WO2007102227A1 - Copolymere sequence olefinique - Google Patents

Copolymere sequence olefinique Download PDF

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Publication number
WO2007102227A1
WO2007102227A1 PCT/JP2006/304648 JP2006304648W WO2007102227A1 WO 2007102227 A1 WO2007102227 A1 WO 2007102227A1 JP 2006304648 W JP2006304648 W JP 2006304648W WO 2007102227 A1 WO2007102227 A1 WO 2007102227A1
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Prior art keywords
olefin
group
groups
polymerization
carbon atoms
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PCT/JP2006/304648
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English (en)
Japanese (ja)
Inventor
Rieko Ohtani
Makoto Mitani
Junji Saito
Yasuhiko Suzuki
Seiichi Ishii
Hiroshi Terao
Terunori Fujita
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Mitsui Chemicals, Inc.
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Priority to PCT/JP2006/304648 priority Critical patent/WO2007102227A1/fr
Publication of WO2007102227A1 publication Critical patent/WO2007102227A1/fr

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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
    • C08F297/06—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 coordination type
    • C08F297/08—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 coordination type polymerising mono-olefins

Definitions

  • the present invention relates to an olefin block copolymer.
  • a block copolymer in which different segments are bonded exhibits various useful physical properties, and thus is very important not only from an academic standpoint but also from an industrial standpoint.
  • the molecular weight distribution (Mw / Mn) of the block copolymer which is an indicator of living polymerizability, is not as narrow as 1.35 or more, and it is not a well-controlled living polymerization. . Therefore, the product is almost always a by-product of large amounts of unblocked polymer.
  • Mw / Mn the molecular weight distribution of the block copolymer
  • the present applicant has found a transition metal compound having a salicylaldimine ligand as a new catalyst for olefin polymerization.
  • these transition metal compounds having a salicylaldimine ligand those having a specific structure can be used at an industrially high temperature and at a very high activity compared to conventionally known living polymerization.
  • Living polymerisation has progressed and the present invention has been completed by finding that a block copolymer can be produced.
  • the inventors have invented a method for efficiently producing such a block copolymer and have completed the present invention.
  • Patent Document 1 International Publication No. 91/12285
  • Patent Document 2 International Publication No.94 / 21700
  • an object of the present invention is to provide a block copolymer in which different segments are bonded and exhibit various useful physical properties.
  • the olefin block copolymer according to the present invention comprises (i) a polymer block obtained from at least one olefin selected from olefins having 2 to 20 carbon atoms, and (ii) 2 carbon atoms.
  • Olefin block copolymer comprising at least one selected from the above-described polymer block (i), and a polymer block different from the polymer block (i) obtained, and any adjacent polymer block different from each other
  • the Mn number average molecular weight
  • MwZMn molecular weight distribution
  • the polymer block is (a) a polymer block obtained from ethylene, and (b) ethylene, and having 4 to 12 carbon atoms. Nohi-o It is characterized by being a random copolymer block obtained from refin.
  • the olefin block copolymer according to the present invention comprises (i) a polymer block obtained from at least one olefin selected from olefin having 2 to 20 carbon atoms, and (ii) 2 to 20 carbon atoms. And a polymer block different from the polymer block (i) to be obtained, and any adjacent polymer block is an olefin block copolymer different from each other. .
  • the olefin block copolymer according to the present invention has an Mn (number average molecular weight) of 500 or more and an MwZMn (molecular weight distribution) of 1.5 or less, preferably 1.3 or less. .
  • the polymer block is composed of (a) a polymer block obtained from ethylene, and (b) ethylene and a 4-olefin having 12 to 12 carbon atoms. It is a random copolymer block obtained.
  • the olefin block copolymer according to the present invention is preferably a diblock copolymer.
  • the polymer block (b) is preferably obtained from ethylene and one kind of olefins selected from ⁇ -olefins having 6 to 10 carbon atoms.
  • Such an olefin block copolymer is excellent in impact resistance, moldability, tensile strength, ductility, blocking resistance, elasticity, rigidity, and film-forming properties, so it can be used in films, sheets, professional molded products, etc. It is suitably used for various molding materials, various additives such as compatibilizers and modifiers, paints and adhesives.
  • the olefin block copolymer according to the present invention comprises:
  • (B-2) an organoaluminum compound
  • transition metal compound (A) is polymerized by an olefin polymerization catalyst characterized by comprising at least one compound selected from compounds that react with (A) to form ion pairs.
  • an olefin polymerization catalyst characterized by comprising at least one compound selected from compounds that react with (A) to form ion pairs.
  • ⁇ ⁇ represents a titanium atom
  • m represents an integer of 1 to 2
  • R 1 represents a fluorine-containing hydrocarbon group having 1 to 30 carbon atoms
  • R 2 to R 5 represent each other.
  • R 6 represents a hydrocarbon group, a hydrogen atom or a hydrocarbon-substituted silyl group which may be the same or different, and two or more of these may be connected to each other to form a ring.
  • n 2 or more
  • a plurality of groups represented by X may be the same as or different from each other, and a plurality of groups represented by X are bonded to each other.
  • a ring may be formed.
  • the (A) transition metal compound used in the present invention is a compound represented by the following general formula (I).
  • N may or may not be coordinated.
  • M is a titanium atom.
  • R 1 represents a fluorine-containing hydrocarbon group having 1 to 30 carbon atoms
  • R 2 to R 5 represent a hydrocarbon group, a hydrogen atom or a hydrocarbon-substituted silyl group which may be the same or different from each other
  • R 6 represents a group selected from the four basic forces of hydrogen, an aliphatic hydrocarbon group, a monocyclic alicyclic hydrocarbon group, and an aromatic hydrocarbon group, and two or more of these are selected. They may be connected to each other to form a ring.
  • fluorine-containing hydrocarbon group having 1 to 30 carbon atoms of R 1 include trifluoromethyl, perfluoroethyl, perfluoropropyl, perfluorobutyl, perfluoropentyl, Perfluoro mouth hexyl, monofluorophenyl, difluorophenyl, trifluorophenol, tetrafluorophenyl, pentafluorophenyl, (trifluoromethylenoyl) phenyl, trifluoromethylphenyl, bis (trifluoromethyl) phenyl, tris ( Trough Norreolomethinole) phenyl, tetrakis (trifluoromethyl) phenyl, pentakis (trifluoromethinole) phenyl, (trifluoromethyl) tetrafluorophenyl, perfluoroethenophenyl, bis (perfluoroethin
  • R 1 is a C6-C30 aromatic hydrocarbon group having a fluorine substituent or a fluorine-containing hydrocarbon substituent, and specifically, monofluorophenyl, difluorophenyl, trifluoro Phenyl, tetrafluorophenyl, pentafluorophenyl, (trifluoromethylolenyl) phenyl, trifluoromethylphenyl, bis (trifluoromethinole) phenyl, tris (trifluoromethylenole) phenyl, tetrakis (trifluoromethyl) Tinole) phenyl, pentakis (trifluoromethyl) phenyl, (trifluoromethyl) tetrafluorophenyl, monofluorophenyl, bis (perfluoroethyl) phenyl, perfluoropropylphenyl, perfluoro Robutyl phenyl,
  • R 1 is an aromatic hydrocarbon group having 6 to 30 carbon atoms having two or more substituents selected from the group consisting of a fluorine substituent or a fluorine-containing hydrocarbon substituent, and specifically, Is difluorophenyl, trifluorophenyl, tetrafluorophenyl, pentafluororerophenyl, (trifluoromethyl) phenyl, bis (trifluoromethyl) phenyl, tris (trifluoromethylenole) phenyl, tetrakis (trifluoromethyl) Tinole) funil, pentakis (trifluoromethyl) phenyl, (trifluoromethyl) tetrafluorophenyl, bis (perfluoroethyl) phenyl, bis (perfluorohexyl) phenyl, and the like.
  • R 1 is a difluorophenyl group, a trifluorophenyl group, a tetrafluorophenyl group, a pentafluorophenyl group, or (trifluoromethyl) tetrafluorophenyl.
  • Specific examples include tetrafluorophenyl.
  • Examples of the hydrocarbon group represented by R 2 to R 5 include those having carbon numbers of! To 30. Specifically, the number of carbon atoms such as methinole, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s_butyl, t-butyl, neopentyl, n-hexyl, etc.
  • the hydrocarbon group may be substituted with another hydrocarbon group, and examples thereof include aryl group-substituted alkyl groups such as benzyl and Tamyl.
  • Examples of the hydrocarbon-substituted silyl group represented by R 2 to R 5 include groups having a total carbon number of 1 to 30. Specific examples include methylsilyl, dimethylsilyl, trimethylsilyl, ethylsilinole, jetylsilyl, triethylsilyl, diphenylmethylsilyl, triphenylsilyl, dimethylphenylsilyl, dimethyl-t-butylsilyl, dimethyl (pentafluorophenyl) silyl, etc. Is mentioned.
  • methylsilyl, dimethylsilyl, trimethylsilylole, ethylsilyl, jetylsilyl, triethynolesilyl, dimethylphenylsilyl, triphenylsilyl and the like are preferable. Particularly preferred are trimethylsilyl, triethylsilyl, triphenylsilyl, and dimethylphenylsilyl.
  • monocyclic alicyclic hydrocarbon groups having 3 to 30, preferably 3 to 8, carbon atoms such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and cyclooctyl.
  • aromatic hydrocarbon group for R 6 examples include those having 6 to 30 carbon atoms. Specific examples include aromatic hydrocarbon groups having 6 to 30 carbon atoms, such as phenyl, naphthyl, biphenylyl, triphenylyl, fluorenyl, anthranolinole, phenanthryl.
  • n is a number satisfying the valence of M, specifically an integer of 2 to 4, and preferably 2.
  • X represents a hydrogen atom, a halogen atom, a hydrocarbon group, an oxygen-containing group, a thio-containing group, a nitrogen-containing group, a boron-containing group, an aluminum-containing group, a phosphorus-containing group, a halogen-containing group, a heterocyclic compound residue A group, a silicon-containing group, a germanium-containing group, or a tin-containing group.
  • n is 2 or more
  • a plurality of groups represented by X may be the same or different from each other, and a plurality of groups represented by X are bonded to each other to form a ring. Also good.
  • Examples of the hydrogen atom and the rogen atom include fluorine, chlorine, bromine and iodine.
  • hydrocarbon group examples include the same groups as those exemplified above for R 2 to R 5 .
  • alkyl groups such as methylol, ethyl, propyl, butyl, hexyl, octyl, noel, dodecyl, eicosyl
  • cycloalkyl having 3 to 30 carbon atoms such as cyclopentyl, cyclohexyl, norbornyl, and adamantyl Groups
  • alkenyl groups such as vinyl, propenyl, cyclohexenyl
  • arylalkyl groups such as benzyl, phenylethyl, phenylpropyl; phenyl, trinole, dimethylphenyl, trimethylphenyl, ethylphenyl, propylphenyl, biphenyl
  • allyl groups such as naphthyl, methylnaphthyl, anthryl, phen
  • the heterocyclic compound residue includes nitrogen-containing compounds such as pyrrole, pyridine, pyrimidine, quinoline and triazine, oxygen-containing compounds such as furan and pyran, and sulfur-containing compounds such as thiophene.
  • nitrogen-containing compounds such as pyrrole, pyridine, pyrimidine, quinoline and triazine
  • oxygen-containing compounds such as furan and pyran
  • sulfur-containing compounds such as thiophene.
  • residues such as compounds, and groups obtained by further substituting substituents such as alkyl groups and alkoxy groups having carbon atoms:! To 30, preferably 1 to 20, to these heterocyclic compound residues.
  • oxygen-containing group examples include hydroxy groups; alkoxy groups such as methoxy, ethoxy, propoxy, and butoxy; aryloxy groups such as phenoxy, methylphenoxy, dimethylphenoxy, and naphthoxy; phenylmethoxy, Forces including aryloxy groups such as phenylethoxy; acetoxy groups; carbonyl groups and the like.
  • thio-containing group examples include methyl sulfonate, trifluoromethane sulfonate, phenyl sulfonate, benzyl sulfonate, p-toluene sulfonate, trimethylbenzene sulfonate, trimethyl sulfonate.
  • Sulfonate groups such as i-butylbenzene sulfonate, p-chlorobenzene sulfonate, pentafluorobenzene sulfonate; methinores norefinate, phenenoles norefinate, pendinoles norefinate , Sulfinate groups such as p-tonolene sulfinate, trimethylbenzene sulfinate, pentafluorobenzene sulfinate; alkylthio groups; arylthio groups and the like, but not limited thereto.
  • nitrogen-containing groups include amino groups; alkylamino groups such as methylamino, dimethylamino, jetylamino, dipropylamino, dibutylamino, dicyclohexylamino, etc .; phenylamino, diphenylamino, ditolylamino, dinaphthylamino, methylphenylamino, etc.
  • a force such as an arylarylamino group or an alkylarylamino group is not limited thereto.
  • boron-containing group examples include BR (R represents hydrogen, an alkyl group, an aryl group which may have a substituent, a halogen atom, or the like).
  • phosphorus-containing groups include trialkylphosphine groups such as trimethylphosphine, tributylphosphine, and tricyclohexylphosphine; triarylphosphine groups such as triphenylphosphine and tolylphosphine; methyl phosphite, ethyl phosphite, phenyl Examples thereof include, but are not limited to, phosphite groups (phosphide groups) such as ruphosphite; phosphonic acid groups; phosphinic acid groups.
  • trialkylphosphine groups such as trimethylphosphine, tributylphosphine, and tricyclohexylphosphine
  • triarylphosphine groups such as triphenylphosphine and tolylphosphine
  • methyl phosphite ethyl phosphite
  • phenyl Examples thereof include, but are not limited to,
  • silicon-containing group examples include fuel silyl, diphenyl silyl, trimethylsilinole, triethinoresilinole, triprovirsilyl, tricyclohexylsilyl, triphenylsilyl, methyldiphenylsilyl, tritolylsilyl, tritriol.
  • examples thereof include hydrocarbon-substituted silanol groups such as naphthylsilyl; hydrocarbon-substituted silyl ether groups such as trimethylsilyl ether; silicon-substituted alkyl groups such as trimethylsilinolemethyl;
  • germanium-containing group examples include groups obtained by substituting the silicon of the above-described group containing a group with germanium.
  • tin-containing group examples include groups obtained by substituting the key of the above-mentioned key-containing group with tin.
  • halogen-containing groups include fluorine-containing groups such as PF and BF, ClO, and SbCl.
  • AIR has hydrogen, an alkyl group, and a substituent.
  • a force such as a aryl group or a halogen atom is not limited thereto.
  • the preferred structure and structure of the transition metal compound (A) used in the present invention includes the general formula (I) wherein M is a titanium atom, m is 2, and R 1 is at least two or more fluorine substituents. It is preferably an aromatic hydrocarbon group having 6 to 30 carbon atoms having R 1 is a difluorophenyl group, a trifluorophenyl group, a tetrafluorophenyl group, or a pentafluorophenyl group, and R 6 is a linear or branched alkyl group of:! To 3 or 3 to 8 A monocyclic hydrocarbon group or an aromatic hydrocarbon group having 6 to 30 carbon atoms is particularly preferable.
  • transition metal compound represented by the general formula (I) are shown below, but are not limited thereto.
  • Me represents a methyl group
  • Et represents an ethyl group
  • ! Represents an i-propyl group
  • 3 ⁇ 4 ⁇ represents a t-butyl group
  • Ph represents a phenyl group.
  • the method for producing such a transition metal compound (A) is not particularly limited and can be produced, for example, as follows.
  • the ligand constituting the transition metal compound (A) is a salicylaldehyde compound, a primary amin compound of the formula ⁇ ⁇ - ⁇ (R 1 is as defined above), for example, an aniline Conversion
  • both starting compounds are dissolved in a solvent.
  • a solvent those commonly used in such a reaction can be used, and among them, alcohol solvents such as methanol and ethanol, and hydrocarbon solvents such as toluene are preferable.
  • the resulting solution is then stirred for about 1 to 48 hours at room temperature to reflux conditions to give the corresponding ligand in good yield.
  • an acid catalyst such as formic acid, acetic acid or toluenesulfonic acid may be used as a catalyst.
  • molecular sieves magnesium sulfate or sodium sulfate is used as a dehydrating agent, or dehydration is performed using a Dean-Stark trap, it is effective for the progress of the reaction.
  • a corresponding transition metal compound can be synthesized by reacting the thus obtained ligand with a transition metal salt-containing compound.
  • the synthesized ligand is dissolved in a solvent and brought into contact with a base as necessary to prepare a phenoxide salt, and then mixed with a metal compound such as a metal halide or metal alkylate at a low temperature.
  • a metal compound such as a metal halide or metal alkylate
  • polar solvents such as ether and tetrahydrofuran (THF), hydrocarbon solvents such as toluene and the like are preferably used.
  • the base used in preparing the phenoxide salt is preferably a metal salt such as a lithium salt such as n-butyllithium, a sodium salt such as sodium hydride, or an organic base such as triethylamine or pyridine. Not as long.
  • the corresponding transition metal compound can be synthesized by directly reacting the ligand and the metal compound without going through the preparation of the phenoxide salt. It is also possible to exchange the metal M in the compound with another transition metal by a conventional method. Also for example! When any of ⁇ to is H, substituents other than H can be introduced at any stage of the synthesis.
  • reaction solution of the ligand and the metal compound is left as it is. It can also be used for polymerization.
  • the above transition metal compounds (A) are used singly or in combination of two or more.
  • organometallic compounds of Groups 1, 2 and 12, 13 of the periodic table described in Japanese Patent Application No. 2002-311685 are used.
  • the (B-2) organoaluminum compound used in the present invention may be a conventionally known aluminoxane or a benzene-insoluble organoaluminum compound as exemplified in JP-A-2-78687. Kissy compound may be used.
  • the compound (B-3) (hereinafter referred to as “ionized ionic compound”) that reacts with the transition metal compound (A) used in the present invention to form an ion pair, JP-A-1-501950, JP-A-1-502036, JP-A-3-179005, JP-A-3-179006, JP-A-3-207703, JP-A-3-207704, USP-5321106, etc.
  • heteropoly compounds and isopoly compounds can also be mentioned.
  • transition metal compound (A) according to the present invention when it is used in combination with an organoaluminum oxide compound (B-2) such as methyl aluminoxane as a promoter component, the olefin compound is greatly reduced. High polymerization activity.
  • an ionized ionic compound (B-3) such as triphenylcarbontetrakis (pentafluorophenyl) borate is used as a promoter component, an olefin polymer having good activity and a very high molecular weight can be obtained.
  • the olefin polymerization catalyst used for the polymerization of the olefin block copolymer according to the present invention may be (A) the transition metal compound represented by (I) may be used alone,
  • B (B-1) an organometallic compound, (B-2) an organoaluminum compound, and
  • these compounds are formed in the polymerization system.
  • the bond between metals M and Y can be covalently bonded, or can be ionic, or can be ionic bonded.
  • Specific examples of 1 ⁇ to 1 6 , M, m, n, and X in the formula are the same as (I).
  • Examples of Y include Chemical Review Journal 88 ⁇ 1405 (1988), Chemical Review Journal 93 ⁇ 927 pages (1993), WO98 / 30612 6 page, weakly coordinating anions are mentioned.
  • AIR— R can be one kind or two or more kinds of oxygen atoms, nitrogen atoms , Rinhara
  • Examples include ensulfonate.
  • the catalyst for olefin polymerization according to the present invention includes the transition metal compound (A), (B-1) an organometallic compound, (B-2) an organoaluminum oxide compound, and (B-3).
  • a carrier (C) as described later can be used as necessary together with at least one compound (B) selected from ionic compounds.
  • the carrier (C) used in the present invention is an inorganic or organic compound and is a granular or particulate solid.
  • the catalyst for olefin polymerization used for the polymerization of the olefin block copolymer according to the present invention includes the transition metal compound (A), (B-1) an organometallic compound, (B-2) an organoaluminum oxy compound, And (B-3) at least one compound (B) selected from ionic and ionic compounds, and optionally a carrier (C) and, if necessary, specific organic compound components (D ) Can also be included.
  • the organic compound component (D) is used for the purpose of improving the polymerization performance and the physical properties of the produced polymer, if necessary.
  • organic compounds include, but are not limited to, alcohols, phenolic compounds, carboxylic acids, phosphorus compounds and sulfonates.
  • FIG. 1 and FIG. 2 show steps for preparing the olefin polymerization catalyst according to the present invention.
  • the method of using each component and the order of addition are arbitrarily selected, and the following methods are exemplified.
  • component (A) and component (B) are added to the polymerization vessel in any order.
  • component (A) is supported on the carrier (C) and the component (B) is added to the polymerization vessel in any order.
  • the unsupported component (B) may be added in any order as necessary.
  • the components (B) may be the same or different.
  • a catalyst component may be further supported on the prepolymerized solid catalyst component that is polymerized and re-polymerized.
  • the olefin block copolymer according to the present invention is a catalyst for olefin polymerization as described above. (A) polymerization of a polymer block obtained from ethylene, and then (b) copolymerization of ethylene and a random copolymer block obtained from ⁇ -olefin linker having 4 to 12 carbon atoms. Is obtained.
  • the polymerization of the olefin block copolymer according to the present invention includes (b) a random copolymer block obtained from ethylene and an ⁇ -olefin having 4 to 12 carbon atoms, and then (a) ) Polymerization of polymer blocks obtained from ethylene, then (b) ethylene and 4 to 4 carbon atoms
  • the polymerization can be carried out even if liquid phase polymerization methods such as solution polymerization and suspension polymerization or gas phase polymerization methods are used.
  • the inert hydrocarbon medium used in the liquid phase polymerization method include fats such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene.
  • Aromatic hydrocarbons such as cyclopentane, cyclohexane, and methylcyclopentane;
  • Aromatic hydrocarbons such as benzene, toluene, and xylene;
  • Halogenated hydrocarbons such as ethylene chloride, chlorobenzene, and dichloromethane or these It is possible to use a mixture of these materials, and olefins themselves can be used as a solvent.
  • Ingredient (A) is, per liter of the reaction volume, usually 10- 12 ⁇ 10- 2 mol, preferably 10- 1Q ⁇ : used in an amount such that 10-3 molar.
  • Component (B-1) is a molar ratio [(B-1) / M] force between component (B-1) and all transition metal atoms (M) in component (A). Usually 0.01 to 100000 Preferable ⁇ is used in an amount such that 0.05 to 50000.
  • Component (B-2) is a monolayer of aluminum atom in component (B-2) and transition metal atom (M) in component (A): ⁇ [(B_2) / M], usually 10 ⁇
  • the amount used is 500000, preferably 20 to 100000.
  • Component (B-3) contains component (B-3) and component (transition metal atom (M) in A molar ratio [(B-3) / M] force usually:! -10, preferably 1 Used in such an amount that it becomes ⁇ 5.
  • the component (D) has a molar ratio [(D) / (B-1)] of usually 0 ⁇ 01 to 10, preferably 0.
  • component (B) is component (B-2) in such an amount as 1 to 5, monole]; ⁇ [(D) / (B-2)] force S Normal 0.001 to 2
  • the molar ratio [(D) / (B-3)] is usually 0. It is used in an amount such that 01 :: 10, preferably 0 ⁇ :!-5.
  • the polymerization temperature of olefin using such an olefin polymerization catalyst is usually in the range of -50 to + 200 ° C, preferably 0 to 170 ° C.
  • the polymerization pressure is usually from normal pressure to 100 kg / cm 2 , preferably from normal pressure to 50 kg / cm 2 , and the polymerization reaction can be carried out in batch, semi-continuous, or continuous methods. You can do it.
  • Mn number average molecular weight
  • Mw / Mn molecular weight distribution
  • a glass autoclave with an internal volume of 500 ml that had been thoroughly purged with nitrogen was charged with 250 ml of Tonolene, and the liquid phase and gas phase were saturated with ethylene, and then only the gas phase was purged with nitrogen.
  • Polymerization was started by adding 2.5 mmol of methylaluminoxane in terms of aluminum atom, and subsequently adding 0.02 mmol of titanium compound (1) (a synthesis example is described in JP-A No. 2004-2640). After 5 minutes of reaction at 25 ° C and complete consumption, 10 ml of 1-hexene was added and reacted for 5 minutes while blowing ethylene gas (50 liters of Zh).
  • the resulting copolymer had an Mn (number average molecular weight) of 80,000, an Mw / Mn (molecular weight distribution) of 1.26, and a 1-hexene content measured by IR of 6.0 monole. %Met.
  • the olefin block copolymer of the present invention is excellent in impact resistance, moldability, tensile strength, ductility, blocking resistance, elasticity, rigidity and film-forming properties. It is expected to make significant industrial contributions in the field of seed additives, paints and adhesives.

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  • Inorganic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
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Abstract

L'invention concerne un copolymère séquencé comprenant différents segments liés les uns aux autres et présentant diverses propriétés physiques utiles, ainsi qu'un procédé de fabrication du copolymère séquencé avec une bonne efficacité. L'invention concerne donc un copolymère séquencé oléfinique comprenant (i) une séquence polymère obtenue à partir d'au moins une oléfine choisie parmi les oléfines ayant de 2 à 20 atomes de carbone et (ii) une séquence polymère obtenue à partir d'au moins une oléfine choisie parmi les oléfines ayant de 2 à 20 atomes de carbone et étant différente de la séquence polymère (i), toutes les séquences polymères adjacentes étant différentes les unes des autres, le copolymère séquencé oléfinique ayant une Mn (masse moléculaire moyenne en nombre) supérieure ou égale à 500 et une valeur Mw/Mn (distribution de masse moléculaire) inférieure ou égale à 1,5.
PCT/JP2006/304648 2006-03-09 2006-03-09 Copolymere sequence olefinique WO2007102227A1 (fr)

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Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005089497A (ja) * 2003-09-12 2005-04-07 Mitsui Chemicals Inc オレフィンブロック共重合体、及びその製造方法

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005089497A (ja) * 2003-09-12 2005-04-07 Mitsui Chemicals Inc オレフィンブロック共重合体、及びその製造方法

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