Classifications

• • 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
  • C08F36/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
  • C08F36/02—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
  • C08F36/04—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
  • C08F36/08—Isoprene

Definitions

• the present invention relates to a method for producing an isoprene-based polymer, particularly a regioselective and high-tacticity isoprene-based polymer, preferably polyisoprene, and a polymerization catalyst composition used therefor.
• Polyisoprene may have the following four different structural units. That is, a 3,4-bonded structural unit represented by the general formula ( ⁇ ), a transformer 1,4-bonded structural unit represented by the general formula ( ⁇ ), a cis 1,4 represented by the general formula ( ⁇ ) Bonded structural units, and 1, 2 bonded structural units represented by general formula (IV).
• Non-Patent Document 1 It is reported that the above polymer is produced by polymerizing isoprene (see Non-Patent Document 1).
• the other is to use a complex in which sparteine is coordinated with FeCl as a polymerization catalyst.
• Non-patent Document 2 It is reported that the above polymer is produced by polymerizing isoprene (Non-patent Document 2).
• polyisoprene having selectively a structural unit represented by the general formula ( ⁇ ) is considered to have greatly different physical properties depending on the tacticity of the arrangement of the structural unit.
• Two types of stereoisomerism can occur in a polymer with two side chain substituents different from each other in the main chain atom, such as polyisoprene, which is a structural unit represented by the general formula ( ⁇ ).
• Tactic City is this solid It means the arrangement or order in the polymer main chain of the part showing isomerism.
• One of the two different side chain substituents is bonded to one side only with respect to the plane formed by the polymer main chain, and the resulting polymer is represented by a isotactic polymer (represented by the following general formula (V)).
• the polymer is a syndiotactic polymer (the following general formula (V)).
• Such a polymer having no regularity is referred to as atactic polymer.
• Non-Patent Document 1 it is described that the obtained polyisoprene is a atactic polymer, and in Non-Patent Document 2, there is no description regarding the tacticity of the obtained polyisoprene. Therefore, a polyisoprene having a general formula ( ⁇ ) selectively and having a high tacticity has been demanded.
• Patent Document 1 a method for producing polyisoprene having high tacticity has been reported.
• polyisoprene is polymerized using a meta-octacene catalyst.
• polyisoprene having high tacticity can be produced by polymerizing isoprene using such a catalyst, there is a problem that the cost of the catalyst is high at present.
• Non-patent Document 3 it has been reported that polyethylene is produced using a non-metacene catalyst containing amidine.
• the yield of polyethylene fluctuates by changing the central metal.
• isoprene-based polymers having high tacticity.
• Patent Document 1 International Publication No. 05Z085306 Pamphlet
• Non-patent literature l Makromolekulare Chem (1964), 77, pp.126-138.
• Non-Patent Document 2 Macromolecules (2003), 36, pp.7953-7958.
• Non-Patent Document 3 J. AM. CHEM. SOC. (2004), 126, pp. 9182-9183.
• the present invention has been made under such circumstances, and is an isoprene-based polymer selectively having a structural unit represented by the following general formula (Y), and the arrangement of the structural units.
• a polymerization catalyst composition for producing an isoprene-based polymer (particularly a isotactic-rich isoprene-based polymer) at a low cost with a high tacticity, and an isoprene having a high tacticity using the polymerization catalyst composition It is an object of the present invention to provide a method for producing a polymer.
• R 4 represents an alkyl group or a alkenyl group having 1 to 10 carbon atoms.
• the present invention is as follows.
• R 1 and R 2 each independently represents an alkyl group, a cyclohexyl group, an aryl group or an aralkyl group,
• R 3 represents an alkyl group, an alkyl group, an alkyl group, an alkyl group, an aryl group or an aralkyl group, an aliphatic, aromatic or cyclic amino group, or a phosphino group, a boryl group, an alkyl or arylthio group, an alkoxy group. Or an aryloxy group,
• M represents any of rare earth elements from lanthanum La to lutetium Lu excluding scandium Sc, yttrium Y or promethium Pm,
• Q 1 and Q 2 each independently represent a mono-on-type ligand
• L represents a neutral Lewis base
• w represents an integer of 0 to 3.
• R 4 represents an alkyl group or a alkenyl group having 1 to 10 carbon atoms.
• R 1 and R 2 in the general formula (A) are 2 , 6-Diisopropylphenol group, R 3 represents a phenyl group,
• M represents any of rare earth elements from lanthanum La to lutetium Lu, excluding scandium Sc, yttrium Y or promethium Pm.
• the complex represented by the general formula (A) is a compound represented by the general formula (C).
• M represents any of rare earth elements from lanthanum La to lutetium Lu except scandium Sc, yttrium Y or promethium Pm.
• catalyst activator according to any one of (1) to (4), wherein the catalyst activator is an ionic compound comprising a non-coordinating cation and a cationic card. Polymerization catalyst composition.
• FIG. 1 is a 1 H-NMR spectrum chart of polyisoprene obtained in Example 1.
• FIG. 2 is a 13 C-NMR ⁇ vector chart of polyisoprene obtained in Example 1.
• FIG. 3 is a GPC chart of polyisoprene obtained in Example 1.
• FIG. 4 is a DSC chart of the polyisoprene obtained in Example 1.
• FIG. 5 is a 1 H-NMR spectrum chart of polyisoprene obtained in Example 4.
• FIG. 6 is a 13 C-NMR ⁇ vector chart of polyisoprene obtained in Example 4.
• FIG. 7 is a DSC chart of the polyisoprene obtained in Example 4.
• FIG. 8 is a 1 H-NMR spectrum chart of polyisoprene obtained in Reference Example 1.
• FIG. 9 is a 13 C-NMR ⁇ vector chart of polyisoprene obtained in Reference Example 1.
• the polymerization catalyst composition of the present invention comprises the complex represented by the general formula (A) and a catalyst activator.
• R 1 and R 2 are each independently an alkyl group, a substituted or unsubstituted cyclohexyl group, an aryl group, or an aralkyl group.
• alkyl group include a methyl group, an ethyl group, an isopropyl group, an n-butyl group, and a t-butyl group.
• substituted cyclohexyl group include a cyclohexyl group having an alkyl group as a substituent, for example, a methylcyclohexyl group.
• Examples of the unsubstituted aryl group include a phenyl group, and examples of the substituted aryl group include a phenyl group having an alkyl group as a substituent.
• Examples of the unsubstituted aralkyl group include a benzyl group, and examples of the substituted aralkyl group include a benzyl group having an alkyl group as a substituent.
• phenyl having an alkyl group as a substituent is preferred, and 2,6-diisopropylphenyl group is particularly preferred.
• R 1 and R 2 may be the same or different! However, both R 1 and R 2 are preferably a phenyl group having an alkyl group as a substituent, more preferably a 2,6-diisopropyl phenol group.
• R 3 represents an alkyl group, an alkyl group, an alkyl group, an alkyl group, an aryl group or an aralkyl group, an aliphatic, aromatic or cyclic amino group, or a phosphino group, a boryl group, an alkyl group or an arylthio group.
• the complex contained in the polymerization catalyst composition of the present invention is a 2, 6-diisopropyl phenol group for both R 1 and R 2 forces, and R 3 is a phenol group. It is preferable to have the structure of —'- bis (2,6-diisopropyl pyridine) benzamidinate (NCN)! /.
• the central metal ⁇ represents any of rare earth elements from lanthanum La to lutetium Lu excluding scandium Sc, yttrium Y or promethium Pm.
• the central metal M tries to polymerize. A force that can be appropriately selected according to the type of monomer, etc. Scandium Sc, yttrium Y or lutetium Lu is preferred, and scandium Sc is particularly preferred.
• Q 1 and Q 2 are mono-on-type ligands.
• Monoarion-type ligands include 1) hydride, 2) halide, 3) substituted or unsubstituted hydrocarbyl group having 1 to 20 carbon atoms, 4) substituted or unsubstituted, 1 to 20 carbon atoms Examples thereof include alkoxy groups or aryloxy groups, 5) substituted or unsubstituted amide groups having 1 to 20 carbon atoms (including silylamide groups), 6) phosphino groups, and the like, and hydrocarbyl groups are preferably exemplified. It is not limited to that.
• Q 1 and Q 2 may be combined with each other, or may be combined to form a di-on coordination.
• di-on ligands include alkylidene, gen, cyclometalated hydrocarbyl groups, or bidentate chelate ligands.
• the halide may be any of chloride, bromide, fluoride, and iodide! / ⁇ .
• the hydrocarbyl group having 1 to 20 carbon atoms is a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tbutyl group, a pentyl group, an amyl group, an isoamyl group, a hexyl group, or a cyclohexyl group.
• Alkyl groups such as xyl group, heptyl group, octyl group, nor group, decyl group, cetyl group, 2-ethylhexyl group, vinyl group, 1 probe group, isopropyl group, aryl group, Alkyl groups such as methallyl groups, crotyl groups, etc., ether groups, alkyl groups such as 3,3-dimethyl-1-buture groups, aryl groups such as phenol groups, tolyl groups, benzyl groups, diphenylmethyl groups, A aralkyl group such as a phenylalkyl group such as a phenylethyl group, a diphenylethyl group, a trialkylsilylmethyl group, a bis (trialkylsilyl) methyl group, a 2-phenyl-thuryl group, a 2- (trimethyl) Lil) Echuru group, main Chirufue - group, Jimechirufu
• Q 1 and Q 2 are preferably a trialkylsilylmethyl group or an aminobenzyl group.
• the three alkyl groups on the silyl element of the trialkylsilylmethyl group are linear or branched groups having about 1 to 6 carbon atoms, preferably about 1 to 4 carbon atoms. More preferably, a methyl group is mentioned.
• Examples of the trialkylsilyl include trimethylsilyl and t-butyldimethylsilyl.
• Preferred examples of the aminobenzyl group include 0-N, N dimethylaminobenzil group.
• the alkoxy group or aryloxy group is preferably a methoxy group, a substituted or unsubstituted phenoxy group, or the like.
• the amide group is preferably a dimethylamide group, a jetylamide group, a methylethylamide group, a dibutylamide group, a diisopropylamide group, an unsubstituted or substituted diphenylamide group, or a bis (trimethylsilyl) amide group.
• the phosphino group is preferably a diphenylphosphino group, a dicyclohexylphosphino group, a diisopropylphosphino group, a jetylphosphino group, a dimethylphosphino group, or the like.
• the alkylidene is preferably methylidene, ethylidene, propylidene, benzylidene, or the like.
• the cyclometallated hydrocarbyl group is preferably propylene, butylene, pentylene, hexylene, octylene or the like.
• the gen is preferably 1,3 butadiene, 1,3 pentagen, 1,4 pentagen, 1,3 hexagen, 1,4 monohexagen, 1,5 hexagen, 2,4 dimethyl 1,3 Pentagen, 2-methyl-1,3 hexagen, 2,4 monohexagen, etc.
• L in the general formula (I) is a neutral Lewis base.
• the neutral Lewis base include tetrahydrofuran (THF), jetyl ether, dimethylamine, trimethylphosphine, lithium chloride and the like. Among these, tetrahydrofuran is preferable.
• the neutral Lewis base L may be combined with Q 1 and Z or Q 2 to form a so-called multidentate ligand.
• the w of L in the general formula (I) represents the number of neutral Lewis bases.
• w is a force that varies depending on the type of the central metal M, and is usually an integer of 0 to 3, preferably 0 or 1.
• the complex represented by the general formula (A) contained in the polymerization catalyst composition of the present invention is preferably a compound represented by the general formula (B) or (C).
• the central metal M represents any of rare earth elements from lanthanum La to lutetium Lu excluding scandium Sc, yttrium Y or promethium Pm.
• the central metal M is a force that can be appropriately selected according to the type of monomer to be polymerized. Scandium Sc, yttrium Y or lutetium Lu is preferred, particularly scandium. Sc is preferred.
• the catalyst activator contained in the polymerization catalyst composition of the present invention is an ionic compound, an alkylaluminum compound, a Lewis acid, or the like, and preferably an ionicity composed of a non-coordinating cation and a cationic catalyst. Includes composites.
• the catalyst activator activates the complex of the present invention and exhibits activity as a polymerization catalyst. As its activation mechanism, the complex reacts with a catalyst activator, and a plurality of the rare earth metal atoms of the complex are coordinated! /, Q 1 or Q 2 is eliminated, and a cationic complex ( It can be considered that active species) are generated.
• non-coordinating key ion of the ionic compound for example, tetravalent boron key and tetrakis (monofluorophenyl) borate are preferable.
• Examples of the cation of the ionic compound include a carbo cation, an oxo cation, an ammonium cation, a phospho cation, a cycloheptatri cation, and a ph- ole cation cation having a transition metal.
• Specific examples of the carbo-cation include tri-substituted carbo-cations such as tri-phenyl cation and tri-substituted carboxylic cation.
• Specific examples of the tri-substituted phenolic cation include tris (methylphenol) carbocation and tris (dimethylphenol) carbocation.
• ammonium cation examples include trimethyl ammonium cation, triethyl ammonium cation, tripropyl ammonium cation, tri tert-butyl ammonium cation.
• Trialkyl ammonium cations such as tri-n-butyl ammonium cation, ,,-dialkyl aluminum cation such as N, N-jetylarium cation, ⁇ , ⁇ -2,4,6-pentamethylarium cation
• dialkylammonium cations such as di (isopropyl) ammonium cation and dicyclohexylammonium cation.
• phosphonium cation examples include triarylphosphonium cations such as triphenylphosphonium cation, tris (methylphenol) phosphonium cation, and tris (dimethylphenol) phosphonium cation.
• a combination of the above-mentioned non-coordinating cation and cation force can be used.
• a combination of the above-mentioned non-coordinating cation and cation force can be used.
• a combination of the above-mentioned non-coordinating cation and cation force can be used.
• triphenylcarbtetrakis (pentafluorophenol) borate triphenylcarbtetrakis (tetrafluorophenol) borate, ⁇ , ⁇ -dimethylarium tetrakis (pentafluorophenol) -L) borate, 1,1, and dimethyl ferroceum tetrax (pentafluorophenol) borate.
• triphenyl calve tetrakis (pentafluorophenol) borate and ⁇ , ⁇ -dimethyl arlium tetrakis (pentafluorophenol) borate it is preferable to use triphenyl calve tetrakis (pentafluorophenol) borate and ⁇ , ⁇ -dimethyl arlium tetrakis (pentafluorophenol) borate.
• One ionic compound may be used, or two or more ionic compounds may be used in combination.
• Lewis acids that can react with transition metal compounds to form cationic transition metal compounds include B (C F), A1 (C F)
• the polymerization catalyst composition of the present invention may contain at least one of the complexes represented by the general formula (A) and at least one of the catalyst activators, but preferably the general formulas (B) and ( At least one of the complexes represented by C) and triphenylcarbtetrakis (pentafluorophenol) borate ([Ph C] [B (CF)]) and ⁇ , ⁇ -dimethylayuyl-tetrakis ( Pentafluorofe
• the complex represented by the general formula (A) can be used in any amount, and the amount of the isoprene-based compound to be polymerized and the purpose of the production.
• Isoprene The molecular weight of the system polymer can be adjusted. Preferably, it can be an amount suitable for use in the production method of an isoprene-based polymer described later.
• the amount of the catalyst activator which can be adjusted similarly is usually 0.5 to 5 moles, preferably about 1 mole per mole of the complex.
• the polymerization catalyst used in the method for producing an isoprene-based polymer may contain a third component such as an organic aluminum compound or an aluminoxane. Addition of organoaluminum compound or aluminoxane is thought to promote removal of impurities in the reaction system and chain transfer, so it is expected that the catalytic activity and the molecular weight of the resulting polymer will change.
• the polymerization catalyst composition of the present invention is used for polymerization of the isoprene-based compound represented by the general formula (X).
• R 1 represents an alkyl group or an alkenyl group.
• the isoprene-based polymer having high isotacticity is obtained by polymerizing the isoprene-based compound represented by the general formula (X) using the complex represented by the general formula (A) and the catalyst activator. It can be manufactured from cocoon.
• the complex represented by the general formula (A) can be produced, for example, according to the following scheme.
• a person skilled in the art can appropriately select starting materials, reaction reagents, reaction conditions, etc., referring to the general synthesis scheme shown below, and appropriately modify or modify these methods as necessary.
• the complex represented by the formula (A) can be easily produced.
• the contents described in J. AM. CHEM. SOC. 2004, 126, 9182-9183 can also be referred to.
• the amount of the complex used is usually from 0.0001 force to 0.05 monolayer, preferably from 0.0001 force to 0.01 monolayer of an isoprene-based compound. It ’s mono. If the amount of the complex relative to isoprene is reduced, the molecular weight of the resulting isoprene-based polymer can be increased. Conversely, if the amount of the complex is increased, the molecular weight of the isoprene-based polymer can be decreased. .
• the amount of the catalyst activator is usually 0.5 to 5 mol, preferably 1 mol with respect to 1 mol of the complex represented by the general formula (A). About 1 mole.
• the method for producing the isoprene-based polymer of the present invention may be an addition polymerization method, a polycondensation method, a polyaddition method, or other methods, and is preferably an addition polymerization method.
• the production method of the isoprene-based polymer of the present invention may be any method such as a gas phase polymerization method, a solution polymerization method, and a slurry polymerization method.
• the solvent used is not particularly limited as long as it is inactive in the polymerization reaction and can dissolve the isoprene-based compound and the catalyst.
• saturated aliphatic hydrocarbons such as butane, pentane, hexane and heptane
• saturated alicyclic hydrocarbons such as cyclopentane and cyclohexane
• aromatic hydrocarbons such as benzene and toluene
• Halogenated hydrocarbons such as carbon tetrachloride, trichloroethylene, norchloroethylene, 1,2-dichloroethane, black benzene, bromobenzene, and black toluene
• ethers such as tetrahydrofuran and jetyl ether .
• solvents those having a melting point lower than 0 ° C are preferred-those having a melting point lower than 20 ° C are more preferred.
• aromatic hydrocarbons particularly black benzene is preferred.
• One solvent may be used alone, or a mixed solvent of two or more may be used.
• the amount of the solvent used can be usually adjusted so that the concentration of the complex contained in the polymerization catalyst is 0.000001 to 0.1M, preferably 0.0001-0.01M.
• the polymerization reaction temperature may be any temperature, for example, in the range of 100 to 100 ° C. Usually, it may be 25 ° C or lower, preferably 0 ° C or lower, more preferably ⁇ 10 ° C or lower, and further preferably ⁇ 20 ° C or lower.
• the tacticity (isotacticity) of the arrangement of the structural units (1 ′) contained in the obtained isoprene-based polymer can be increased. In other words, by adjusting the polymerization temperature The isotacticity can be adjusted.
• the reaction time is, for example, about 1 minute to 100 hours, usually 1 minute to 24 hours, preferably 5 to 60 minutes.
• these reaction conditions can be appropriately selected according to the polymerization reaction temperature, the type and amount of the monomer, the type and amount of the catalyst composition, etc., and should be limited to the ranges exemplified above. There is no.
• the method for producing an isoprene-based polymer of the present invention may be carried out by adding a complex, an isoprene-based compound, a catalyst activator, and other compounds in an arbitrary order to the reaction system.
• a catalyst activator is added to a mixture of a complex and an isoprene-based compound.
• the molecular weight distribution curve of the obtained isoprene-based polymer may have a plurality of peaks (that is, A mixture of isoprene-based polymers having different molecular weight distribution peaks may be obtained).
• a known polymerization terminator for example, BHT (methanol containing 2,6-bis (t-butyl) -4-methylphenol)
• BHT methanol containing 2,6-bis (t-butyl) -4-methylphenol
• the isoprene-based polymer obtained by polymerizing the isoprene-based compound represented by the general formula (X) using the production method of the present invention has the following general formulas (1), ( ⁇ ), (III),
• the structural unit represented by (IV) (hereinafter, also simply referred to as “structural units (1), ( ⁇ ), (III), (IV)”) may be included in any ratio.
• R 4 in the structural units (I) to (IV) is an alkyl group or an alkenyl group. More preferably, R 4 is a methyl group, that is, the most preferred isoprene-based polymer produced by the production method of the present invention is polyisoprene.
• R 4 is also preferably exemplified by a 4-methyl-3-pentenyl group, that is, a preferred polymer is a myrcene polymer.
• the proportion of the structural unit (I) contained in the isoprene-based polymer produced by the production method of the present invention in the microstructure of the polymer is usually 60% or more, preferably 90% or more. Preferably it is 95% or more, more preferably 99% or more.
• the isoprene-based polymer produced by the production method of the present invention can contain structural units (II) to (IV) in an arbitrary ratio in addition to the structural unit (I).
• the proportion of the structural unit (I) in the microstructure is calculated by measuring the NMR vector of the obtained isoprene-based polymer, obtaining the integral value of the peak attributed to each structural unit, and comparing it. be able to. This calculation will be described later in the specification of the present application.
• the structural unit (I) contained in the isoprene-based polymer is usually arranged in a head-to-tail manner, and the following two stereoisomerisms can occur in the arrangement.
• the structural units (I) contained in the isoprene-based polymer produced by the production method of the present invention are arranged with stereoregularity, preferably arranged in a highly isotactic manner.
• Highly isotactic arrangement means that the 1-alkylbule group or 1-alkenylvinyl group (or hydrogen atom) in general formula (I) is on one side of the plane formed by the polymer main chain. Is selectively arranged.
• the isotacticity of the arrangement of structural units (I) contained in the isoprene-based polymer produced by the production method of the present invention is at least 60% mm or more in triad display, usually It is 80% mm or more, preferably 90% mm or more, more preferably 95% mm or more, more preferably 99% mm or more, and most preferably 99% mm mm or more in the pentat display.
• I structural units in the isoprene-based polymer
• triazide Three types of structural units (I) in the isoprene-based polymer (referred to as “triazide”) can be considered as follows: three isotactic triads, heterotactic triads, and syndiotactic triads. It is done. Isotacticity in terms of triad means the ratio of “isotactic triad, heterotriad” in the polymer, and the percentage is expressed as '% mm'.
• isotacticity by pentad display refers to the proportion of isotactic pentads in the pentad, focusing on the five chains of structural units (I) (referred to as "pentads") in the same manner as triad display. The percentage of the percentage is displayed as '% mmmm'.
• the isotacticity of the sequence of the structural unit (I) contained in the isoprene-based polymer can be represented by triad display or pentad display as described above.
• the isotacticity of the isoprene-based polymer by triad display or pentad display can also calculate the NMR ⁇ vector data (preferably 13 C-NMR) force of the obtained isoprene-based polymer. This calculation is described later in this specification.
• the average molecular weight of the isoprene-based polymer produced by the production method of the present invention is an arbitrary power-average molecular weight of at least 5,000, usually 50,000 or more, preferably 100,000 or more.
• the upper limit of the number average molecular weight is not particularly limited, but can be 6 million or less as a guide.
• the number average molecular weight means a number average molecular weight measured by a GPC method, and can be measured using, for example, a GPC measuring apparatus (TOSOH HLC 8220 GPC).
• the molecular weight distribution of the isoprene-based polymer produced by the production method of the present invention is usually 6 or less, preferably 3 or less, more preferably 1.7 or less when expressed in M / M.
• the molecular weight distribution means a molecular weight distribution measured by a GPC method, and can be measured using, for example, a GPC measuring apparatus (TOS OH HLC 8220 GPC).
• the isoprene-based polymer produced by the production method of the present invention has a 1-alkylbutyl group or a 1-alkylcarbyl group containing a carbon double bond as a side chain.
• the carbon double bond of the bur group can be hydrosilylated or hydroborated or epoxyized.
• the isoprene-based polymer produced by the production method of the present invention may include not only a homopolymer but also a copolymer.
• a copolymer may be, for example, a copolymer of isoprene and an isoprene-based compound other than isoprene, or a copolymer of isoprene and a conjugate. Further, it may be a copolymer of an isoprene-based compound and a nonpolar monomer (including ethylene, styrene, etc.) or a polar monomer (including latathone, acrylate ester, etc.).
• the isoprene-based polymer can be identified by ⁇ H-NMR analysis, 13 C-NMR analysis, measurement of average molecular weight and molecular weight distribution by GPC method, IR measurement, mass spectrometry and the like.
• NMR analysis means analysis by nuclear magnetic resonance spectroscopy at a frequency of 400 MHz.
• the analysis can be performed by using JNM-AL-400RN manufactured by JEOL, which is an NMR analyzer.
• NMR ⁇ vector data means the analysis Means the spectrum data obtained by The measurement solvent is heavy black mouth form CDC1
• Measurement temperature is 25 ° C (room temperature).
• the proportion of the isoprene-based polymer in the microstructure of the structural unit (3,4-structure) represented by the general formula (I) is as follows (WM Dong, T. Masuda, J. Polym. Sci., Part A: Poly m. Chem., 40, 1838 (2002), AS Khatchaturov, ER Dolinskaya, LK Prozenko, EL Abramenko and VA Kormer, Polymer, 18, 871, (1976)). NMR spectrum data can be obtained.
• the isotacticity of the sequence of the structural unit (structural unit (I)) represented by the general formula (I) contained in the isoprene-based polymer can be determined from NMR vector data.
• FIGS. 8 and 9 show polyisoprene, the proportion of structural unit (I) in the microstructure is 92%, and the isotacticity of the structural unit (I) is 36% mm.
• 1 is a measurement chart of 1 H-NMR and 13 C-NMR of a polymer. In Figs.
• FIGS. 1 and 2 show polyisoprene, in which the proportion of structural units (I) in the microstructure is 99.8% and the isotacticity of the arrangement of structural units (I) is 99%. Measurement chart of 1 H-NMR and 13 C-NMR of a polymer of mmmm, FIGS.
• the compounds obtained in the following examples are 1 H-NMR, 13 C-NMR (JEOL JNM-AL 400RN), GPC (TOSOH HLC-8220), UV (SHIMAZDZU CORPRATION UV-PC SERIES U V-2400PC / UV -2500PC). Elemental analysis for RIKEN Chemical Analysis Laboratory More analyzed.
• the solution is dropped into a mixed solution containing isoprene and (NCN) Sc (CH 2 SiMe) (THF) in the flask,
• a polymer was obtained in the same manner as in Example 1 except that the reaction time in Example 1 was changed from 20 minutes to 10 minutes.
• Example 1 The reaction time in Example 1 was changed from 20 minutes to 5 minutes and (NCN) Sc (CH SiMe) (TH).
• Example 2 The same procedure as in Example 1 was conducted except that (NCN) Y (CH SiMe) (THF) was used instead of (F).
• Example 1 a polymer was obtained in the same manner as in Example 1 except that the reaction temperature was changed from ⁇ 10 ° C. to room temperature and the reaction time was changed from 20 minutes to 5 minutes.
• FIG. 5 shows a 1 H-NMR ⁇ vector chart of the obtained polymer
• FIG. 6 shows a 13 C-NMR ⁇ vector chart.
• NMR ⁇ vectors were measured at room temperature using heavy chloroform as a solvent.
• Figure 7 shows the DSC chart.
• Example 4 instead of [Ph C] [B (C F)], [PhMe NH] [B (C F)] was used.
• a polymer was obtained in the same manner as in Example 4 except for the above.
• Example 4 instead of (NCN) Sc (CH SiMe) (THF), (NCN) Y (CH SiMe) (THF)
• a polymer was obtained in the same manner as in Example 4 except that 2 3 2 2 3 2 was used.
• Example 6 instead of [Ph C] [B (C F)], [PhMe NH] [B (C F)] was used.
• FIG. 8 shows a 1 H-NMR ⁇ vector chart of the obtained polymer
• FIG. 9 shows a 13 C-NMR ⁇ vector chart.
• NMR ⁇ vector was measured at room temperature using deuterated form as solvent.
• a polymer was obtained in the same manner as in Example 4 except that.
• Example 7 instead of (NCN) Sc (CH SiMe) (THF), (NCN) Y (CH SiMe) (THF)
• a polymer was obtained in the same manner as in Example 7 except that 2 3 2 2 3 2 was used.
• Example 9 In Example 7, instead of (NCN) Sc (CH SiMe) (THF), (NCN) Lu (CH SiMe) (THF)
• a polymer was obtained in the same manner as in Example 7 except that 2 3 2 2 3 2 was used.
• Example 7 instead of (NCN) Sc (CH SiMe) (THF), (NCN) Sc (CH C H NMe -o)
• a polymer was obtained in the same manner as in Example 7 except that 2 3 2 2 6 4 2 was used.
• Example 7 instead of (NCN) Sc (CH SiMe) (THF), (NCN) Y (CH C H NMe -o)
• a polymer was obtained in the same manner as in Example 7 except that 2 3 2 2 6 4 2 2 was used.
• Example 7 a polymer was obtained in the same manner as in Example 7, except that the reaction temperature was changed from room temperature to -10 ° C and the reaction time was changed from 5 minutes to 20 minutes.
• Example 11 instead of (NCN) Sc (CH SiMe) (THF), (NCN) Y (CH SiMe) (THF)
• a polymer was obtained in the same manner as in Example 11 except that 2 3 2 2 3 2 was used.
• a polymer was obtained in the same manner as in Example 11 except that F) was used.
• Example 11 instead of (NCN) Sc (CH SiMe) (THF), (NCN) Sc (CH C H NMe-
• a polymer was obtained in the same manner as in Example 11 except that 2 3 2 2 6 4 2 o) was used.
• a polymer was obtained in the same manner as in Example 14, except that the reaction time was changed from 20 minutes to 30 minutes in Example 14.
• Example 14 (NCN) Sc (CH C H NMe -o) was previously added in [Ph C] [B (C F)] for 10 minutes.
• Example 17 In Example 14, instead of (NCN) Sc (CH CH NMe -o), (NCN) Y (CH CH NMe-
• a polymer was obtained in the same manner as in Example 14 except that 2 6 4 2 2 2 6 4 2 o) was used.
• Example 8 a polymer was obtained in the same manner as in Example 8 except that the reaction temperature was changed from room temperature to 20 ° C.
• Table 1 shows the yield (%) of polyisoprene obtained in Examples and Reference Examples, number average molecular weight M, molecular weight distribution M / M, ratio of 3,4-polyisoprene to total polyisoprene (%). , Isotacticity (%) in triad display and pentad display, glass transition temperature T (° C) g
• polyisoprene having a high isotacticity can be produced by appropriately selecting the reaction conditions using the polymerization catalyst composition of the present invention.
• (NCN) Sc (CH SiMe) (THF) or (NCN) Sc (CH C H NMe -o) is used as a complex and used as a catalyst activator.
• Len can be produced.
• NCN Sc (CH SiMe) (THF)
• NCN Y (CH SiMe) (THF)
• reaction temperature was set to room temperature, the reaction time was 30 minutes, and the reaction was carried out in the same manner as in the Examples.
• B and C represent complexes represented by the general formula (B) and the general formula (C), respectively, and the parenthesis represents the central metal M.
• a is [Ph 3 C] [B (C 6 F 5 ) 4]
• b is [PhMe 2 NH] [B (C 6 F 5 ) 4 ]
• c is B (C 6 F 5 ) 3 is shown.
• the isoprene-based polymer produced by the production method using the polymerization catalyst composition of the present invention is considered to exhibit excellent mechanical or thermal durability with high isotacticity. Therefore, it is expected to be used as a plastic material.
• the polymerization catalyst composition of the present invention is low in cost, the double bond of the 1-alkylvinyl group or 1-alkenylvinyl group in the side chain of the isoprene-based polymer is chemically modified. Therefore, it is considered useful for the development of new functional polymers.

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