WO2017122295A1 - オレフィン-芳香族ビニル化合物系共重合体の製造方法及びクロス共重合体の製造方法 - Google Patents
オレフィン-芳香族ビニル化合物系共重合体の製造方法及びクロス共重合体の製造方法 Download PDFInfo
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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
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
- C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
- C08F4/6592—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
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- 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
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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
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
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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
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/06—Hydrocarbons
- C08F212/08—Styrene
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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
- C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
- C08F297/02—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type
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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
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/52—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides selected from boron, aluminium, gallium, indium, thallium or rare earths
Definitions
- the present invention relates to a method for producing an olefin-aromatic vinyl compound copolymer and a method for producing a cross copolymer.
- the present invention provides a method for producing an olefin-aromatic vinyl compound copolymer which can increase the polymerization activity per catalyst and reduce the catalyst cost in the production of an olefin-aromatic vinyl compound copolymer. Is an issue.
- the present inventor in the production of olefin-aromatic vinyl compound copolymer, especially cross-copolymer, in the process of repeatedly studying to increase the production efficiency per polymerization catalyst and reduce the catalyst cost, It was found that the content of phenylacetylene greatly affects the production efficiency per polymerization catalyst. Based on this knowledge, when producing an olefin-aromatic vinyl compound copolymer by coordination polymerization, the content of phenylacetylene in the raw material styrene is kept below a certain value, thereby increasing the production efficiency per catalyst. It has been found that this can be done, and the present invention has been completed.
- the content of phenylacetylene in the aromatic vinyl compound monomer is 50 ppm or less in the step of obtaining the olefin-aromatic vinyl compound copolymer by bringing the raw material monomer into contact with the single site coordination polymerization catalyst. Particularly preferably, it is 30 ppm or less.
- the polymerization activity per catalyst can be increased, and the catalyst cost can be reduced.
- olefin / aromatic vinyl compound copolymer includes “olefin / aromatic vinyl compound copolymer” and “olefin / aromatic vinyl compound / aromatic polyene copolymer”. It is.
- the method for producing an olefin-aromatic vinyl compound copolymer according to the present invention comprises contacting an olefin monomer and a raw material monomer containing an aromatic vinyl compound monomer with a single-site coordination polymerization catalyst to bring the olefin-aromatic vinyl compound copolymer into contact with each other. It has a coordination polymerization step for producing a coalescence.
- the method for producing an olefin-aromatic vinyl compound-aromatic polyene copolymer comprises contacting an olefin monomer, an aromatic vinyl compound monomer, and a raw material monomer containing an aromatic polyene monomer with a single-site coordination polymerization catalyst. It has a coordination polymerization step for producing an olefin-aromatic vinyl compound-aromatic polyene copolymer.
- the raw material monomer includes an olefin monomer and an aromatic vinyl compound monomer when an olefin-aromatic vinyl compound copolymer is obtained. Further, when obtaining an olefin-aromatic vinyl compound-aromatic polyene copolymer, an aromatic polyene monomer is further included.
- the olefin monomer include ethylene and ⁇ -olefins having 3 to 20 carbon atoms, that is, propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene and the like.
- the olefin includes a cyclic olefin, and examples of the cyclic olefin include vinylcyclohexane, cyclopentene, norbornene and the like.
- ethylene or a mixture of ethylene and an ⁇ -olefin, that is, propylene, 1-butene, 1-hexene, 1-octene, or the like is used, and more preferably, ethylene is used.
- aromatic vinyl compound monomers examples include styrene and various substituted styrenes such as p-methylstyrene, m-methylstyrene, o-methylstyrene, ot-butylstyrene, mt-butylstyrene, and pt-butyl. Examples thereof include styrene, p-chlorostyrene, o-chlorostyrene and the like. Industrially, styrene, p-methylstyrene, p-chlorostyrene, and particularly preferably styrene is used.
- the content of phenylacetylene in the aromatic vinyl compound monomer is 50 ppm or less.
- the content of phenylacetylene in the aromatic vinyl compound monomer is particularly preferably a styrene monomer of 30 ppm or less.
- a method for producing an aromatic vinyl compound monomer (styrene) satisfying such conditions can be obtained by a known method such as JP-A-06-157364, JP-A-07-278021, JP-A-2000-191557. Can do.
- the content of phenylacetylene in the aromatic vinyl compound monomer can be determined by a known method, but can be generally determined by a gas chromatographic method.
- the aromatic polyene monomer is a monomer having a carbon number of 10 to 30 and having a plurality of double bonds (vinyl group) and one or a plurality of aromatic groups and capable of coordination polymerization.
- One of the vinyl groups) is an aromatic polyene in which the double bond remaining in the polymerized state is used for coordination polymerization and can be anionically polymerized or radically polymerized.
- the aromatic polyene one or a mixture of two or more of orthodivinylbenzene, paradivinylbenzene and metadivinylbenzene is preferably used.
- the total of the mass of units derived from the olefin and the aromatic vinyl compound is 90% by mass or more, preferably 95% by mass or more of the entire copolymer. It is a polymer.
- the composition of the olefin-aromatic vinyl compound copolymer is arbitrary within the above range. For example, an olefin-aromatic vinyl compound copolymer having an olefin content of 95 mol% to 50 mol% and an aromatic vinyl compound content of 5 mol% to 50 mol% can be obtained.
- molecular weight is also arbitrary, generally the weight average molecular weight (Mw) is 3000 or more and 1 million or less, and is 10,000 or more and 500,000 or less when considering mechanical properties and molding processability.
- the molecular weight distribution (Mw / Mn) is also arbitrary.
- the Mw / Mn can be 1.5 to 6, preferably 1.8 to 4.
- the olefin-aromatic vinyl compound copolymer can be obtained by bringing a raw material olefin monomer and an aromatic vinyl compound monomer into contact with a coordination polymerization catalyst, preferably in the presence of a solvent.
- a coordination polymerization catalyst preferably in the presence of a solvent.
- the olefin-aromatic vinyl compound copolymer and the production method thereof are disclosed in Japanese Patent No. 2623070, Japanese Patent Laid-Open No. 09-309925, or Japanese Patent Laid-Open No. 11-130808, each of which is incorporated herein by reference. It is described in the publication.
- the single site coordination polymerization catalyst is used as a coordination polymerization catalyst.
- Preferred single-site coordination polymerization catalysts are disclosed in WO2000 / 37517, US Pat. No. 6,559,234, WO2007 / 139116, and US Pat. No. 2,623,070, each of which is incorporated herein by reference in its entirety. Those described in JP-A-9-309925 or JP-A-11-130808 can be used.
- the single site coordination polymerization catalyst is preferably a single site coordination polymerization catalyst composed of a transition metal compound represented by the following general formula (1) or (2) and a promoter.
- a and B may be the same or different and are unsubstituted or substituted benzoindenyl group, unsubstituted or substituted cyclopentadienyl group, unsubstituted or substituted indenyl group, or unsubstituted or substituted fluorenyl. It is a group selected from groups.
- a substituted benzoindenyl group, a substituted cyclopentadienyl group, a substituted indenyl group, or a substituted fluorenyl group is an alkyl group in which one or more substitutable hydrogen atoms are 1 to 20 carbon atoms, or an aryl having 6 to 10 carbon atoms.
- R represents a hydrocarbon group having 1 to 10 carbon atoms
- a and B may be the same or different, and at least one of A and B is a group selected from an unsubstituted or substituted benzoindenyl group, or an unsubstituted or substituted indenyl group. is there.
- a and B may be the same or different, and A and B are both an unsubstituted or substituted benzoindenyl group, or a group selected from an unsubstituted or substituted indenyl group.
- the unsubstituted benzoindenyl group includes 4,5-benzo-1-indenyl group (also known as benzo (e) indenyl group), 5,6-benzo-1-indenyl group, and 6,7-benzo-1-indenyl group. Can be illustrated.
- Examples of the substituted benzoindenyl group include ⁇ -acenaphtho-1-indenyl group, 3-cyclopenta [c] phenanthryl group, and 1-cyclopenta [l] phenanthryl group.
- Examples of the unsubstituted indenyl group include a 1-indenyl group.
- Examples of the substituted indenyl group include a 4-methyl-1-indenyl group, a 5-ethyl-1-indenyl group, a 4-phenyl-1-indenyl group, and a 4-naphthyl-1-indenyl group.
- a and B may be the same or different and are a group selected from an unsubstituted or substituted benzoindenyl group or an unsubstituted or substituted indenyl group.
- Y has a bond with A and B, and also has a hydrogen atom or a hydrocarbon group having 1 to 15 carbon atoms as a substituent (the other substituent includes 1 to 3 nitrogen atoms, oxygen atoms, sulfur atoms) , Which may contain a phosphorus atom or a silicon atom), a methylene group, a silylene group, an ethylene group, a germylene group, or a boron group.
- the substituents which these groups have may be different from each other or the same.
- Y may have a cyclic structure.
- Y preferably has a bond with A and B, and additionally has a hydrogen atom or a hydrocarbon group having 1 to 15 carbon atoms as a substituent (other substituents include 1 to 3 nitrogen atoms, oxygen atoms , A sulfur atom, a phosphorus atom, or a silicon atom).
- X is a hydrogen atom, a hydroxyl group, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a silyl group having a hydrocarbon substituent having 1 to 4 carbon atoms, or 1 to An amide group having 20 hydrocarbon substituents.
- Two Xs may have a bond.
- M is zirconium, hafnium, or titanium.
- the transition metal compound can be a racemate, it is preferably a racemate.
- transition metal compound represented by the general formula (1) examples include dimethylmethylenebis (4,5-benzo-1-indenyl) zirconium dichloride (also known as dimethylmethylenebis (benzo [e] indenyl) zirconium dichloride), Di-n-propylmethylenebis (4,5-benzo-1-indenyl) zirconium dichloride, diisopropylmethylenebis (4,5-benzo-1-indenyl) zirconium dichloride, cyclohexylidenebis (4,5-benzo-1- Indenyl) zirconium dichloride, cyclopentylidenebis (4,5-benzo-1-indenyl) zirconium dichloride, diphenylmethylenebis (4,5benzo-1-indenyl) zirconium dichloride, dimethylmethylene (cyclopentadienyl) (4,5 Benzo-1-indenyl) zirconium dichloride, dimethylmethylene (1-indenyl) (
- transition metal compound shown by following General formula (2) can also be used suitably.
- Cp represents an unsubstituted or substituted cyclopentaphenanthryl group, an unsubstituted or substituted benzoindenyl group, an unsubstituted or substituted cyclopentadienyl group, an unsubstituted or substituted indenyl group, or unsubstituted or It is a group selected from substituted fluorenyl groups.
- a substituted cyclopentaphenanthryl group, substituted benzoindenyl group, substituted cyclopentadienyl group, substituted indenyl group, or substituted fluorenyl group is an alkyl group in which one or more substitutable hydrogen atoms have 1 to 20 carbon atoms.
- Y ′ is a methylene group, a silylene group, an ethylene group, a germylene group, or a boron group that has a bond with Cp and Z, and further has a hydrogen atom or a hydrocarbon group having 1 to 15 carbon atoms.
- the substituents which these groups have may be different from each other or the same.
- Y ' may have a cyclic structure.
- Z is a ligand containing a nitrogen atom, an oxygen atom or a sulfur atom, coordinated to M ′ by a nitrogen atom, an oxygen atom or a sulfur atom, and having a bond with Y ′; This is a group having 15 substituents.
- M ′ is zirconium, hafnium, or titanium.
- X ′ has a hydrogen atom, a halogen atom, an alkyl group having 1 to 15 carbon atoms, an aryl group having 6 to 10 carbon atoms, an alkylaryl group having 8 to 12 carbon atoms, or a hydrocarbon substituent having 1 to 4 carbon atoms.
- n is an integer of 1 or 2.
- transition metal compound represented by the general formula (2) is described in International Publication No. WO99 / 14221, European Patent Application Publication No. 416815, and US Patent Application Publication No. 6254556.
- Examples of the transition metal compound represented by the general formula (2) include (tertiary butylamide) (tetramethyl- ⁇ 5-cyclopentadienyl) -1,2-ethanediylzirconium dichloride, (tertiary butylamide) (Tetramethyl- ⁇ 5-cyclopentadienyl) -1,2-ethanediyltitanium dichloride, (methylamide) (tetramethyl- ⁇ 5-cyclopentadienyl) -1,2-ethanediylzirconium dichloride, (methylamide) (tetra Methyl- ⁇ 5-cyclopentadienyl) -1,2-ethanediyltitanium dichloride, (ethylamide) (te
- a single site coordination polymerization catalyst composed of the transition metal compound represented by the above general formula (1) and a promoter is used.
- the amount of transition metal compound used is not particularly limited. In general, the amount used (mass) can be about 0.001 ppm to 100 ppm relative to the mass of the polymerization solution.
- a known cocatalyst conventionally used in combination with a transition metal compound can be used.
- an alumoxane or boron compound such as methylaluminoxane (hereinafter also referred to as “methylalumoxane” or “MAO”) is preferably used.
- alkylaluminum such as triisobutylaluminum and triethylaluminum may be used together with these alumoxanes and boron compounds.
- promoters include European Patent Application No. 0874922, Japanese Patent Application Laid-Open No. 11-130808, Japanese Patent Application Laid-Open No. 9-309925, International Publication No. WO00 / 20426, and European Patent Application Publication No. 0985589. And promoters and alkylaluminum compounds described in JP-A-6-184179.
- alumoxane examples include methylalumoxane (MAO) and methylalumoxane modified and modified with other alkylaluminums, such as MMAO. These can be purchased from Tosoh Finechem Corporation (formerly Tosoh Akzo Corporation) or Albemarle.
- MAO methylalumoxane
- MMAO methylalumoxane modified and modified with other alkylaluminums
- the content ratio is 0.1 to 100,000, preferably 10 to 10,000, in terms of aluminum atom / transition metal atom ratio to the metal of the transition metal compound. If it is less than 0.1, the transition metal compound may not be activated effectively, and if it exceeds 100,000, it may be economically disadvantageous.
- boron that can be used as a promoter a known boron promoter that has been used in combination with a transition metal compound can be used.
- Such boron promoters are disclosed in, for example, JP-A-03-207703, JP-A-05-194461, JP-A-08-034809, JP-A-08-034810, h.H. Brintzinger, D. Fischer. , R. Muelhaupt, R. Rieger, R. Waymout, Angew. Chem. 1995, 107, 1255-1283, European Patent Application Publication No. 558158, European Patent Application Publication No. 4266737, European Patent Application Publication No. 427697 It is described in the specification.
- Examples of boron that can be used as a co-catalyst include trispentafluorophenylborane, triphenylcarbenium tetrakis (pentafluorophenyl) borate ⁇ trityltetrakis (pentafluorophenyl) borate ⁇ , lithium tetrakis (pentafluorophenyl) borate, Trimethylammonium tetraphenylborate, triethylammonium tetraphenylborate, tripropylammonium tetraphenylborate, tri (n-butyl) ammonium tetraphenylborate, tri (n-butyl) ammonium tetra (p-tolyl) phenylborate, tri (n- Butyl) ammonium tetra (p-ethylphenyl) borate, tri (n-butyl) ammonium tetra (p
- the most preferred boron promoter is a boron promoter having boron and a fluorine-substituted aromatic group bonded thereto.
- examples include trispentafluorophenylborane, triphenylcarbenium tetrakis (pentafluorophenyl) borate ⁇ trityltetrakis (pentafluorophenyl) borate ⁇ , lithium tetrakis (pentafluorophenyl) borate, tri (n-butyl) Ammonium tetra (pentafluorophenyl) borate, tropylium tetrakispentafluorophenylborate, N, N′-dimethylanilinium tetrakis (pentafluorophenyl) borate and the like.
- a phenyl group is exemplified as an example of a fluorine-substituted aromatic group, but a condensed aromatic group such as a naphthyl group similarly substituted with fluorine can also be preferably used.
- organoaluminum compounds may be used simultaneously.
- an organoaluminum compound when a boron promoter is used, the addition of an organoaluminum compound is effective for removing impurities that adversely affect the polymerization such as water contained in the polymerization system.
- organoaluminum compounds include triisobutylaluminum, triethylaluminum, trimethylaluminum, and trioctylaluminum.
- the amount of these organic aluminums to be used for the boron promoter is generally in the range of 1 to 1000, preferably 1 to 100, as the molar ratio of aluminum to boron.
- a boron compound When a boron compound is used as the cocatalyst, it is preferably used at a boron atom / transition metal atom ratio of 0.01 to 100, more preferably 0.1 to 10, particularly preferably 1. If it is less than 0.01, the transition metal compound may not be activated effectively, and if it exceeds 100, it may be economically disadvantageous.
- the transition metal compound and the cocatalyst may be mixed and prepared outside the polymerization equipment, or may be mixed inside the equipment at the time of polymerization.
- polymerization is performed in a liquid monomer without using a solvent, or pentane, hexane, heptane, cyclohexane, benzene, toluene, ethylbenzene, xylene, chloro-substituted benzene, chloro-substituted toluene, methylene chloride, chloroform.
- a saturated aliphatic or aromatic hydrocarbon or halogenated hydrocarbon alone or in a mixed solvent.
- a mixed alkane solvent, cyclohexane, toluene, ethylbenzene or the like is used.
- the polymerization form may be either solution polymerization or slurry polymerization.
- well-known methods such as batch polymerization, continuous polymerization, prepolymerization, and multistage polymerization, can be used as needed.
- Pipe-shaped polymerization cans include various known mixers such as dynamic or static mixers and static mixers that also remove heat, and various known mixers such as coolers equipped with heat removal thin tubes. You may have a cooler. Moreover, you may have a batch type prepolymerization can. Furthermore, methods such as gas phase polymerization can be used.
- the polymerization temperature is suitably ⁇ 78 ° C. to 200 ° C.
- a polymerization temperature lower than ⁇ 78 ° C. may be industrially disadvantageous, and if it exceeds 200 ° C., decomposition of the transition metal compound may occur.
- industrially preferred is 0 ° C to 160 ° C, particularly preferred is 30 ° C to 160 ° C.
- the pressure at the time of polymerization is suitably 0.1 to 100 atm, preferably 1 to 30 atm, particularly industrially particularly preferably 1 to 10 atm.
- the olefin-aromatic vinyl compound-aromatic polyene copolymer obtained by the above-described production method can be used as an intermediate in the production of a cross copolymer. Therefore, the above-described method for producing an olefin-aromatic vinyl compound copolymer can be suitably applied as a coordination polymerization step in the production of a cross copolymer.
- a cross-copolymer is a copolymer obtained by a production method comprising a coordination polymerization step followed by an anion or radical polymerization step.
- an olefin-aromatic vinyl compound-aromatic polyene copolymer is produced from an olefin, an aromatic vinyl compound, and an aromatic polyene monomer using a single site coordination polymerization catalyst.
- a cross-copolymer can be obtained by anionic polymerization or radical polymerization in the presence of the olefin-aromatic vinyl compound-aromatic polyene copolymer and aromatic vinyl compound monomer.
- This cross-copolymer is composed of an olefin-aromatic vinyl compound-aromatic polyene copolymer chain (sometimes described as a main chain) and an aromatic vinyl compound polymer chain (sometimes described as a side chain).
- the olefin-aromatic vinyl compound-aromatic polyene copolymer is preferably an ethylene-styrene-divinylbenzene copolymer.
- the composition is arbitrary depending on the purpose and application, but generally the styrene content is 0.03 mol% or more and 96 mol% or less, preferably 5 mol% or more and 40 mol% or less, and the diene content is 0.0001 mol% or more. 3 mol% or less, the balance being ethylene.
- the molecular weight is not particularly limited, but generally the weight average molecular weight is 10,000 or more, preferably 30,000 or more, particularly preferably 60,000 or more, and 1,000,000 or less, preferably 500,000 or less.
- the molecular weight distribution (Mw / Mn) is 6 or less, preferably 4 or less.
- the most preferably used cross-copolymer is an ethylene-styrene-divinylbenzene copolymer obtained by coordination polymerization and a copolymer obtained by anionic polymerization in the presence of a styrene monomer. It is a copolymer having a divinylbenzene copolymer chain (may be described as a main chain and is a soft component) and a polystyrene chain (may be described as a side chain and a hard component). .
- the softness of the cross-copolymer depends on the styrene content of the ethylene-styrene-divinylbenzene copolymer chain, which is the soft polymer chain component (soft segment), the ratio of the soft component and the hard component, the soft component chain Content of divinylbenzene component that binds to the hard component chain, molecular fluidity of the entire cross-copolymer defined by the molecular weight of ethylene-styrene-divinylbenzene copolymer chain and polystyrene chain and the divinylbenzene content (MFR) Value) and the like.
- MFR divinylbenzene content
- the storage modulus is mainly as the styrene content of the ethylene-styrene-divinylbenzene copolymer chain increases and the crystallinity of the ethylene chain decreases or is softer. It decreases as the content of the component ethylene-styrene-divinylbenzene copolymer chain increases.
- the weight average molecular weight (Mw) and the number average molecular weight (Mn) in terms of standard polystyrene were determined using GPC (gel permeation chromatography). The measurement was performed under the following conditions. Column: TSK-GEL MultiporeHXL-M ⁇ 7.8 ⁇ 300 mm (manufactured by Tosoh Corporation) was connected in series. Column temperature: 40 ° C Detector: RI Solvent: THF Liquid feed flow rate: 1.0 ml / min. Sample concentration: 0.1 wt / vol% Sample injection volume: 100 ⁇ L
- styrene monomers having different phenylacetylene contents are used, and the effects thereof in the production of an ethylene-styrene copolymer and an ethylene-styrene-divinylbenzene copolymer are shown.
- Example 1 Synthesis of ethylene-styrene copolymer using MAO as cocatalyst
- rac-dimethylmethylenebis (1-indenyl) zirconium dichloride as the transition metal in the single-site coordination polymerization catalyst
- Polymerization was carried out using an autoclave with a capacity of 50 L, a stirrer and a heating / cooling jacket.
- the ethylene introduction line was equipped with a mass flow meter, and the ethylene flow rate and integrated flow rate were measured.
- Cyclohexane 21.3 kg, styrene (phenylacetylene content 26 ppm) 3.2 kg, Nippon Steel Chemical Co., Ltd.
- divinylbenzene metal, para-mixed product, 61 mmol as divinylbenzene
- a flow rate of 30 L / min for 10 minutes to purge the water in the system and the polymerization liquid (replace with nitrogen gas).
- 30 mmol of triisobutylaluminum and 100 mmol of methylalumoxane were added based on Al, and the inside of the system was purged (substituted) immediately with ethylene.
- the internal temperature was raised to 90 ° C., ethylene was introduced, and after stabilizing at a pressure of 0.35 MPaG (3.5 Kg / cm 2 G), from a catalyst tank installed on the autoclave, About 50 ml of a toluene solution in which 100 ⁇ mol of rac-dimethylmethylenebis (1-indenyl) zirconium dichloride and 1 mmol of triisobutylaluminum were dissolved was added to the autoclave. Furthermore, the polymerization was carried out while maintaining the pressure at 0.35 MPaG while maintaining the internal temperature at 90 ° C. and ethylene consumed in the reaction (coordination polymerization step).
- the ethylene-styrene copolymer obtained in Example 1 has a styrene content of 18 mol%, a weight average molecular weight (Mw) of 88,000, and a molecular weight distribution (Mw / Mn) of 2.1.
- the ethylene-styrene copolymer obtained in Comparative Example 1 had substantially the same composition and molecular weight as the copolymer obtained in Example 1.
- Example 2 Synthesis of ethylene-styrene-divinylbenzene copolymer using MAO as cocatalyst
- rac-dimethylmethylenebis (4,5-benzo-1-indenyl) zirconium dichloride as the transition metal compound in the single site coordination polymerization catalyst
- the ethylene-styrene-divinylbenzene copolymer obtained in Example 2 has a styrene content of 26 mol%, a divinylbenzene content of 0.06 mol%, and a weight average molecular weight (Mw) of 100,000,
- the molecular weight distribution (Mw / Mn) is 2.3
- the ethylene-styrene-divinylbenzene copolymer obtained in Comparative Example 2 has substantially the same composition as that of the copolymer obtained in Example 2. Had a molecular weight.
- Example 3 Synthesis of ethylene-styrene-divinylbenzene copolymer using boron compound as co-catalyst
- rac-dimethylmethylenebis (4,5-benzo-1-indenyl) zirconium dichloride as the transition metal in the single-site coordination polymerization catalyst.
- Polymerization was carried out using the same autoclave and equipment as in Example 1. 21.3 kg of cyclohexane, 3.2 kg of styrene (phenylacetylene content 17 ppm) and divinylbenzene (meta, para-mixed product, 61 mmol as divinylbenzene) manufactured by Nippon Steel Chemical Co., Ltd.
- Triphenylcarbenium tetrakis (pentafluorophenyl) borate ⁇ trityltetrakis) was added to about 20 ml of a toluene solution in which 100 ⁇ mol of rac-dimethylmethylenebis (4,5-benzo-1-indenyl) zirconium dichloride and 1 mmol of triisobutylaluminum were dissolved.
- (Pentafluorophenyl) borate ⁇ A catalyst solution added with 10 ml of a toluene solution in which 120 ⁇ mol was dissolved was injected into the polymerization solution of the autoclave from the catalyst tank on the autoclave with a small amount of pressurized nitrogen gas.
- the polymerization was carried out while the internal temperature was 95 ° C. and ethylene consumed in the reaction was supplemented and the pressure was maintained at 0.30 MPaG (coordination polymerization step).
- the polymerization time was 30 minutes, the polymerization was in progress without substantial deactivation, but the polymerization was stopped in the same manner as in Example 1.
- Ethylene consumed in the polymerization time of 30 minutes was 580 L in the standard state.
- the obtained polymerization solution was added little by little into a large amount of vigorously stirred methanol solution to recover the polymer.
- the polymer was air-dried at room temperature for one day and then dried at 80 ° C. in a vacuum until no mass change was observed.
- the ethylene-styrene-divinylbenzene copolymer obtained in Example 3 had a styrene content of 26 mol%, a divinylbenzene content of 0.06 mol%, and a weight average molecular weight (Mw) of 140,000.
- the molecular weight distribution (Mw / Mn) was 3.2.
- Example 3 when MAO is used as a co-catalyst, a styrene monomer having a low phenylacetylene content satisfying the conditions of the present invention is used, so that the polymerization activity is higher than that of Comparative Examples 1 and 2. Indicates. As shown in Example 3, when a boron compound is used as a cocatalyst, a clearer effect is recognized. That is, as shown in Example 3, high polymerization activity can be exhibited by using a styrene monomer having a low phenylacetylene content that satisfies the conditions of the present invention. When a styrene monomer having a high acetylene content outside the range of the present invention is used, the polymerization does not proceed substantially.
- an olefin-aromatic vinyl compound copolymer particularly an olefin-aromatic vinyl compound-aromatic polyene copolymer, which is an intermediate for the production of a cross-copolymer
- the low phenylacetylene content defined by the present invention By using an aromatic vinyl compound monomer, it is possible to obtain higher polymerization activity per unit catalyst, and it is possible to produce industrially with a smaller amount of catalyst used and to reduce the catalyst cost.
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Abstract
Description
本発明において「オレフィン-芳香族ビニル化合物系共重合体」とは、「オレフィン-芳香族ビニル化合物共重合体」と「オレフィン-芳香族ビニル化合物-芳香族ポリエン共重合体」とを包含する概念である。本発明に係るオレフィン-芳香族ビニル化合物共重合体の製造方法は、オレフィンモノマー及び芳香族ビニル化合物モノマーを含む原料モノマーとシングルサイト配位重合触媒とを接触させてオレフィン-芳香族ビニル化合物共重合体を製造する配位重合工程を有する。また、オレフィン-芳香族ビニル化合物-芳香族ポリエン共重合体の製造方法は、オレフィンモノマー、芳香族ビニル化合物モノマー、および芳香族ポリエンモノマーを含む原料モノマーとシングルサイト配位重合触媒とを接触させてオレフィン-芳香族ビニル化合物-芳香族ポリエン共重合体を製造する配位重合工程を有する。
原料モノマーは、オレフィン-芳香族ビニル化合物共重合体を得る場合は、オレフィンモノマー及び芳香族ビニル化合物モノマーを含む。また、オレフィン-芳香族ビニル化合物-芳香族ポリエン共重合体を得る場合は、さらに芳香族ポリエンモノマーを含む。
オレフィンモノマーとしては、エチレン、炭素数3~20のα-オレフィン、すなわちプロピレン、1-ブテン、1-ヘキセン、4-メチル-1-ペンテン、1-オクテン等が挙げられる。オレフィンには、環状オレフィンも含まれ、環状オレフィンの例としては、ビニルシクロヘキサンやシクロペンテン、ノルボルネン等が挙げられる。好ましくは、エチレン、又はエチレンとα-オレフィンすなわちプロピレン、1-ブテン、1-ヘキセン、あるいは1-オクテン等との混合物が用いられ、更に好ましくは、エチレンが用いられる。
シングルサイト配位重合触媒は、配位重合触媒として用いられる。好ましいシングルサイト配位重合触媒は、その全体の記載をそれぞれ出典明示によりここに援用する、国際公開第WO2000/37517号、米国特許第6559234号、国際公開第WO2007/139116号、特許2623070号公報、特開平9-309925号公報、又は特開平11-130808号公報に記載されているものを用いることができる。
Mは、ジルコニウム、ハフニウム、又はチタンである。さらに、遷移金属化合物は、ラセミ体となることができる場合には、ラセミ体であることが好ましい。
配位重合工程でオレフィン-芳香族ビニル化合物共重合体又はオレフィン-芳香族ビニル化合物-芳香族ポリエン共重合体を製造するにあたっては、上記に例示した各モノマー、遷移金属化合物及び助触媒を接触させるが、接触の順番、接触方法は任意の公知の方法を用いることができる。以上の共重合の方法としては溶媒を用いずに液状モノマー中で重合させる方法、あるいはペンタン、ヘキサン、ヘプタン、シクロヘキサン、ベンゼン、トルエン、エチルベンゼン、キシレン、クロロ置換ベンゼン、クロロ置換トルエン、塩化メチレン、クロロホルム等の飽和脂肪族又は芳香族炭化水素又はハロゲン化炭化水素の単独又は混合溶媒を用いる方法がある。好ましくは、混合アルカン系溶媒、シクロヘキサン、トルエン、エチルベンゼン等を用いる。
上記した製造方法で得られるオレフィン-芳香族ビニル化合物-芳香族ポリエン共重合体は、クロス共重合体製造における中間体として用いることができる。よって、上記したオレフィン-芳香族ビニル化合物系共重合体の製造方法は、クロス共重合体の製造における配位重合工程として好適に適用することができる。クロス共重合体とは、配位重合工程と引き続くアニオン又はラジカル重合工程からなる製造方法により得られる共重合体である。具体的には、まず配位重合工程において、シングルサイト配位重合触媒を用い、オレフィン、芳香族ビニル化合物、芳香族ポリエンモノマーからオレフィン-芳香族ビニル化合物-芳香族ポリエン共重合体を製造する。引き続き、このオレフィン-芳香族ビニル化合物-芳香族ポリエン共重合体及び芳香族ビニル化合物モノマーの共存下で、アニオン重合又はラジカル重合を行うことにより、クロス共重合体を得ることができる。このクロス共重合体は、オレフィン-芳香族ビニル化合物-芳香族ポリエン共重合体鎖(主鎖と記載される場合もある)と芳香族ビニル化合物重合体鎖(側鎖と記載される場合もある)を有する共重合体である。クロス共重合体及びその製造方法は、その全体の記載をそれぞれ出典明示によりここに援用する、国際公開第WO2000/37517号、米国特許第6559234号、又は国際公開第WO2007/139116号に記載されている。芳香族ビニル化合物モノマー、オレフィンモノマー及び芳香族ポリエンについては、上記したものを用いることができる。
(共重合体の組成)
共重合体中のスチレンユニット含量の決定は、1H-NMRで行い、機器は日本電子株式会社製α-500及びBRUCKER社製AC-250を用いた。重1,1,2,2-テトラクロロエタンに溶解し、測定は、80~100℃で行った。TMSを基準としてフェニル基プロトン由来のピーク(6.5~7.5ppm)とアルキル基由来のプロトンピーク(0.8~3ppm)の面積強度比較で行った。
共重合体中のジビニルベンゼンユニット含量は、ガスクロマトグラフィ分析により求めた重合液中の未反応ジビニルベンゼン量と重合に用いたジビニルベンゼン量との差から求めた。
分子量は、GPC(ゲルパーミエーションクロマトグラフィー)を用いて標準ポリスチレン換算の重量平均分子量(Mw)と数平均分子量(Mn)を求めた。測定は以下の条件で行った。
カラム:TSK-GEL MultiporeHXL-M φ7.8×300mm(東ソ-株式会社製)を2本直列に繋いで用いた。
カラム温度:40℃
検出器:RI
溶媒:THF
送液流量:1.0ml/min.
サンプル濃度:0.1wt/vol%
サンプル注入量:100μL
シングルサイト配位重合触媒中の遷移金属として、rac-ジメチルメチレンビス(1-インデニル)ジルコニウムジクロライドを用い、以下のように実施した。
容量50L、攪拌機及び加熱冷却用ジャケット付のオートクレーブを用いて重合を行った。なお、エチレン導入ラインにはマスフローメーターが装備され、エチレンの流速及び積算流量を計測した。
シクロヘキサン21.3kg、スチレン(フェニルアセチレン含有量26ppm)3.2kg、新日鉄化学社製ジビニルベンゼン(メタ、パラ混合品、ジビニルベンゼンとして61mmol)を仕込み、内温60℃に調整し攪拌(220rpm)した。乾燥窒素ガスを30L/分の流量で10分、液中にバブリングして系内及び重合液の水分をパージ(窒素ガスに置換)した。次いで、トリイソブチルアルミニウム30mmol、メチルアルモキサン(東ソーアクゾ社製、TMAO-211/ヘキサン溶液)をAl基準で100mmol加え、ただちにエチレンで系内をパ-ジ(置換)した。
十分にパ-ジした後、内温を90℃に昇温してエチレンを導入し、圧力0.35MPaG(3.5Kg/cm2G)で安定した後に、オートクレーブ上に設置した触媒タンクから、rac-ジメチルメチレンビス(1-インデニル)ジルコニウムジクロライドを100μmol、トリイソブチルアルミニウム1mmolを溶かしたトルエン溶液約50mlをオートクレーブ中に加えた。さらに、内温を90℃、反応で消費されるエチレンを補いながら圧力を0.35MPaGに維持しながら重合を実施した(配位重合工程)。重合時間が30分経過した時点で重合は実質的に失活無く進行中であったが、少量のイソプロパノールを含むトルエン溶液を重合液に添加し重合を停止させ、エチレンの供給を停止し気相エチレンを排気した。重合時間30分間で消費されたエチレンは標準状態で620Lであった。得られた重合液を、激しく攪拌した大量のメタノール液中に少量ずつ投入して、ポリマーを回収した。このポリマーを、室温で1昼夜風乾した後に80℃、真空中、質量変化が認められなくなるまで乾燥した。1.5kgのポリマー(エチレン-スチレン共重合体)を得た。触媒あたりの生産効率は、触媒1molあたり反応時間1時間で製造可能なポリマー質量として、30×106g-ポリマー/mol-触媒・hであった。
スチレンモノマーを、フェニルアセチレン含有量が80ppmであるスチレンに変更した以外は、実施例1と同様にして重合を実施した。重合時間30分間で消費されたエチレンは標準状態で380Lであった。0.9kgのポリマーを回収した。触媒あたりの生産効率は、触媒1molあたり反応時間1時間で製造可能なポリマー質量として、18×106g-ポリマー/mol-触媒・hであった。
シングルサイト配位重合触媒中の遷移金属化合物としてrac-ジメチルメチレンビス(4,5-ベンゾ-1-インデニル)ジルコニウムジクロライドを用い、以下のように実施した。実施例1と同じオートクレーブ及び設備を用いて重合を行った。シクロヘキサン21.3kg、スチレン(フェニルアセチレン含量17ppm)3.2kg、新日鉄化学株式会社製ジビニルベンゼン(メタ、パラ混合品、ジビニルベンゼンとして61mmol)を仕込み、内温60℃に調整し攪拌(220rpm)した。乾燥窒素ガスを30L/分の流量で10分、液中にバブリングして系内及び重合液の水分をパージした。次いで、トリイソブチルアルミニウム30mmol、メチルアルモキサン(東ソー・アクゾ株式会社製、TMAO-211/ヘキサン溶液)をAl基準で50mmol加え、ただちにエチレンで系内をパ-ジした。十分にパ-ジした後、内温を90℃に昇温してエチレンを導入し、圧力0.30MPaG(3.0Kg/cm2G)で安定した後に、オートクレーブ上に設置した触媒タンクから、rac-ジメチルメチレンビス(4,5-ベンゾ-1-インデニル)ジルコニウムジクロライドを80μmol、トリイソブチルアルミニウム1mmolを溶かしたトルエン溶液約50mlをオートクレーブ中に加えた。さらに、内温を90℃、反応で消費されるエチレンを補いながら圧力を0.30MPaGに維持しながら重合を実施した(配位重合工程)。重合時間が30分経過した時点で重合は実質的に失活無く進行中であったが、少量のイソプロパノールを含むトルエン溶液を重合液に添加し重合を停止させ、エチレンの供給を停止し気相エチレンを排気した。重合時間30分間で消費されたエチレンは標準状態で530Lであった。得られた重合液を、激しく攪拌した大量のメタノール液中に少量ずつ投入して、ポリマーを回収した。このポリマーを、室温で1昼夜風乾した後に80℃、真空中、質量変化が認められなくなるまで乾燥した。1.6kgのポリマー(エチレン-スチレン-ジビニルベンゼン共重合体)を得た。触媒あたりの生産効率は、触媒1molあたり反応時間1時間で製造可能なポリマー質量として、40×106g-ポリマー/mol-触媒・hであった。
スチレンモノマーを、フェニルアセチレン含有量が80ppmであるスチレンに変更した以外は、実施例2と同様にして重合を実施した。重合時間30分間で消費されたエチレンは標準状態で240Lであった。0.7kgのポリマーを回収した。触媒あたりの生産効率は、触媒1molあたり反応時間1時間で製造可能なポリマー質量として、18×106g-ポリマー/mol-触媒・hであった。
シングルサイト配位重合触媒中の遷移金属として、rac-ジメチルメチレンビス(4,5-ベンゾ-1-インデニル)ジルコニウムジクロライドを用い、以下のように実施した。
実施例1と同じオートクレーブ及び設備を用いて重合を行った。シクロヘキサン21.3kg、スチレン(フェニルアセチレン含量17ppm)3.2kg及び新日鉄化学社製ジビニルベンゼン(メタ、パラ混合品、ジビニルベンゼンとして61mmol)を仕込み、内温60℃に調整し攪拌(220rpm)した。乾燥窒素ガスを30L/分の流量で10分、液中にバブリングして系内及び重合液の水分をパージした。次いで、トリイソブチルアルミニウム30mmolを加え、ただちにエチレンで系内をパ-ジした。十分にパ-ジした後、内温を95℃に昇温してエチレンを導入し、圧力0.30MPaG(3.0Kg/cm2G)で安定させた。
触媒であるrac-ジメチルメチレンビス(4,5-ベンゾ-1-インデニル)ジルコニウムジクロライドを100μmol、トリイソブチルアルミニウム1mmolを溶かしたトルエン溶液約20mlにトリフェニルカルベニウムテトラキス(ペンタフルオロフェニル)ボレート{トリチルテトラキス(ペンタフルオロフェニル)ボレート}120μmolを溶かしたトルエン溶液10mlを加えた触媒溶液を、オートクレーブ上の触媒タンクから、少量の加圧窒素ガスによりオートクレーブの重合液中に注入した。
さらに、内温を95℃、反応で消費されるエチレンを補い圧力を0.30MPaGに維持しながら重合を実施した(配位重合工程)。重合時間が30分経過した時点で重合は実質的に失活無く進行中であったが、実施例1と同様にして重合を停止した。重合時間30分間で消費されたエチレンは標準状態で580Lであった。得られた重合液を、激しく攪拌した大量のメタノール液中に少量ずつ投入して、ポリマーを回収した。このポリマーを、室温で1昼夜風乾した後に80℃、真空中、質量変化が認められなくなるまで乾燥した。1.7kgのポリマー(エチレン-スチレン-ジビニルベンゼン共重合体)を得た。触媒あたりの生産効率は、触媒1molあたり反応時間1時間で製造可能なポリマー質量として、34×106g-ポリマー/mol-触媒・hであった。
スチレンモノマーを、フェニルアセチレン含有量が80ppmであるスチレンに変更した以外は、実施例3と同様にして重合を実施した。重合時間30分間で消費されたエチレンは標準状態で10L以下であった。すなわち実質的に重合は進行しなかったのでポリマーの回収は行わなかった。
スチレンモノマーを、フェニルアセチレン含有量が57ppmであるスチレンに変更した以外は、実施例2と同様にして重合を実施した。重合時間30分間で消費されたエチレンは標準状態で30L以下であった。すなわち実質的に重合は進行しなかったのでポリマーの回収は行わなかった。
Claims (5)
- オレフィンモノマー及び芳香族ビニル化合物モノマーを含む原料モノマーとシングルサイト配位重合触媒とを接触させてオレフィン-芳香族ビニル化合物系共重合体を得る工程を有し、
芳香族ビニル化合物モノマー中のフェニルアセチレンの含有量が50ppm以下である、オレフィン-芳香族ビニル化合物系共重合体の製造方法。 - シングルサイト配位重合触媒が、下記一般式(1)又は(2)で表される遷移金属化合物と助触媒とからなる、請求項1に記載のオレフィン-芳香族ビニル化合物系共重合体の製造方法。
式(1)中、A及びBは同一でも異なっていてもよく、非置換もしくは置換ベンゾインデニル基、非置換もしくは置換シクロペンタジエニル基、非置換もしくは置換インデニル基、又は非置換もしくは置換フルオレニル基から選ばれる基である。置換ベンゾインデニル基、置換シクロペンタジエニル基、置換インデニル基、又は置換フルオレニル基とは、置換可能な水素原子の1個以上が炭素数1~20のアルキル基、炭素数6~10のアリール基、炭素数7~20のアルキルアリール基、ハロゲン原子、OSiR3基、SiR3基又はPR2基(Rは、いずれも炭素数1~10の炭化水素基を表す)で置換された、ベンゾインデニル基、シクロペンタジエニル基、インデニル基、又はフルオレニル基である。
Yは、A及びBと結合を有し、他に置換基として水素原子もしくは炭素数1~15の炭化水素基(該炭化水素基は他に1~3個の窒素原子、酸素原子、硫黄原子、燐原子、又は珪素原子を含んでもよい)を有する、メチレン基、シリレン基、エチレン基、ゲルミレン基、又は硼素基である。これらの基が有する置換基は、互いに異なっていても同一でもよい。また、Yは環状構造を有していてもよい。
Xは、水素原子、水酸基、ハロゲン原子、炭素数1~20の炭化水素基、炭素数1~20のアルコキシ基、炭素数1~4の炭化水素置換基を有するシリル基、又は炭素数1~20の炭化水素置換基を有するアミド基である。2個のXは結合を有してもよい。
Mは、ジルコニウム、ハフニウム、又はチタンである。
式(2)中、Cpは、非置換もしくは置換シクロペンタフェナンスリル基、非置換もしくは置換ベンゾインデニル基、非置換もしくは置換シクロペンタジエニル基、非置換もしくは置換インデニル基、又は非置換もしくは置換フルオレニル基から選ばれる基である。置換シクロペンタフェナンスリル基、置換ベンゾインデニル基、置換シクロペンタジエニル基、置換インデニル基、又は置換フルオレニル基とは、置換可能な水素原子の1個以上が炭素数1~20のアルキル基、炭素数6~10のアリール基、炭素数7~20のアルキルアリール基、ハロゲン原子、OSiR3基、SiR3基又はPR2基(Rは、いずれも炭素数1~10の炭化水素基を表す)で置換された、シクロペンタフェナンスリル基、ベンゾインデニル基、シクロペンタジエニル基、インデニル基、又はフルオレニル基である。
Y’は、Cp及びZと結合を有し、他に水素原子もしくは炭素数1~15の炭化水素基を有する、メチレン基、シリレン基、エチレン基、ゲルミレン基、又は硼素基である。これらの基が有する置換基は、互いに異なっていても同一でもよい。また、Y’は環状構造を有していてもよい。
Zは、窒素原子、酸素原子又は硫黄原子を含み、窒素原子、酸素原子又は硫黄原子でM’に配位する配位子でY’と結合を有し、他に水素原子もしくは炭素数1~15の置換基を有する基である。
M’はジルコニウム、ハフニウム、又はチタンである。
X’は、水素原子、ハロゲン原子、炭素数1~15のアルキル基、炭素数6~10のアリール基、炭素数8~12のアルキルアリール基、炭素数1~4の炭化水素置換基を有するシリル基、炭素数1~10のアルコキシ基、又は炭素数1~6のアルキル置換基を有するジアルキルアミド基である。
nは、1又は2の整数である。 - 助触媒が、硼素化合物からなる、請求項2に記載のオレフィン-芳香族ビニル化合物系共重合体の製造方法。
- 原料モノマーが、さらに芳香族ポリエンモノマーを含み、オレフィン-芳香族ビニル化合物系共重合体が、オレフィン-芳香族ビニル化合物-芳香族ポリエン共重合体である、請求項1~3のいずれか一項に記載のオレフィン-芳香族ビニル化合物系共重合体の製造方法。
- 配位重合工程に引き続き、アニオン重合工程又はラジカル重合工程を有し、配位重合工程が、請求項4に記載のオレフィン-芳香族ビニル化合物系共重合体の製造方法からなる、クロス共重合体の製造方法。
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