WO1997034934A1 - Free radical polymer chain initiation with unreactive unsaturates - Google Patents
Free radical polymer chain initiation with unreactive unsaturates Download PDFInfo
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- WO1997034934A1 WO1997034934A1 PCT/US1997/004326 US9704326W WO9734934A1 WO 1997034934 A1 WO1997034934 A1 WO 1997034934A1 US 9704326 W US9704326 W US 9704326W WO 9734934 A1 WO9734934 A1 WO 9734934A1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
- C08F290/04—Polymers provided for in subclasses C08C or C08F
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
Definitions
- This invention relates to a method by which olefinically-unsaturated organic molecules, which are otherwise unreactive and non-polymerizable. may be used to initiate polymer chains from free-radical monomers through the use of cobalt chain transfer catalysis, and the products of that method.
- U.S. Pat. No. 5,587,431 describes a method of preparing compositions of terminally unsaturated polymers by reinitiating the terminated ends of a terminally unsaturated oligomer with additional chain transfer catalyst (CTC) for further oligomerization.
- CTC chain transfer catalyst
- UO otherwise non-polymerizable organic molecules
- This invention concerns an improvement in a process for the free- radical polymerization of one or more monomers, hereinafter referred to as "Conventional Monomers” (CM).
- CM Conventional Monomers
- the polymers formed have vinyl-terminated end groups.
- the polymerization is initiated by a functional group derived from an olefinically-unsaturated organic molecule.
- X is selected from the group consisting of CH 3 ,and CH 2 OH; Y is selected from the group consisting of OR. 0 2 CR. halogen.
- R is selected from the group consisting of substituted and unsubstituted alkyl, substituted and unsubstituted aryl, substituted and unsubstituted heteroaryl, substituted and unsubstituted aralkyl, substituted and unsubstituted alkaryl, and substituted and unsubstituted organosilyl, the substituents being the same or different and selected from the group consisting of carboxylic acid, carboxylic ester, epoxy, hydroxyl, alkoxy, primary amino, secondary amino, tertiary amino, isocyanato, sulfonic acid and halogen; and the number of carbons in said alkyl groups is from 1 to 12; and R' is selected from the aromatic group consisting of substituted and unsubstituted aryl, substituted and unsubstituted heteroaryl, the substituents being the same or different and selected from the group consisting of carboxylic acid, carboxylic ester, epoxy, hydroxyl, alkoxy,
- R 1 and R 3 are each independently selected from the group (I) consisting of
- R 1 or R 3 are selected from group II, R 1 and R 3 may optionally form a cyclic structure; and R 2 and R 4 are each independently selected from the group (III) consisting of H, -CH(O), -CN and halogen, and from the group (IV) consisting of -C(O)OR 5 , -C(O)NR 6 R 7 , -CR 8 (0), -C(0)OC(O)R 9 , -C(0)NR'°COR 1 1 , -OC(O)R
- R 1 and R 12 are H, alkyl. aryl. substituted alkyl or substituted aryl:
- R 13 is alkyl. aryl, substituted alkyl or substituted aryl; wherein the alkyl and substituted alkyl are C,-C
- R 1 and R 2 are hydrogen
- R 3 and R 4 are each independently selected from the group (I) consisting of -CH(O), -CN and halogen, and from the group (II) consisting of -C(O)OR 5 , -C(O)NR 6 R 7 , -CR 8 (O), -C(O)OC(O)R 9 , -C(O)NR'°COR' >, -OC(O)R' 2 , -OR 13 , alkyl, substituted alkyl, aryl, and substituted aryl; wherein when R 3 or R 4 are selected from group II, R 3 and R 4 may optionally form a cyclic structure; or an embodiment where:
- R 3 and R 4 are each independently selected from the group (III) consisting of H, -CH(O), -CN and halogen, and from the group (IV) consisting of -C(O)OR 5 , -C(O)NR6R 7 , -CR 8 (0), -C(O)OC(O)R 9 , -C(O)NR 10 COR ! ', -OC(O)R 12 , -OR 13 , alkyl, substituted alkyl, aryl, and substituted aryl; wherein when R 3 or R 4 are selected from group IV, R 1 and R 2 may optionally form a cyclic structure;
- RS, R 6 , R 7 , R 8 , R 9 , R 10 , Rl l, and R 12 are H, alkyl, aryl, substituted alkyl or substituted aryl;
- R 13 is alkyl, aryl, substituted alkyl or substituted aryl; wherein the alkyl and substituted alkyl are C,-C, 2 , and the substituents on the substituted alkyl or aryl contain no functionality which would substantially interfere with free radical polymerization (e.g., groups known to be free-radical chain terminators such as thiols or nitroxides).
- This invention further relates to the products made by the above process.
- This invention further relates to a macromonomer comprised of an olefinically-unsaturated organic molecule and at least one conventional monomer, said macromonomer represented by
- R 1 . R 2 , R 3 and R 4 are each independently selected from the group consisting of H. -CH(O). -CN. halogen, -C(0)OR 5 . -C(O)NR6R 7 . -CR 8 (0),
- R 1 and R 3 or R 2 and R 4 may be combined in a cyclic structure when R 1 , R 2 , R 3 , or R 4 are C(O)OR 5 , -C(O)NR 6 R 7 .
- R 1 , R 2 , R 3 and R 4 can be H;
- R 5 , R 6 , R 7 , R 8 , R 9 , R l O , R l l , and R 12 are H, alkyl, aryl, substituted alkyl or substituted aryl;
- R 13 is alkyl, aryl, substituted alkyl or substituted aryl; wherein the alkyl and substituted alkyl are C,-C 12 , and the substituents on the substituted alkyl or aryl contain no functionality which would substantially interfere with free radical polymerization (e.g., groups known to be free-radical chain terminators such as thiols or nitrox
- Y is selected from the group consisting of OR, O 2 CR, halogen, CO 2 H, COR, CO 2 R, CN, CONH 2 , CONHR, CONR 2 and R';
- R is selected from the group consisting of substituted and unsubstituted alkyl, substituted and unsubstituted aryl, substituted and unsubstituted heteroaryl, substituted and unsubstituted aralkyl, substituted and unsubstituted alkaryl, and substituted and unsubstituted organosilyl, the substituents being the same or different and selected from the group consisting of carboxylic acid, carboxylic ester, epoxy, hydroxyl, alkoxy, primary amino, secondary amino, tertiary amino, isocyanato, sulfonic acid and halogen; and the number of carbons in said alkyl groups is from 1 to 12; and
- R' is selected from the aromatic group consisting of substituted and unsubstituted aryl, substituted and unsubstituted heteroaryl, the substituents being the same or different and selected from the group consisting of carboxylic acid, carboxylic ester, epoxy, hydroxyl, alkoxy. primary amino, secondary amino, tertiary amino, isocyanato, sulfonic acid, substituted and unsubstituted alkyl, substituted and unsubstituted aryl, substituted and unsubstituted olefin and halogen; said conventional monomer (CM) is selected from the group consisting of styrenes, acrylates, vinyl pyridines, methacrylates.
- the macromonomers of this invention are formed by the polymerization of unreactive, olefinically-unsaturated organic molecules (UO) with other conventional monomers (CM herein) in the presence of cobalt complexes capable of effecting chain transfer catalysis (CTC).
- UO is generally meant an internal olefinic monomer or other unsaturated monomeric species which does not homopolymerize or copolymerize to an appreciable extent with conventional monomers (CM) which are known to be subject to CTC - for instance, methacrylates, methacrylonitrile, ⁇ -methylstyrene and the like, as well as their fluorinated analogs.
- Preferred metallic chain transfer catalysts for use in making the present materials are cobalt (II) and (III) chelates.
- cobalt compounds are disclosed in U.S. Pat. No. 4,680,352, U.S. Pat. No. 4,694,054, U.S. Pat. No. 5,324,879, WO 87/03605 published June 18, 1987, U.S. Pat. No. 5,362,826, and
- cobalt (II) and cobalt (III) chain transfer catalysts include, but are not limited to, those represented by the following structures:
- L can be a variety of additional neutral ligands commonly known in coordination chemistry. Examples include water, amines, ammonia, phosphines,
- the catalysts can also include cobalt complexes of a variety of po ⁇ hyrin molecules such as tetraphenylpo ⁇ hyrin, tetraanisylpo ⁇ hyrin, tetramesitylpo ⁇ hyrin and other substituted species.
- Q is an organic radical (e.g., alkyl or substituted alkyl); preferred Q groups are isopropyl, 1 -cyanoethyl, and 1 -carbomethoxyethyl.
- YPC CH 2 wherein Y is selected from the group consisting of OR. 0 2 CR, halogen. C0 2 H. COR. C0 2 R. CN. CONH 2 , CONHR. CONR 2 and R " :
- R is selected from the group consisting of substituted and unsubstituted alkyl. substituted and unsubstituted aryl. substituted and unsubstituted heteroaryl, substituted and unsubstituted aralkyl. substituted and unsubstituted alkaryl, and substituted and unsubstituted organosilyl. the substituents being the same or different and selected from the group consisting of carboxylic acid, carboxylic ester, epoxy, hydroxyl, alkoxy, primary amino, secondary amino. tertiary amino, isocyanato, sulfonic acid and halogen; and the number of carbons in said alkyl groups is from 1 to 12; and
- R ' is selected from the aromatic group consisting of substituted and unsubstituted aryl, substituted and unsubstituted heteroaryl, the substituents being the same or different and selected from the group consisting of carboxylic acid, carboxylic ester, epoxy, hydroxyl, alkoxy, primary amino, secondary amino, tertiary amino, isocyanato, sulfonic acid, substituted and unsubstituted alkyl, substituted and unsubstituted aryl, substituted and unsubstituted olefin and halogen; and P is a polymeric or oligomeric group resulting from addition of a conventional monomer to polymeric or oligomeric radicals.
- Equation 1 The general reaction scheme may be summarized as Equation 1 :
- CM coproduct designated (CM) p is unavoidable, but its presence can be minimized by starved-feed reaction conditions.
- p ranges from 2 to 100, and is generally similar to m.
- Equation 2 Equation 2
- the degree of polymerization (n) is controlled by the reactivity ratio of the UO and the CM, but n is generally 2 and seldom higher than 4.
- the resulting macromonomers will contain one UO and two to 20 CM; thus, the mole ratio of UO:CM will range from about 1 :2 to about 1 :20.
- the control experiments described within the examples demonstrate this.
- R 1 and R 3 are each independently selected from the group (I) consisting of -CH(O), -CN and halogen, and from the group (II) consisting o -C(0)OR 5 .
- R 1 or R 3 may optionally form a cyclic structure
- R 2 and R 4 are each independently selected from the group (III) consisting of H, -CH(O), -CN and halogen, and from the group (IV) consisting of -C(O)OR 5 , -C(O)NR 6 R 7 , -CR 8 (O), -C(O)OC(O)R 9 , -C ⁇ NR ⁇ COR 1 ', -OC(0)R 12 , -OR 13 , alkyl, substituted alkyl, aryl, and substituted aryl; wherein when R 2 or R 4 are selected from group IV, R 2 and R 4 may optionally form a cyclic structure;
- R5, R6, R 7 , R 8 , R9, RlO, Rl 1, and R 12 are H, alkyl, aryl, substituted alkyl or substituted aryl;
- R 13 is alkyl, aryl, substituted alkyl or substituted aryl; wherein the alkyl and substituted alkyl are C,-C, 2 , and the substituents on the substituted alkyl or aryl contain no functionality which would substantially interfere with free radical polymerization (e.g., groups known to be ⁇ ee-radical chain terminators such as thiols or nitroxides).
- said conventional monomer (CM) is one or more monomers selected from the group consisting of methacrylates, methacrylonitrile, ⁇ -methylstyrene, vinyl pyrrolidone, chloroprene, and other monomers known to undergo catalytic chain transfer in the presence of cobalt chain transfer catalysts;
- said cobalt chain transfer catalyst is selected from the group consisting of cobalt(II) or (III) chelates, cobalt po ⁇ hyrins, cobalt phthalocyanines, cobalt tetraazopo ⁇ hyrins, cobalt glyoximes, cobalt cobaloximes and other suitable cobalt(II) and cobalt(III) chelates.
- CM monomers
- 2-ethylhexyl 2-hydroxymethylacrylate isobornyl 2-hydroxymethylacrylate. methyl 2-chloromethylacryiate, ethyl 2-chloromethylacrylate. propyl 2-chloromethylacrylate (all isomers). butyl 2-chloromethylacrylate (all isomers). 2-ethyihexyl 2-chloromethylacrylate. isobornyl 2-chloromethylacryiate, chloroprene. and vinylpyrrolidone.
- Preferred olefinically unsaturated organic molecules are: butenenitrile (all isomers), pentenenitrile (all isomers), methyl butenecarboxylate (all isomers), ethyl butenecarboxylate (all isomers).
- propyl butenecarboxylate (all isomers), butyl butenecarboxylate (all isomers), 2-ethylhexyl butenecarboxylate (all isomers), methyl pentenecarboxylate (all isomers), ethyl pentenecarboxylate (all isomers), perfluoro(propylvinyl)ether, methyl cinnamate, ethyl cinnamate.
- propyl cinnamate (all isomers), cinnamonitrile, methylmaleic anhydride, cyclopenten-1-one, cyclohexen-1-one, cyclohepten-1-one, dimethyl maleate, dimethyl fumarate, diethyl maleate, methyl crotonate, ethyl crotonate, crotonaldehyde, crotononitrile, methylfumaronitrile, diphenylethylene (all isomers), triphenylethylene, methyl octadecen-2-oate, ethyl octadecen-2-oate, methyl hexadecen-2-oate, ethyl hexadecen-2-oate, coumarin, methyl coumarin-3- carboxylate, and methylitaconic anhydride.
- the UO can be utilized as the polymerization "solvent", in that there is a preponderance of it, and the other monomer(s) (CM) ideally would be added in a starved-feed manner to allow optimum control of the design of the product.
- CM monomer(s)
- the UO is truly monomeric, i.e., no macromonomers are present as starting material.
- initiator which produces carbon-centered radicals, sufficiently mild not to destroy the metal chelate chain transfer catalyst, is typically also employed in preparing the polymers.
- Suitable initiators are azo compounds having the requisite solubility and appropriate half life, including azocumene; 2,2'-azobis(2- methyl)-butanenitrile; 2.2 , -azobis(isobutyronitrile)(AIBN); 4,4'-azobis(4- cyanovaleric acid); and 2-(t-butylazo)-2-cyanopropane. and other compounds known to those skilled in the art.
- the polymerization process employing the above described metallic chain transfer catalysts, is suitably carried out at a temperature ranging from about room temperature to about 240°C or higher, preferably about 50°C to 150°C.
- the polymers made by the inventive process are typically prepared in a polymerization reaction by standard solution polymerization techniques, but may aiso be prepared by emulsion, suspension or bulk polymerization processes.
- a continuous (CSTR) polymerization process may also be used.
- the polymerization process can be carried out as either a batch, semi-batch, or continuous process. When carried out in the batch mode, the reactor is typically charged with metal chain transfer catalyst, a conventional monomer, and the unsaturated organic, optionally with a solvent.
- the terminally unsaturated oligomers or macromonomers prepared according to the present invention can be employed, not only as non-metallic chain transfer agents, but as useful components or intermediates in the production of graft copolymers, non-aqueous dispersed polymers, microgels, star polymers, branched polymers, and ladder polymers.
- Oligomers, macromonomers and polymers made by the present process are useful in a wide variety of coating and molding resins.
- Other potential uses can include cast, blown, spun or sprayed applications in fiber, film, sheet, composite materials, multilayer coatings, photopolymerizable materials, photoresists, surface active agents, dispersants, adhesives, adhesion promoters, coupling agents, and others.
- End products taking advantage of available characteristics can include, for example, automotive and architectural coatings or finishes, including high solids, aqueous, or solvent based finishes.
- Polymers, such as those produced in this invention would find use in, for example, structured polymers for use as pigment dispersants.
- freeze-pump-thaw cycle as used in the examples below is described in D.F.shriver, et al., "The Manipulation of Air Sensitive Compounds", 2nd ed., Wiley Interscience, 1986.
- K + IDS mass spectroscopy is an ionization method that produces pseudomolecular ions in the form of [M]K + with little or no fragmentation. Intact organic molecules are desorbed by rapid heating. In the gas phase the organic molecules are ionized by potassium attachment. Potassium ions are generated from an aluminosilicate matrix that contains K 0. All of these experiments were performed on a Finnegan Model 4615 GC/MS quadrupole mass spectrometer ( Finnegan MAT (USA). San Jose. CA). An electron impact source configuration operating at 200°C and a source pressure of ⁇ 1 x 1 O *6 torr was used.
- MW and DP measurements were based on gel permeation chromatography (GPC) using styrene as a standard, and performed on a WISP 712 Chromatograph with 100 A, 500 A. 1000 A and 5000 A phenogel columns (Waters Co ⁇ .,
- M pic is a measure of the molecular weight of the largest molecular ion signal obtained with K + IDS. and is generally a value between MN and MW.
- TAPCo meso-tetra(4-methoxyphenyl)po ⁇ hyrin-Co
- VAZO-88® l,r-azobis(cyclohexane-l-carbonitrile (DuPont Co.,
- AIBN 2,2'-azobis(isobutyronitrile)
- THPCo tetrakis(4-hexylphenyl)po ⁇ hyrin-Co
- DMM dimethyl maleate
- EC ethyl crotonate
- a solution of 2 mg of TAPCo, 2.6 mg of VAZO®-88, 0.6 mL of 1,2-dichloroethane, 0.4 mL of 2-PN and 0.04 mL of MMA was degassed by three freeze-pump-thaw cycles, sealed and immersed into a 90°C circulating bath for 2 hours. The solution was sealed and another portion of 0.04 mL of MMA was added promptly. Then it was degassed as described above and immersed into a 90°C isothermal bath for an additional 2 hours.
- Example 2 Initiation of MMA with 2-cvano-2-butene A solution of 4 mg of TAPCo. 2 mg of AIBN. 0.7 mL of chloroform. 0.3 mL of 2-cyano-2-butene and 0.08 mL of MMA was degassed by three freeze- pump-thaw cycles, sealed and immersed into a 70°C circulating bath for 2 hours.
- the solution was sealed and 0.06 mL of MMA was added promptly. Then it was degassed as described above and immersed into a 70°C isothermal bath for an additional three hours. Then another 0.06 L of MMA was added and the solution was kept at 70°C for another three hours.
- Example 3 Initiation of MMA with crotonaldehvde A 0.04 mL aliquot of MMA was added to a reaction mixture which contained 5 mg THPCo, 0.9 mL of crotonaldehyde and 8 mg VAZO®-88. The reaction solution was then degassed by three freeze-pump-thaw cycles, sealed and immersed into a 100°C circulating bath for one hour.
- Example 6 Initiation of MMA with DEM A 0.08 mL aliquot of MMA was added to a reaction mixture containing 2 mg THPCo, 1.8 mL DEM and 16 mg VAZO®-88. The reaction solution was then degassed by three freeze-pump-thaw cycles, sealed and immersed into a 100°C circulating bath for one hour.
- Example 7 Initiation of MMA with CPO A 0.08 mL aliquot of MMA was added to a reaction mixture which contained 1 mg bis(diphenylglyoxime)-(triphenylphosphine)cobalt(III)chloride, 1.8 mL CPO and 16 mg VAZO®-88. The reaction solution was then degassed by three freeze-pump-thaw cycles, sealed and immersed into a 100°C circulating bath for 40 min. The above procedure was repeated two more times, but with 90 min and
- MMA was added to a reaction mixture which contained 10 mg THPCo, 6 mL dichloroethane, 0.12 g VAZO®-88, 3 mL FREON-1 13 and 9 mL PPVE.
- the MMA was added three times and after each addition, the reaction solution was degassed and kept at 100 °C for 60 minutes.
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Priority Applications (8)
Application Number | Priority Date | Filing Date | Title |
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JP53363397A JP3798027B2 (en) | 1996-03-21 | 1997-03-19 | Free radical polymer chain initiation using inert unsaturates |
KR10-1998-0707437A KR100472683B1 (en) | 1996-03-21 | 1997-03-19 | Free Radical Polymer Chain Initiation with Unreactive Unsaturates |
NZ331464A NZ331464A (en) | 1996-03-21 | 1997-03-19 | Free radical polymer chain initiation with unreactive unsaturates |
BR9708185A BR9708185A (en) | 1996-03-21 | 1997-03-19 | Process for polymerization via free radical to macromonomer |
AU23328/97A AU727977B2 (en) | 1996-03-21 | 1997-03-19 | Free radical polymer chain initiation with unreactive unsaturates |
EP97916060A EP0888388B1 (en) | 1996-03-21 | 1997-03-19 | Free radical polymer chain initiation with unreactive unsaturates |
CA002249438A CA2249438C (en) | 1996-03-21 | 1997-03-19 | Free radical polymer chain initiation with unreactive unsaturates |
DE69703097T DE69703097T2 (en) | 1996-03-21 | 1997-03-19 | FREE RADICAL POLYMER CHAIN INITIATION WITH NON-REACTIVE UNSATURATED CONNECTIONS |
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US1379996P | 1996-03-21 | 1996-03-21 | |
US60/013,799 | 1996-03-21 | ||
US08/818,860 | 1997-03-17 |
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1113025A2 (en) * | 1999-12-27 | 2001-07-04 | Sumitomo Chemical Company, Limited | Catalyst component for addition polymerization, catalyst for addition polymerization, and process for producing addition polymer |
US6472463B1 (en) | 1999-12-17 | 2002-10-29 | E. I. Du Pont De Nemours And Company | Graft copolymer pigment dispersant |
US6495618B1 (en) | 1999-12-17 | 2002-12-17 | E. I. Du Pont De Nemours And Company | Graft copolymer with an amide functional group as a pigment dispersant |
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WO1987003605A1 (en) * | 1985-12-03 | 1987-06-18 | Commonwealth Scientific And Industrial Research Or | Oligomerization process |
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Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6472463B1 (en) | 1999-12-17 | 2002-10-29 | E. I. Du Pont De Nemours And Company | Graft copolymer pigment dispersant |
US6495618B1 (en) | 1999-12-17 | 2002-12-17 | E. I. Du Pont De Nemours And Company | Graft copolymer with an amide functional group as a pigment dispersant |
EP1113025A2 (en) * | 1999-12-27 | 2001-07-04 | Sumitomo Chemical Company, Limited | Catalyst component for addition polymerization, catalyst for addition polymerization, and process for producing addition polymer |
EP1113025A3 (en) * | 1999-12-27 | 2001-07-25 | Sumitomo Chemical Company, Limited | Catalyst component for addition polymerization, catalyst for addition polymerization, and process for producing addition polymer |
US6852809B2 (en) | 1999-12-27 | 2005-02-08 | Sumitomo Chemical Company, Limited | Catalyst component for addition polymerization, catalyst for addition polymerization, and process for producing addition polymer |
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