WO2013031779A1 - Procédé de fabrication de polymère de α-oléfine - Google Patents

Procédé de fabrication de polymère de α-oléfine Download PDF

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WO2013031779A1
WO2013031779A1 PCT/JP2012/071722 JP2012071722W WO2013031779A1 WO 2013031779 A1 WO2013031779 A1 WO 2013031779A1 JP 2012071722 W JP2012071722 W JP 2012071722W WO 2013031779 A1 WO2013031779 A1 WO 2013031779A1
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group
carbon atoms
component
olefin polymer
olefin
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PCT/JP2012/071722
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English (en)
Japanese (ja)
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藤村　剛経
南　裕
岡本　卓治
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出光興産株式会社
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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
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F10/14—Monomers containing five or more carbon atoms
    • 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
    • C08F2420/00—Metallocene catalysts
    • C08F2420/10—Heteroatom-substituted bridge, i.e. Cp or analog where the bridge linking the two Cps or analogs is substituted by at least one group that contains a heteroatom
    • 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
    • C08F4/65908—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an ionising compound other than alumoxane, e.g. (C6F5)4B-X+
    • 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
    • C08F4/65912—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an organoaluminium compound

Definitions

  • the present invention relates to a method for producing an ⁇ -olefin polymer.
  • Hydrocarbon waxes are used in various applications such as inks, paints, emulsions, and toner release agents. Hydrocarbon waxes are also used in applications other than those described above, for example, reforming of fuel oils such as resin modifiers, adhesive components, adhesive components, lubricating oil components, organic-inorganic composite materials, heat storage materials, and light oil. Applications include quality agents, asphalt modifiers, high-performance waxes, and cosmetics. Various performances are required for hydrocarbon waxes used in these applications. For example, low molecular weight can be achieved due to ease of handling, moderate melting point (20 to 120 ° C.), moderate hardness, And excellent temperature response characteristics. However, it has not been easy to achieve the desired level simultaneously, such as decreasing the molecular weight and decreasing the melting point.
  • Patent Document 1 discloses that a boron atom or a phosphorus atom is a bridging atom for the purpose of producing an ⁇ -olefin polymer having a weight average molecular weight of 5,000 or less suitable as a wax and having an excellent balance between the molecular weight and the melting point.
  • a method for producing an ⁇ -olefin polymer is disclosed in which an ⁇ -olefin having 20 to 40 carbon atoms is polymerized in the presence of a polymerization catalyst containing a transition metal compound.
  • a material having a further low molecular weight and a high melting point is desired.
  • the problem to be solved by the present invention is a low molecular weight and high melting point ⁇ having an excellent balance between the molecular weight and the melting point, a weight average molecular weight of 5,000 or less, and a melting point controlled in the range of 25 to 120 ° C. -To provide a method for efficiently producing an olefin polymer.
  • the present invention provides the following method for producing an ⁇ -olefin polymer and the ⁇ -olefin polymer produced thereby.
  • ⁇ 1> (A) a meso-type transition metal compound represented by the following general formula (I), and (B) (B-1) a meso-type transition metal compound of component (A) or a derivative thereof (C) an ⁇ -olefin having 16 to 40 carbon atoms is polymerized in the presence of a compound capable of forming an ionic complex and (B-2) a polymerization catalyst containing at least one selected from aluminoxane.
  • a process for producing an ⁇ -olefin polymer (A) a meso-type transition metal compound represented by the following general formula (I), and (B) (B-1) a meso-type transition metal compound of component (A) or a derivative thereof (C) an ⁇ -olefin having 16 to 40 carbon atoms is polymerized in the presence of a compound capable of
  • M represents a metal element of Groups 3 to 10 of the periodic table.
  • X represents a ⁇ -bonding ligand, and when there are a plurality of Xs, the plurality of Xs may be the same or different.
  • Y represents a Lewis base, and when there are a plurality of Y, the plurality of Y may be the same or different.
  • a 1 and A 2 each independently represent a crosslinking group selected from a hydrocarbon group having 1 to 20 carbon atoms, a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, a germanium-containing group, and a tin-containing group. , A 1 and A 2 are different from each other.
  • q is an integer of 1 to 5 and represents [(valence of M) -2], and r represents an integer of 0 to 3.
  • E is a group represented by the following formula (II), and two E may be the same or different from each other.
  • R 1 represents a group selected from a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogen-containing hydrocarbon group having 1 to 4 carbon atoms, a silicon-containing group, and a heteroatom-containing group.
  • P represents an integer of 0 to 5. When several R ⁇ 1 > exists, they may mutually be same or different.
  • the bond indicated by the wavy line represents a bond with the bridging groups -A 1 -and -A 2- .
  • the bridging group represented by -A 1- is a group represented by the following general formula (III-1)
  • the bridging group represented by -A 2- is The method for producing an ⁇ -olefin polymer according to the above ⁇ 1>, which is a group represented by the general formula (III-2).
  • B 1 and B 2 each independently represent a carbon atom, a silicon atom, a germanium atom, or a tin atom
  • R 2a , R 3a , R 2b, and R 3b Are each independently a hydrogen atom, an aliphatic hydrocarbon group having 1 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms, an oxygen atom-containing group having 1 to 20 carbon atoms, or an amine having 1 to 20 carbon atoms.
  • a halogen-containing group having 1 to 20 carbon atoms are each independently an integer of 1 or more, and m + n is 3 or more.
  • ⁇ 6> The catalyst for polymerization according to any one of the above items ⁇ 1> to ⁇ 5>, wherein at least the components (A) and (B) and (D) organoaluminum previously contacted are used as the polymerization catalyst.
  • ⁇ 7> The above-mentioned polymerization catalyst, wherein at least the component (A), the component (B), the component (C) and the component (D) are previously contacted with each other, is used as the polymerization catalyst.
  • ⁇ 8> An ⁇ -olefin polymer produced by the method according to any one of ⁇ 1> to ⁇ 7>.
  • a low molecular weight and high melting point ⁇ -olefin having an excellent balance between the molecular weight and the melting point, a weight average molecular weight of 5000 or less, and a melting point controlled in the range of 25 to 120 ° C.
  • a polymer can be produced efficiently.
  • the method for producing an ⁇ -olefin polymer of the present invention comprises (A) a meso type transition metal compound represented by the following general formula (I), and (B) (B-1) a meso type transition of the component (A). In the presence of a compound capable of reacting with a metal compound or a derivative thereof to form an ionic complex, and (B-2) a polymerization catalyst containing at least one selected from aluminoxane, (C) a carbon number of 16 to 40 The ⁇ -olefin is polymerized.
  • M represents a metal element of Groups 3 to 10 of the periodic table.
  • X represents a ⁇ -bonding ligand, and when there are a plurality of Xs, the plurality of Xs may be the same or different.
  • Y represents a Lewis base, and when there are a plurality of Y, the plurality of Y may be the same or different.
  • a 1 and A 2 each independently represent a crosslinking group selected from a hydrocarbon group having 1 to 20 carbon atoms, a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, a germanium-containing group, and a tin-containing group. , A 1 and A 2 are different from each other.
  • E is a group represented by the following formula (II), and two E may be the same or different from each other.
  • R 1 represents a group selected from a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogen-containing hydrocarbon group having 1 to 4 carbon atoms, a silicon-containing group, and a heteroatom-containing group.
  • P represents an integer of 0 to 5.
  • R ⁇ 1 > exists, they may mutually be same or different.
  • the bond indicated by the wavy line represents a bond with the bridging groups -A 1 -and -A 2- .
  • the molecular weight and the melting point are increased.
  • an ⁇ -olefin polymer having a low molecular weight and a high melting point which has an excellent balance with the above, a weight average molecular weight of 5,000 or less and a melting point controlled in the range of 25 to 120 ° C. can be efficiently produced.
  • the specific meso type transition metal compound represented by the general formula (I) is disclosed in JP-A-2002-308893.
  • the invention disclosed in the publication is aimed at obtaining an olefin polymer having a high molecular weight and a narrow molecular weight distribution, and does not describe the production of an ⁇ -olefin polymer having a low molecular weight and a high melting point.
  • the olefin used as the monomer ethylene or ⁇ -olefin having 3 to 20 carbon atoms is generally described, but only polymerization of ethylene is described in the examples.
  • the present inventors used a specific meso-type transition metal compound represented by the above general formula (I) as a catalyst, and polymerized a higher ⁇ -olefin having 16 to 40 carbon atoms as a monomer.
  • the ligand is connected by two bridging groups A 1 and A 2 and is represented by A 1 and A 2. It was found that the difference in the structure of the two cross-linking groups makes it possible to control the steric restriction during the insertion reaction of the monomer into the catalyst and to produce an ⁇ -olefin polymer having a low molecular weight and a high melting point.
  • the present invention has been completed based on such findings.
  • the raw ⁇ -olefin used in the method for producing an ⁇ -olefin polymer of the present invention is an ⁇ -olefin having 16 to 40 carbon atoms.
  • the number of carbon atoms of the ⁇ -olefin is preferably 20 to 40, more preferably 22 to 40, and more preferably 25 to 35 from the viewpoint of controlling the melting point of the polymer and the olefin polymerization activity.
  • the ⁇ -olefin has a larger carbon number.
  • the polymer complex represented by the above formula (I) is used and an ⁇ -olefin having a large carbon number is used as a raw material. It is important to use as The production method of the present invention aims to reduce the molecular weight while maintaining high melting point while maintaining high melting point, and this effect is more prominent particularly in the case of 22 to 40 carbon atoms.
  • ⁇ -olefin having 16 to 40 carbon atoms include 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, 1-icocene, 1-docosene, 1-hexacosene, 1-octacosene and 1-tria.
  • Examples include content, 1-dotria content, 1-tetratria content, 1-hexatria content, 1-octatria content and 1-tetra content.
  • these ⁇ -olefins may be used alone or in combination of two or more.
  • the polymerization catalyst used in the method for producing an ⁇ -olefin polymer of the present invention includes (A) a meso-type transition metal compound represented by the general formula (I), and (B) (B-1) (A And (B-2) a compound capable of forming an ionic complex by reacting with the component meso transition metal compound or a derivative thereof, and (B-2) containing at least one selected from aluminoxane.
  • the meso-type transition metal compound refers to a transition metal compound in which two bridging groups bridge two Es in a bonding mode of (1, 1 ′) (2, 2 ′).
  • M represents a metal element of Groups 3 to 10 of the periodic table, and specific examples include titanium, zirconium, hafnium, yttrium, vanadium, chromium, manganese, nickel, cobalt, palladium, and lanthanoid series. Metal etc. are mentioned.
  • a metal element belonging to Group 4 of the periodic table is preferable from the viewpoint of olefin polymerization activity and the like, and titanium, zirconium and hafnium are preferable.
  • X represents a ⁇ -bonded ligand, and specific examples thereof include a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and a carbon number. 6-20 aryloxy groups, amide groups having 1-20 carbon atoms, silicon-containing groups having 1-20 carbon atoms, phosphide groups having 1-20 carbon atoms, sulfide groups having 1-20 carbon atoms, 1-20 carbon atoms And the acyl group.
  • q is an integer of 1 to 5 and represents [(M valence) -2]. When q is 2 or more, a plurality of Xs may be the same or different.
  • halogen atom examples include a chlorine atom, a fluorine atom, a bromine atom, and an iodine atom.
  • hydrocarbon group having 1 to 20 carbon atoms include alkyl groups such as methyl group, ethyl group, propyl group, butyl group, hexyl group, cyclohexyl group and octyl group; alkenyl groups such as vinyl group, propenyl group and cyclohexenyl group An arylalkyl group such as benzyl group, phenylethyl group, phenylpropyl group; phenyl group, tolyl group, dimethylphenyl group, trimethylphenyl group, ethylphenyl group, propylphenyl group, biphenyl group, naphthyl group, methylnaphthyl group, anthracenyl group Group, aryl group such as phenanthonyl group
  • alkoxy group having 1 to 20 carbon atoms examples include methoxy group, ethoxy group, propoxy group, butoxy group, phenylmethoxy group, and phenylethoxy group.
  • aryloxy group having 6 to 20 carbon atoms examples include a phenoxy group, a methylphenoxy group, and a dimethylphenoxy group.
  • Examples of the amide group having 1 to 20 carbon atoms include a dimethylamide group, a diethylamide group, a dipropylamide group, a dibutylamide group, a dicyclohexylamide group, and a methylethylamide group; a divinylamide group, a dipropenylamide group, Examples include alkenylamide groups such as dicyclohexenylamide groups; arylalkylamide groups such as dibenzylamide groups, phenylethylamide groups, and phenylpropylamide groups; arylamide groups such as diphenylamide groups and dinaphthylamide groups.
  • Examples of the silicon-containing group having 1 to 20 carbon atoms include monohydrocarbon-substituted silyl groups such as methylsilyl group and phenylsilyl group; dihydrocarbon-substituted silyl groups such as dimethylsilyl group and diphenylsilyl group; trimethylsilyl group, triethylsilyl group, Trihydrocarbon-substituted silyl such as tripropylsilyl group, dimethyl (t-butyl) silyl group, tricyclohexylsilyl group, triphenylsilyl group, dimethylphenylsilyl group, methyldiphenylsilyl group, tolylsilylsilyl group, trinaphthylsilyl group, etc.
  • monohydrocarbon-substituted silyl groups such as methylsilyl group and phenylsilyl group
  • dihydrocarbon-substituted silyl groups such as
  • a hydrocarbon-substituted silyl ether group such as a trimethylsilyl ether group; a silicon-substituted alkyl group such as a trimethylsilylmethyl group; a silicon-substituted aryl group such as a trimethylsilylphenyl group; a dimethylhydrosilyl group and a methyldihydrosilyl group;
  • phosphide group having 1 to 20 carbon atoms include dimethyl phosphide group, methylphenyl phosphide group, diphenyl phosphide group, dicyclohexyl phosphide group and dibenzyl phosphide group.
  • Examples of the sulfide group having 1 to 20 carbon atoms include alkyl sulfide groups such as methyl sulfide group, ethyl sulfide group, propyl sulfide group, butyl sulfide group, hexyl sulfide group, cyclohexyl sulfide group, octyl sulfide group; vinyl sulfide group, propenyl sulfide Group, alkenyl sulfide group such as cyclohexenyl sulfide group; arylalkyl sulfide group such as benzyl sulfide group, phenylethyl sulfide group, phenylpropyl sulfide group; phenyl sulfide group, tolyl sulfide group, dimethylphenyl sulfide group, trimethylphenyl sulfide group, E
  • acyl group having 1 to 20 carbon atoms examples include formyl group, acetyl group, propionyl group, butyryl group, valeryl group, palmitoyl group, stearoyl group, oleoyl group and other alkyl acyl groups, benzoyl group, toluoyl group, salicyloyl group, Examples thereof include arylacyl groups such as cinnamoyl group, naphthoyl group and phthaloyl group, and oxalyl group, malonyl group and succinyl group respectively derived from dicarboxylic acid such as oxalic acid, malonic acid and succinic acid.
  • Y represents a Lewis base, and specific examples thereof include amines, ethers, phosphines, and thioethers.
  • r represents an integer of 0 to 3, and when r is 2 or 3, a plurality of Y may be the same or different.
  • the amine include amines having 1 to 20 carbon atoms, specifically, methylamine, ethylamine, propylamine, butylamine, cyclohexylamine, methylethylamine, dimethylamine, diethylamine, dipropylamine, dibutylamine, dicyclohexyl.
  • Alkylamines such as amine, methylethylamine, trimethylamine, triethylamine, tri-n-butylamine; alkenylamines such as vinylamine, propenylamine, cyclohexenylamine, divinylamine, dipropenylamine, dicyclohexenylamine; phenylmethylamine, phenylethylamine Arylalkylamines such as phenylpropylamine; arylamines such as diphenylamine and dinaphthylamine; or ammonia, aniline, N Methylaniline, diphenylamine, N, N-dimethylaniline, methyldiphenylamine, pyridine and p- bromo -N, N-dimethylaniline.
  • ethers include aliphatic single ether compounds such as methyl ether, ethyl ether, propyl ether, isopropyl ether, butyl ether, isobutyl ether, n-amyl ether, isoamyl ether; methyl ethyl ether, methyl propyl ether, methyl isopropyl Aliphatic hybrid ether compounds such as ether, methyl-n-amyl ether, methyl isoamyl ether, ethyl propyl ether, ethyl isopropyl ether, ethyl butyl ether, ethyl isobutyl ether, ethyl-n-amyl ether, ethyl isoamyl ether; vinyl ether, allyl ether Aliphatic unsaturated ether compounds such as methyl vinyl ether, methyl allyl ether, ethyl vinyl ether, and eth
  • phosphine examples include phosphine having 1 to 20 carbon atoms. Specifically, monohydrocarbon-substituted phosphines such as methylphosphine, ethylphosphine, propylphosphine, butylphosphine, hexylphosphine, cyclohexylphosphine, octylphosphine; dimethylphosphine, diethylphosphine, dipropylphosphine, dibutylphosphine, dihexylphosphine, dicyclohexyl Dihydrocarbon-substituted phosphines such as phosphine and dioctylphosphine; Trimethylphosphine, triethylphosphine, tripropylphosphine, tributylphosphine, trihexylphosphine, tricyclohexylphosphine, and tri
  • E is a group represented by the formula (II), and two E may be the same or different from each other.
  • R 1 represents a group selected from a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogen-containing hydrocarbon group having 1 to 4 carbon atoms, a silicon-containing group and a heteroatom-containing group
  • p represents an integer of 0 to 5.
  • R ⁇ 1 > exists, they may mutually be same or different.
  • the bond indicated by the wavy line represents a bond with the bridging groups -A 1 -and -A 2- .
  • R 1 is bonded to the 3rd to 7th positions of the indenyl group, and preferably bonded to the 3rd position of the indenyl group.
  • the halogen atom and the hydrocarbon group having 1 to 20 carbon atoms are the same as those described above as specific examples of X.
  • Specific examples of the halogen-containing hydrocarbon group having 1 to 4 carbon atoms include chloromethyl group, bromomethyl group, bromoethyl group, p-fluorophenyl group, p-fluorophenylmethyl group, 3,5-difluorophenyl group, pentachlorophenyl.
  • silicon-containing groups include monohydrocarbon-substituted silyl groups such as methylsilyl and phenylsilyl groups; dihydrocarbon-substituted silyl groups such as dimethylsilyl and diphenylsilyl groups; trimethylsilyl, triethylsilyl, and tripropylsilyl Groups, trihydrocarbon-substituted silyl groups such as dimethyl (t-butyl) silyl group, tricyclohexylsilyl group, triphenylsilyl group, dimethylphenylsilyl group, methyldiphenylsilyl group, tolylsilylsilyl group, trinaphthylsilyl group; Examples include hydrocarbon-substituted silyl ether groups such as methylsilyl and phenylsilyl groups; dihydrocarbon-substituted silyl groups such as dimethylsilyl and diphenylsilyl groups; tri
  • a 1 and A 2 are each independently a hydrocarbon group having 1 to 20 carbon atoms, a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, a germanium-containing group, and a tin-containing group.
  • a crosslinking group selected from a group is shown, and A 1 and A 2 are different from each other.
  • two substituted or unsubstituted indenyl groups E are double-bridged.
  • a 1 and A 2 are different from each other, for example, in the case of a hydrocarbon group, means that (—CH 2 —) and (—CH 2 —CH 2 —) are different from each other.
  • the bridging group represented by -A 1 - is preferably a group represented by the following general formula (III-1), and the bridging group represented by -A 2- is A group represented by general formula (III-2) is preferable.
  • B 1 and B 2 each independently represent a carbon atom, a silicon atom, a germanium atom or a tin atom
  • R 2a , R 3a , R 2b and R 3b are , Each independently containing a hydrogen atom, an aliphatic hydrocarbon group having 1 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms, an oxygen atom-containing group having 1 to 20 carbon atoms, and an amine having 1 to 20 carbon atoms Represents a group or a halogen-containing group having 1 to 20 carbon atoms.
  • m and n are each independently an integer of 1 or more, and m + n is 3 or more.
  • B 1 and B 2 are preferably the same, m and n are preferably different from each other, and B 1 and B 2 are a carbon atom or a silicon atom. It is preferable.
  • Examples of the aliphatic hydrocarbon group having 1 to 20 carbon atoms and the aromatic hydrocarbon group having 6 to 20 carbon atoms include alkyl groups, alkenyl groups, which are the hydrocarbon groups having 1 to 20 carbon atoms described above as specific examples of X, The same thing as an arylalkyl group and an aryl group is mentioned.
  • Examples of the oxygen atom-containing group having 1 to 20 carbon atoms include those similar to the alkoxy group having 1 to 20 carbon atoms and the aryloxy group having 6 to 20 carbon atoms described above as specific examples of X.
  • Examples of the amine-containing group having 1 to 20 carbon atoms include monovalent groups obtained by removing one hydrogen atom from the above-described amines having 1 to 20 carbon atoms as a specific example of Y.
  • Examples of the halogen-containing group having 1 to 20 carbon atoms are the same as those described above as specific examples of R 1 .
  • crosslinking group represented by the general formulas (III-1) and (III-2) include an ethylene group, a tetramethylethylene group, a 1,2-cyclohexylene group, a tetramethyldisylylene group, and dimethylsilylene.
  • examples include a methylene group, dimethylsilylene isopropylidene group, and tetramethyldiggermylene group.
  • ethylene group, dimethylsilylene group and tetramethyldisilene group are preferred from the viewpoint of higher polymerization activity, and more specifically, the above general formulas (III-1) and (III-2) ) Is preferably a dimethylsilylene group and the other is a tetramethyldisilylene group.
  • a transition metal compound having a double-bridged bisindenyl derivative represented by the following general formula (IV) as a ligand is preferable.
  • a 1 , A 2 , R 1 , M, X, Y, q, and r are A 1 , A 2 , R 1 , M, X, Y, in the general formula (I). Same as q and r.
  • meso-type transition metal compound represented by the general formula (I) include (1,1′-dimethylsilylene) (2,2′-tetramethyldisilylene) bis (indenyl) zirconium dichloride, (1 , 1'-dimethylsilylene) (2,2'-tetramethyldisiylene) bis (3-methylindenyl) zirconium dichloride, (1,1'-dimethylsilylene) (2,2'-tetramethyldisilene) bis (3-Trimethylsilylmethylindenyl) zirconium dichloride, (1,1′-dimethylsilylene) (2,2′-ethylene) bis (indenyl) zirconium dichloride, (1,1′-dimethylsilylene) (2,2′- Ethylene) bis (3-methylindenyl) zirconium dichloride, (1,1'-dimethylsilylene) (2,2'- Tylene) bis (3-trimethylsily
  • a method for synthesizing the transition metal compound represented by the general formula (I) is described in, for example, “J. Organomet. Chem.”, Volume 369, Page 359 (1989) ”. It can be synthesized by the method described. That is, it can be synthesized by a reaction between a corresponding substituted cycloalkenyl anion and a metal halide represented by M in the general formula (I).
  • any compound that can form an ionic complex by reacting with the transition metal compound of the component (A) can be used.
  • a compound represented by formula (V) or (VI) can be preferably used. ([L 1 ⁇ R 4 ] k + ) a ([Z] ⁇ ) b (V) ([L 2 ] k + ) a ([Z] ⁇ ) b (VI)
  • L 1 represents a Lewis base.
  • the Lewis base include ammonia, methylamine, aniline, dimethylamine, diethylamine, N-methylaniline, diphenylamine, N, N-dimethylaniline, Amines such as trimethylamine, triethylamine, tri-n-butylamine, methyldiphenylamine, pyridine, p-bromo-N, N-dimethylaniline, p-nitro-N, N-dimethylaniline, triethylphosphine, triphenylphosphine, diphenylphosphine Phosphines such as tetrahydrothiophene, esters such as ethyl benzoate, nitriles such as acetonitrile and benzonitrile, and the like.
  • R 4 represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylaryl group, or an arylalkyl group. Specific examples of R 4 include a hydrogen atom, a methyl group, an ethyl group, a benzyl group, and a trityl group.
  • [Z] ⁇ is a non-coordinating anion, and examples of [Z] ⁇ include [Z 1 ] ⁇ and [Z 2 ] ⁇ shown below.
  • [Z 1 ] ⁇ represents an anion having a plurality of groups bonded to the element, ie, [M 1 G 1 G 2 ... G f ] ⁇ .
  • M 1 represents a group 5 to 15 element of the periodic table, preferably a group 13 to 15 element of the periodic table.
  • Specific examples of M 1 include B, Al, Si, P, As and Sb, and B and Al are preferable.
  • G 1 to G f are a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a dialkylamino group having 2 to 40 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and an aryl group having 6 to 20 carbon atoms, respectively.
  • Two or more of G 1 to G f may form a ring.
  • f represents an integer of [(valence of central metal M 1 ) +1].
  • G 1 to G f include dimethylamino group and diethylamino group as dialkylamino group, methoxy group, ethoxy group, n-butoxy group, phenoxy group and the like as alkoxy group or aryloxy group, and methyl group as hydrocarbon group.
  • [Z 2 ] ⁇ is a Bronsted acid alone having a logarithm (pKa) of the reciprocal of the acid dissociation constant or a conjugate base of a combination of Bronsted acid and Lewis acid, or an acid generally defined as a super strong acid.
  • the conjugate salt of In addition, a Lewis base may be coordinated.
  • [Z 2 ] ⁇ include trifluoromethanesulfonate anion (CF 3 SO 3 ) ⁇ , bis (trifluoromethanesulfonyl) methyl anion, bis (trifluoromethanesulfonyl) benzyl anion, bis (trifluoromethanesulfonyl) amide, Perchlorate anion (ClO 4 ) ⁇ , trifluoroacetate anion (CF 3 CO 2 ) ⁇ , hexafluoroantimony anion (SbF 6 ) ⁇ , fluorosulfonate anion (FSO 3 ) ⁇ , chlorosulfonate anion (ClSO 3 ) -, fluorosulfonic acid anion / antimony pentafluoride (FSO 3 / SbF 5) - , fluorosulfonic acid anion / 5- fluoride arsenic (FSO 3 / AsF 5)
  • L 2 represents M 2 , R 5 R 6 M 3 , R 7 3 C or R 8 M 3 .
  • M 2 includes elements in groups 1 to 3, 11 to 13, and 17 of the periodic table, and M 3 represents elements in groups 7 to 12 of the periodic table.
  • Specific examples of M 2 include Li, Na, K, Ag, Cu, Br, I and I 3.
  • Specific examples of M 3 include Mn, Fe, Co, Ni and Zn. Can be mentioned.
  • R 5 and R 6 each represent a cyclopentadienyl group, a substituted cyclopentadienyl group, an indenyl group, a substituted indenyl group, a fluorenyl group, or a substituted fluorenyl group.
  • R 5 and R 6 include a cyclopentadienyl group, a methylcyclopentadienyl group, an ethylcyclopentadienyl group, and a pentamethylcyclopentadienyl group.
  • R 7 represents an alkyl group having 1 to 20 carbon atoms, an aryl group, an alkylaryl group or an arylalkyl group. Specific examples of R 7 include a phenyl group, a p-tolyl group, and a p-methoxyphenyl group.
  • R 8 represents a macrocyclic ligand, and specific examples thereof include tetraphenylporphine and phthalocyanine.
  • the compound (B-1) include triethylammonium tetraphenylborate, tri-n-butylammonium tetraphenylborate, trimethylammonium tetraphenylborate, tetraethylammonium tetraphenylborate, methyl tetraphenylborate (tri-n -Butyl) ammonium, benzyl (tri-n-butyl) ammonium tetraphenylborate, dimethyldiphenylammonium tetraphenylborate, triphenyl (methyl) ammonium tetraphenylborate, trimethylanilinium tetraphenylborate, methylpyridinium tetraphenylborate, tetraphenyl Benzylpyridinium borate, methyl tetraphenylborate (2-cyanopyridinium), tetrakis (pentafluor
  • Examples of the aluminoxane of the component (B-2) in the component (B) include a chain aluminoxane represented by the following general formula (VII) and a cyclic aluminoxane represented by the following general formula (VIII).
  • R 9 represents a hydrocarbon group such as an alkyl group, an alkenyl group, an aryl group or an arylalkyl group having 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms or a halogen atom, and w represents an average degree of polymerization, Usually, it is an integer of 2 to 50, preferably 2 to 40.
  • Each R 9 may be the same or different.
  • aluminoxane represented by the general formula (VII) or (VIII) include methylaluminoxane, ethylaluminoxane, and isobutylaluminoxane.
  • the method for producing the aluminoxane include a method in which an alkylaluminum is brought into contact with a condensing agent such as water, but the means thereof is not particularly limited and may be reacted according to a known method.
  • the aluminoxane may be insoluble in toluene. These aluminoxanes may be used alone or in combination of two or more.
  • the use ratio of the component (A) and the component (B) in the polymerization catalyst used in the production method of the present invention is preferably a molar ratio when the compound (B-1) is used as the component (B).
  • the range is from 10: 1 to 1: 100, more preferably from 2: 1 to 1:10. If it exists in this range, the catalyst cost per unit mass polymer will not become so high, and it is practical.
  • the ratio of the component (A) to the component (B-2) is preferably 1: 1 to 1: 1000000, more preferably 1:10 in terms of molar ratio. It is in the range of ⁇ 1: 10000. If it exists in this range, the catalyst cost per unit mass polymer will not become so high, and it is practical.
  • the catalyst component (B) the compound of the component (B-1) and / or the compound of the component (B-2) can be used alone or in combination of two or more.
  • an organoaluminum compound can be used as the component (D) in addition to the components (A) and (B).
  • the organoaluminum compound of the component (D) a compound represented by the following general formula (IX) can be used.
  • R 10 v AlJ 3-v (IX) [Wherein R 10 represents an alkyl group having 1 to 10 carbon atoms, J represents a hydrogen atom, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a halogen atom, and v represents 1 to 3 carbon atoms. It is an integer. ]
  • Specific examples of the compound represented by the general formula (IX) include trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, dimethylaluminum chloride, diethylaluminum chloride, methylaluminum dichloride, ethylaluminum dichloride, dimethylaluminum fluoride. , Diisobutylaluminum hydride, diethylaluminum hydride, ethylaluminum sesquichloride and the like.
  • an organoaluminum compound to which a hydrocarbon group having 4 or more carbon atoms is bonded is preferable from the viewpoint of excellent high-temperature stability, and a hydrocarbon group having 4 to 8 carbon atoms is more preferable from this viewpoint. More preferably, when the reaction temperature is 100 ° C. or higher, a hydrocarbon group having 6 to 8 carbon atoms is more preferable.
  • the organoaluminum compound may be used singly or in combination of two or more.
  • the amount of organoaluminum used as component (D) is preferably 1: 1 to 1: 10000, more preferably 1: 5 to 1: 2000, and still more preferably 1 in terms of the molar ratio of component (A) to component (D). : The range is 10 to 1: 1000.
  • the polymerization activity per transition metal can be improved.
  • (A) :( D) is in the range of 1: 1 to 1: 10000, the balance between the effect of addition of component (D) and economy is good, and the resulting ⁇ -olefin polymer has a good balance. There is no fear of a large amount of aluminum.
  • At least one of the catalyst components can be supported on a suitable carrier and used.
  • the type of the carrier is not particularly limited, and any of inorganic oxide carriers, other inorganic carriers, and organic carriers can be used. In particular, inorganic oxide carriers or other inorganic carriers are preferable.
  • the inorganic oxide carrier examples include SiO 2 , Al 2 O 3 , MgO, ZrO 2 , TiO 2 , Fe 2 O 3 , B 2 O 3 , CaO, ZnO, BaO, ThO 2 and mixtures thereof.
  • examples thereof include silica alumina, zeolite, ferrite, glass fiber and the like. Of these, SiO 2 and Al 2 O 3 are particularly preferable.
  • the inorganic oxide carrier may contain a small amount of carbonate, nitrate, sulfate and the like.
  • a magnesium compound represented by the general formula MgR 11 x X 1 y typified by MgCl 2 , Mg (OC 2 H 5 ) 2 or the like, a complex salt thereof, or the like can be given.
  • R 11 represents an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms
  • X 1 represents a halogen atom or an alkyl group having 1 to 20 carbon atoms
  • x is 0 to 2
  • y is 0 to 2
  • x + y 2.
  • Each R 11 and each X 1 may be the same or different.
  • the organic carrier examples include polymers such as polystyrene, styrene-divinylbenzene copolymer, polyethylene, poly 1-butene, substituted polystyrene, polyarylate, starch, carbon and the like.
  • the carrier for the polymerization catalyst used in the present invention MgCl 2 , MgCl (OC 2 H 5 ), Mg (OC 2 H 5 ) 2 , SiO 2 , Al 2 O 3 and the like are preferable.
  • the properties of the carrier vary depending on the type and production method, but the average particle size is usually 1 to 300 ⁇ m, preferably 10 to 200 ⁇ m, more preferably 20 to 100 ⁇ m.
  • the specific surface area of the carrier is usually 1 to 1000 m 2 / g, preferably 50 to 500 m 2 / g, and the pore volume is usually 0.1 to 5 cm 3 / g, preferably 0.3 to 3 cm 3 / g. is there. When either the specific surface area or the pore volume deviates from the above range, the catalytic activity may decrease.
  • the specific surface area and pore volume can be determined, for example, from the volume of nitrogen gas adsorbed according to the BET method [J. Am. Chem. Soc. , 60, 309 (1983)].
  • the carrier is an inorganic oxide carrier, it is usually used by firing at 150 to 1000 ° C., preferably 200 to 800 ° C.
  • at least one catalyst component is supported on the carrier, it is preferable to support at least one of the component (A) and the component (B), preferably both the component (A) and the component (B).
  • the method for supporting at least one of the component (A) and the component (B) on the carrier is not particularly limited. For example, (1) at least one of the component (A) and the component (B) is mixed with the carrier.
  • Method (2) A method in which a support is treated with an organoaluminum compound or a halogen-containing silicon compound and then mixed with at least one of the component (A) and the component (B) in an inert solvent, (3) the support and (A) Method of reacting component and / or component (B) with organoaluminum compound or halogen-containing silicon compound, (4) (B) component or (A) after (A) component or (B) component is supported on a carrier ) A method of mixing with the component, (5) a method of mixing the contact reaction product of the component (A) with the component (B) with the carrier, and (6) a carrier during the contact reaction of the component (A) with the component (B). Use a method to coexist Rukoto can.
  • an organoaluminum compound as the component (C) can also be added.
  • a catalyst can be produced
  • the component (A) and the component (B), a carrier, and if necessary, the organoaluminum compound of the component (D) are added, and an olefin such as ethylene is added in an amount of 0.1 to 2 MPa (Gauge), and ⁇ 20
  • the ratio of the component (B-1) to the support used in the catalyst used in the present invention is preferably 1: 5 to 1: 10000, more preferably 1:10 to 1: 500 by mass ratio.
  • the use ratio of the component (B-2) to the carrier is preferably 1: 0.5 to 1: 1000, more preferably 1: 1 to 1:50 by mass ratio.
  • carrier is in the said range by mass ratio.
  • the ratio of the component (A) to the carrier used is preferably 1: 5 to 1: 10000, more preferably 1:10 to 1: 500 in terms of mass ratio.
  • the average particle diameter of the polymerization catalyst thus prepared is usually 2 to 200 ⁇ m, preferably 10 to 150 ⁇ m, particularly preferably 20 to 100 ⁇ m, and the specific surface area is usually 20 to 1000 m 2 / g, preferably 50-500 m 2 / g. If the average particle size is less than 2 ⁇ m, fine powder in the polymer may increase, and if it exceeds 200 ⁇ m, coarse particles in the polymer may increase.
  • the activity may decrease, and when it exceeds 1000 m 2 / g, the bulk density of the polymer may decrease.
  • the amount of transition metal in 100 g of the support is usually 0.05 to 10 g, particularly preferably 0.1 to 2 g. If the amount of transition metal is outside the above range, the activity may be lowered. In this way, a polymer having an industrially advantageous high bulk density and an excellent particle size distribution can be obtained by supporting it on a carrier.
  • the polymerization method is not particularly limited, and any method such as a slurry polymerization method, a gas phase polymerization method, a bulk polymerization method, a solution polymerization method, and a suspension polymerization method may be used.
  • a polymerization method is particularly preferred.
  • the polymerization temperature is usually 0 to 200 ° C., more preferably 20 to 200 ° C., particularly preferably 70 to 200 ° C.
  • the ratio of the catalyst to the reaction raw material is preferably from 1 to 100 million, more preferably from 1 to 1000, as the raw material monomer / the component (A) (molar ratio).
  • the polymerization time is usually 5 minutes to 30 hours, preferably 15 minutes to 25 hours.
  • the hydrogen pressure is usually 0 to 10 MPa (Gauge).
  • the hydrogen pressure is preferably from 0.1 to 5.0 MPa (Gauge), and more preferably from 0.1 to 1.0 MPa (Gauge).
  • the polymerization activity improves as the hydrogenation amount increases. However, even if the amount exceeds 10 MPa (Gauge) or more, there is little influence on the activity, and conversely, problems such as enlargement of production facilities occur.
  • a polymerization solvent for example, aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene and decalin, alicyclic hydrocarbons such as cyclopentane, cyclohexane and methylcyclohexane, aliphatics such as pentane, hexane, heptane and octane Hydrocarbons, halogenated hydrocarbons such as chloroform and dichloromethane can be used. These solvents may be used alone or in combination of two or more. Moreover, it can carry out without a solvent depending on the polymerization method.
  • aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene and decalin
  • alicyclic hydrocarbons such as cyclopentane, cyclohexane and methylcyclohexane
  • aliphatics such as pentane, hexane
  • a polymerization catalyst may be prepared by performing preliminary polymerization.
  • the prepolymerization can be performed, for example, by bringing a small amount of olefin into contact with the catalyst component, but the method is not particularly limited, and a known method can be used.
  • the olefin used in the prepolymerization is not particularly limited, and examples thereof include an ⁇ -olefin having 3 to 18 carbon atoms, or a mixture thereof. The same as the ⁇ -olefin used as a raw material in the polymerization (C) It is advantageous to use an ⁇ -olefin having 16 to 40 carbon atoms as a component.
  • the polymerization catalyst is prepared by previously contacting the components (A), (B) and (C), or the components (A), (B), (C) and Examples include preparing a polymerization catalyst by bringing the component (D) into contact in advance.
  • the prepolymerization temperature is usually ⁇ 20 to 200 ° C., preferably ⁇ 10 to 130 ° C., more preferably 0 to 80 ° C.
  • aliphatic hydrocarbons, aromatic hydrocarbons, monomers and the like can be used as solvents.
  • the intrinsic viscosity [ ⁇ ] (measured in 135 ° C.
  • the degree of polymerization tends to decrease, and when a monomer having a small carbon number is used, the degree of polymerization tends to increase.
  • the ⁇ -olefin polymer obtained by the production method of the present invention has a weight average molecular weight (Mw) of 5000 or less and a melting point (Tm) in the range of 25 to 120 ° C.
  • the ⁇ -olefin polymer of the present invention has a melting component amount of ( ⁇ -olefin polymer melting point ⁇ 20) ° C. of 12% or less, or a dimer component content of 10% by mass or less.
  • it can be controlled by the manufacturing method of the present invention described above.
  • the weight average molecular weight of the ⁇ -olefin polymer obtained by the production method of the present invention is 5000 or less, preferably 1000 to 5000, more preferably 3000 to 4500.
  • a low molecular weight that is, low viscosity
  • the weight average molecular weight is 5000 or less, such a function as a wax is satisfied. Fluidity is obtained.
  • the weight average molecular weight is 1000 or more, it has a property that is distinguished from a monomer that is a liquid.
  • the weight average molecular weight in the present invention is a weight average molecular weight in terms of polystyrene measured by the gel permeation chromatography (GPC) method using the apparatus and conditions described in the examples.
  • the melting point (Tm) of the ⁇ -olefin polymer obtained by the production method of the present invention is in the range of 25 to 120 ° C., and the required range varies depending on the use. ° C, more preferably 60 to 80 ° C, still more preferably 70 to 80 ° C.
  • the melting point (Tm) of the ⁇ -olefin polymer needs to be set to an appropriate melting point according to various uses such as inks, paints, emulsions, and toner release agents.
  • Tm melting point
  • storage durability at 55 ° C. is required from the viewpoint of toner storage and storage in a warehouse, and the amount of a component that melts at a temperature of 55 ° C. or less in an ⁇ -olefin polymer (55 When the amount of the melting component at 0 ° C. or less is increased, toner aggregation occurs and the storage durability is poor.
  • the crystalline ⁇ -olefin polymer obtained by using a specific metallocene catalyst has a narrow molecular weight distribution and is a sharp melt, so that the melting point is preferably 50 ° C. or higher, and if the melting point is 70 ° C. or higher.
  • the amount of the melting component at 55 ° C. or less in the ⁇ -olefin polymer is remarkably reduced, and the storage durability is excellent.
  • a low-temperature melting component amount will reduce significantly if melting
  • a component that melts at a temperature of 20 ° C. or less from the melting point of the ⁇ -olefin polymer is defined as a “low-temperature melting component”, and the total amount of heat absorbed when the entire ⁇ -olefin polymer melts is defined.
  • the ratio of the endothermic amount of the low-temperature melting component is defined as “low-temperature melting component amount (%)”, which is indicated as “(Tm-20) ° C. melting component amount (%)”.
  • Tm represents the melting point of the ⁇ -olefin polymer.
  • the amount of the melting component at (Tm-20) ° C. in the ⁇ -olefin polymer of the present invention is preferably 12% or less, more preferably 10% or less, still more preferably 7% or less.
  • the small amount of low-temperature melting component in the ⁇ -olefin polymer means that the ⁇ -olefin polymer has a uniform crystal size and few crystal components that melt to near the melting point, that is, high temperature storage durability.
  • the material is excellent and does not cause problems such as stickiness to the vicinity of the melting point.
  • the amount of the low-temperature melting component can be reduced to 12% or less, and the amount of the low-temperature melting component can be reduced by using a specific catalyst or adjusting the polymerization conditions.
  • the melting component amount of ( ⁇ -olefin polymer melting point ⁇ 20) ° C. in the ⁇ -olefin polymer is calculated from the endothermic peak area in the DSC chart by the following formula.
  • (Tm ⁇ 20) Melting component amount at% (%) ⁇ H (Tm ⁇ 20) / ⁇ H (whole) ⁇ 100
  • Tm represents the melting point of the ⁇ -olefin polymer.
  • ⁇ H (Tm-20) indicates the amount of heat absorbed by melting to “(Tm-20) ° C.” at the endothermic peak of the DSC chart, and ⁇ H (overall) indicates the amount of heat of the entire endothermic peak in the DSC chart.
  • the proportion of low isomers such as 5-6 mers increases, and the amount of dimer components in particular among the low isomers is increased. It is considered that the melting point is lowered by increasing the amount of.
  • the weight average molecular weight is 5000 or less, the amount of dimer component is small, and the decrease in melting point and the increase in low-temperature melting component amount can be suppressed.
  • An ⁇ -olefin polymer having a high melting point can be produced efficiently.
  • the content of the dimer component in the ⁇ -olefin polymer of the present invention is preferably 10% by mass or less, more preferably 8% by mass or less, and still more preferably 5% by mass or less. Content of said dimer can be calculated
  • GC gas chromatography
  • the content of the dimer component can be 10% by mass or less, and the content of the dimer component can be reduced by using a specific catalyst or adjusting the polymerization conditions. be able to.
  • DSC measurement Using a differential scanning calorimeter (manufactured by Perkin Elmer, trade name: DSC-7), 10 mg of a sample is held at ⁇ 10 ° C. for 5 minutes in a nitrogen atmosphere, and then heated to 120 ° C. at 10 ° C./min. The peak end of the endothermic peak observed on the highest temperature side of the melting endothermic curve obtained as described above was taken as the melting point (Tm). In addition, the peak width at 50% height of the endothermic peak when the melting point was measured was defined as the half width.
  • the amount of the melting component of 55 ° C. or less in the ⁇ -olefin polymer obtained by polymerizing the mixture of ⁇ -olefins having 26 and 28 carbon atoms is the area of the portion of 55 ° C. or less in the endothermic peak of the DSC chart.
  • the amount of the melting component of ( ⁇ -olefin polymer melting point ⁇ 20) ° C. in the ⁇ -olefin polymer was calculated from the endothermic peak area in the DSC chart by the following formula.
  • (Tm ⁇ 20) Melting component amount at% (%) ⁇ H (Tm ⁇ 20) / ⁇ H (whole) ⁇ 100
  • Tm represents the melting point of the ⁇ -olefin polymer.
  • ⁇ H (Tm-20) indicates the amount of heat absorbed by melting to “(Tm-20) ° C.” at the endothermic peak of the DSC chart
  • ⁇ H (overall) indicates the amount of heat of the entire endothermic peak in the DSC chart.
  • Example 1 First, in the same manner as in Example 2 described in JP-A No. 2002-308893, (1,1′-tetramethyldisilene) (2,2′-dimethylsilylene) bis (indenyl) zirconium dichloride (hereinafter, “Complex (1)”) was synthesized.
  • Complex (1) (1,1′-tetramethyldisilene) (2,2′-dimethylsilylene) bis (indenyl) zirconium dichloride
  • Examples 2-4 An ⁇ -olefin polymer was produced in the same manner as in Example 1 except that the polymerization temperature was changed as shown in Table 1 in Example 1.
  • Example 2 the catalyst was prepared from (1,1′-Me 2 SiSiMe 2 ) (2,2 ′-(i-Pr) 2 NB) bis (described in Preparation Example 1 of WO 08/102729). Indenyl) Zirconium dichloride (hereinafter referred to as “complex (2)”) was prepared in the same manner as in Example 1 except that the hydrogen pressure and polymerization time were changed as shown in Table 1. did.
  • Example 5 In a 1 L autoclave that had been dried by heating, 200 ml of a mixture of ⁇ -olefins having 26 and 28 carbon atoms (C26: 56.9% by mass, C28: 39.4% by mass), 0.5 mmol of triisobutylaluminum, complex (1 ) 1 ⁇ mol and 4 ⁇ mol of dimethylanilinium tetrakispentafluorophenylborate were added, hydrogen was further introduced at 0.05 MPa (G), and polymerization was carried out at a polymerization temperature of 150 ° C. for 60 minutes. After the completion of the polymerization reaction, the reaction product was precipitated with acetone, followed by drying under heating and reduced pressure to obtain 128 g of an ⁇ -olefin polymer.
  • Example 6 In a 1 L autoclave that had been heat-dried, 400 ml of a mixture of ⁇ -olefins having 20, 22 and 24 carbon atoms (C20: 42% by mass, C22: 36% by mass, C24: 21% by mass), 0.5 mmol of triisobutylaluminum Then, 1 ⁇ mol of complex (1) and 4 ⁇ mol of dimethylanilinium tetrakispentafluorophenyl borate were added, hydrogen was further introduced at 0.05 MPa (G), and polymerization was performed at a polymerization temperature of 110 ° C. for 60 minutes. After the completion of the polymerization reaction, the reaction product was precipitated with acetone, followed by drying under heating and reduced pressure to obtain 185 g of an ⁇ -olefin polymer.
  • a mixture of ⁇ -olefins having 20, 22 and 24 carbon atoms C20: 42% by mass, C22: 36% by mass, C24: 21% by mass
  • Example 7 In a 1 L autoclave that had been dried by heating, 400 ml of a mixture of ⁇ -olefins having 16 and 18 carbon atoms (C16: 10% by mass, C18: 90% by mass), 0.5 mmol of triisobutylaluminum, 1 ⁇ mol of complex (1), dimethyl Anilinium tetrakispentafluorophenylborate (4 ⁇ mol) was added, hydrogen was further introduced at 0.05 MPa (G), and polymerization was carried out at a polymerization temperature of 110 ° C. for 60 minutes. After the completion of the polymerization reaction, the reaction product was precipitated with acetone, followed by drying under heating and reduced pressure to obtain 205 g of an ⁇ -olefin polymer.
  • Comparative Example 3 In a heat-dried 1 liter autoclave, 400 ml of a mixture of ⁇ -olefins having 20, 22 and 24 carbon atoms (C20: 42% by mass, C22: 36% by mass, C24: 21% by mass), 1 mmol of triisobutylaluminum, complex ( 3) 1 ⁇ mol and tetrakispentafluorophenyl borate 8 ⁇ mol were added, and hydrogen 0.15 MPa (G) was further introduced. Polymerization was conducted for 1 hour at 110 ° C. with stirring. After completion of the polymerization reaction, the reaction solution was transferred into acetone. The precipitate was filtered and then heated and dried under reduced pressure to obtain 90 g of an ⁇ -olefin oligomer.
  • Comparative Example 4 In a heat-dried 1 liter autoclave, 400 ml of a mixture of ⁇ -olefins having 26 and 28 carbon atoms (C26: 56.9% by mass, C28: 39.4% by mass), 1 mmol of triisobutylaluminum, 1 ⁇ mol of complex (3), Tetrakis pentafluorophenyl borate (8 ⁇ mol) was added, and hydrogen (0.15 MPa (G)) was further introduced. Polymerization was conducted for 1 hour at 120 ° C. with stirring. After completion of the polymerization reaction, the reaction solution was transferred into acetone. The precipitate was filtered and then heated and dried under reduced pressure to obtain 80 g of an ⁇ -olefin oligomer.
  • Comparative Example 1 the amount of melting component at 55 ° C. or less, which is considered as a factor for lowering the melting point, is as high as 19.8%, the amount of melting component at (Tm-20) ° C. is also high as 14.3%, and ⁇ -olefin weight The melting point of the coalescence was less than 70 ° C. The yield was as low as 37% by mass. Similarly, in Comparative Examples 2 to 4, the amount of melting components at (Tm-20) ° C. was large and the yield was low. In contrast, in Examples 1 to 4, low molecular weight and high melting point ⁇ -olefin polymers having a weight average molecular weight of 5000 or less and a melting point controlled in the range of 70 to 120 ° C. were obtained.
  • Example 5 Although the weight average molecular weight was as low as 2500, the melting point was as high as 70 ° C. or higher. In Example 6, the melting point was higher than that in Comparative Example 3 having the same number of monomer carbons, although the weight average molecular weight was low. Generally, when the number of monomer carbon atoms is small, the melting point of the polymer tends to decrease. However, comparing Comparative Example 3 using 18 carbon atoms and Example 7 using 16 or 18 carbon monomers, Example 7 yielded an ⁇ -olefin polymer having a lower molecular weight and a higher melting point. It was the result.
  • the ⁇ -olefin polymer produced by the method of the present invention has a low molecular weight and a high melting point, and is useful for various applications such as inks, paints, emulsions, and toner release agents.

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Abstract

L'invention concerne un polymère de α-oléfine qui est caractéristique en ce que (C) une α-oléfine de 16 à 40 atomes de carbone est polymérisée en présence d'un catalyseur de polymérisation comprenant : (A) un composé métal de transition de type méso spécifique; et (B) au moins un élément choisi parmi (B-1) un composé formant un complexe ionique par réaction avec (A) le composé métal de transition de type méso spécifique ou son dérivé, et (B-2) un aluminoxane.
PCT/JP2012/071722 2011-09-01 2012-08-28 Procédé de fabrication de polymère de α-oléfine WO2013031779A1 (fr)

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Cited By (1)

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WO2023147078A1 (fr) * 2022-01-31 2023-08-03 Nucera Solutions Llc Procédé de polymérisation de poly(alpha-oléfine)

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