) 3 was obtained as from Boulder Scientific Company and used without further purification for preparative reactions, or purified by recrystallization from hexane at -35 °C for NMR-scale reactions.
  • Trimethylaluminum (AlMe ) in toluene or hexanes, aluminum tri-isopropoxide (Al(O ! Pr) 3 ), and pentafluorophenol were purchased from Aldrich Chemical Co.
  • AlCO'Prfo was freshly vacuum distilled prior to use.
  • This example illustrates a method for producing tris(perfluorophenyl)alane catalyst.
  • Tris(perfluorophenyl)alane (A1(C 6 F 5 ) 3 as a toluene adduct) catalyst was prepared by exchange reaction between tris(perfluorophenyl)borane and trimethylaluminum as disclosed in U.S. Patent No. 5,602269, issued to Biagini, et al., which is incorporated herein by reference in its entirety.
  • Example 2
  • This example illustrates a method for producing a mixture of catalysts.
  • a mixture of B(C 6 F 5 ) 3 and AlMe 3 was prepared by mixing B(C 6 F 5 ) 3 and
  • This example illustrates a method for producing Al(OC 6 F 5 ) 3 .
  • initiator is methanol.
  • initiator is 1,4-butanediol.
  • initiator is 2,5-hexanediol.
  • initiator is benzyl alcohol.
  • /. initiator is C 6 H 5 COOH.
  • initiator is C 6 H 5 OH.
  • h. initiator is H 2 O.
  • This example illustrates polymerization of cyclohexene oxide using variety of polymerization catalysts of the present invention.
  • polymerization catalysts of the present invention comprising aluminum metal are particularly useful in olefin polymerization reaction.
  • This example illustrates end-capping of a polyoxypropylene polyol with ethylene oxide.
  • Catalysts were tested for EO capping in a 300 ml Parr Raeactor.
  • the apparatus was controlled via a Camile laboratory system.
  • the reactor is equipped with a hollow agitator shaft and a gas dispersion impeller.
  • the gaseous EO feed take was maintained with a pad of at least 60 psig nitrogen. At termination of the feed, the system was vented and the product removed. The results of the
  • the rate is measured as ml EO/hr/1000 ppm catalyst. NMR analysis of the product polymer was used to estimate the extent of the EO capping.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyethers (AREA)

Abstract

L'invention concerne un procédé de polymérisation d'un époxyde ou d'une oléfine en présence d'un catalyseur composé de bore, d'aluminium ou de gallium et d'un ligand sélectionné parmi un aryle halogéné, un aryloxy halogéné, un biaryle halogéné, un biaryloxy halogéné, un arylène halogéné, ou un mélange de ceux-ci. Ce procédé, qui ne nécessite pas l'extraction du catalyseur du produit polymérisé, est suffisamment souple pour être utilisé avec une multitude d'initiateurs.
PCT/US2002/019965 2001-06-20 2002-06-20 Procedes de polymerisation faisant intervenir un catalyseur hautement actif Ceased WO2003000750A1 (fr)

Applications Claiming Priority (2)

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US29963101P 2001-06-20 2001-06-20
US60/299,631 2001-06-20

Publications (1)

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WO2003000750A1 true WO2003000750A1 (fr) 2003-01-03

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008038678A1 (fr) 2006-09-27 2008-04-03 Asahi Glass Company, Limited Procédé servant à produire une mousse de polyuréthane souple
WO2010127230A2 (fr) 2009-04-30 2010-11-04 E. I. Du Pont De Nemours And Company Procédé d'alcoxylation d'alcools

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5602269A (en) * 1994-07-29 1997-02-11 Enichem Elastomeri S.R.L. Organometallic derivatives of group IIIA and process for their preparation
WO2000002952A1 (fr) * 1998-07-10 2000-01-20 Sanyo Chemical Industries, Ltd. Nouveaux polyoxyalkylenepolyols et procede de production d'un polymere a cycle ouvert
JP2000344813A (ja) * 1999-06-01 2000-12-12 Nippon Shokubai Co Ltd カチオン重合方法およびそれに使用するカチオン重合用触媒

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5602269A (en) * 1994-07-29 1997-02-11 Enichem Elastomeri S.R.L. Organometallic derivatives of group IIIA and process for their preparation
WO2000002952A1 (fr) * 1998-07-10 2000-01-20 Sanyo Chemical Industries, Ltd. Nouveaux polyoxyalkylenepolyols et procede de production d'un polymere a cycle ouvert
JP2000344813A (ja) * 1999-06-01 2000-12-12 Nippon Shokubai Co Ltd カチオン重合方法およびそれに使用するカチオン重合用触媒

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
DATABASE CAPLUS [online] SUN ET AL.: "Al-, Nb-, Ta-based perfluoroalkyl oxide anions as cocatalysts for metallocene-mediated Ziegler-Natta olefin polymerization", XP002957780, Database accession no. 2000:215370 *
DATABASE CAPLUS [online] XP002957778, Database accession no. 2000:53769 *
DATABASE CAPLUS [online] XP002957779, Database accession no. 2000:873318 *
ORGANOMETALLICS, vol. 19, no. 9, 2000, pages 1625 - 1627 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008038678A1 (fr) 2006-09-27 2008-04-03 Asahi Glass Company, Limited Procédé servant à produire une mousse de polyuréthane souple
WO2010127230A2 (fr) 2009-04-30 2010-11-04 E. I. Du Pont De Nemours And Company Procédé d'alcoxylation d'alcools
EP2424830A4 (fr) * 2009-04-30 2014-09-17 Du Pont Procédé d'alcoxylation d'alcools
AU2010242869B2 (en) * 2009-04-30 2016-06-16 The Chemours Company Fc, Llc. Process for the alkoxylation of alcohols

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