WO2002092641A1 - Procede de production de copolymeres ethylene-cycloolefines - Google Patents

Procede de production de copolymeres ethylene-cycloolefines Download PDF

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Publication number
WO2002092641A1
WO2002092641A1 PCT/JP2002/004484 JP0204484W WO02092641A1 WO 2002092641 A1 WO2002092641 A1 WO 2002092641A1 JP 0204484 W JP0204484 W JP 0204484W WO 02092641 A1 WO02092641 A1 WO 02092641A1
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Prior art keywords
group
ethylene
dimethylsilylene
compound
carbon atoms
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PCT/JP2002/004484
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English (en)
Japanese (ja)
Inventor
Masami Kanamaru
Junichi Matsumoto
Takuji Okamoto
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Idemitsu Petrochemical Co., Ltd.
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Priority to JP2002589522A priority Critical patent/JP4053891B2/ja
Priority to DE10296812T priority patent/DE10296812T5/de
Publication of WO2002092641A1 publication Critical patent/WO2002092641A1/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
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/02—Ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/6592—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
    • C08F4/65922—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not
    • C08F4/65927—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not two cyclopentadienyl rings being mutually bridged

Definitions

  • the present invention relates to a method for producing an ethylene-cyclic olefin copolymer. More specifically, the present invention uses an inexpensive and highly active polymerization catalyst and has a uniform composition and a narrow molecular weight distribution even in a non-aromatic solvent. The present invention relates to a method for efficiently producing an ethylene monocyclic copolymer having high molecular weight and high molecular weight. Background art
  • a catalyst comprising a combination of a transition metal compound and an aluminoxane
  • Japanese Patent Publication No. 58-193309 Japanese Patent Application Laid-Open No.
  • a cationic species is useful as an active species of a soluble catalyst for the polymerization of olefins [see “Journal of Obb'American”. Chemical 'Society' (J. Am. Chem. Soc.), Volume 81, page 81 (1959), Volume 82, page 195 ( 1960), Vol. 107, Vol. 7219 (Page 1985)].
  • the present invention uses an inexpensive and highly active polymerization catalyst, has a uniform composition and a narrow molecular weight distribution even in a non-aromatic solvent, without reducing the molecular weight, and
  • An object of the present invention is to provide a method for efficiently producing an ethylene-cyclic oligomer copolymer having a high molecular weight.
  • a crystalline component in which the cyclic olefin content in the copolymer is extremely low hereinafter sometimes referred to as a polyethylene component.
  • polyethylene component increases, physical properties such as transparency decrease.
  • the present inventors have conducted intensive studies to achieve the above object, and as a result, copolymerized ethylene and cyclic olefin using a polymerization catalyst containing a transition metal compound having a specific structure and an activation promoter. It has been found that the purpose can be achieved by doing so.
  • the present invention is based on this finding. It was completed.
  • the present invention provides: (a) -general formula (I)
  • M is a metal element of Groups 3 to 10 of the periodic table or a lanthanide series
  • R 1 and R 3 are each independently a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, 1 to 20 represents a halogen-containing hydrocarbon group, a silicon-containing group, an oxygen-containing group, an oxygen-containing group, a nitrogen-containing group or a phosphorus-containing group
  • R 2 and R 4 are each independently a hydrogen atom or a halogen atom.
  • R 1 and R 2 and R 2 and R 3 may be bonded to each other to form a ring.
  • a 1 and A 2 represent a divalent group which forms a crosslinked structure by bonding to two cyclopentenyl groups, which may be the same or different.
  • X represents a ⁇ -binding ligand, and when there are a plurality of Xs, the plurality of Xs may be the same or different, and may be cross-linked to another X or a cyclopentenyl group or ⁇ .
  • ⁇ represents a Lewis base, and when there are a plurality of ⁇ , a plurality of ⁇ may be the same or different, and other ⁇ or cyclopentagenenyl It may be cross-linked to a group or X.
  • q is an integer of 1 to 5 and represents ((M atomic value) — 2], and r is an integer of 0 to 3. ]
  • a method for producing an ethylene-monocyclic olefin copolymer comprising copolymerizing ethylene and a cyclic olefin in the presence of a catalyst for polymerization containing a transition metal compound represented by the formula (b) and an activation cocatalyst: It provides BEST MODE FOR CARRYING OUT THE INVENTION
  • the polymerization catalyst comprises (a) a transition metal compound, (b) an activating catalyst and, if necessary, (c) an organoaluminum compound. Those containing are used.
  • the transition metal compound of the component (a) is represented by the general formula (I):
  • M represents a metal element belonging to Groups 3 to 10 of the periodic table or a lanthanide series, and specific examples thereof include titanium, zirconium, hafnium, yttrium, Metal, chromium, manganese, nickel, cobalt, palladium, and lanthanide-based metals.
  • titania is considered from the viewpoint of polymerization activity and the like.
  • Zirconium and hafnium are preferred.
  • R 1 and R 3 are as described above, and specific examples of the halogen atom include a chlorine atom, a bromine atom, a fluorine atom, and an iodine atom, and have 1 to 20 carbon atoms.
  • the hydrocarbon group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isopropyl group, a tert-butyl group, an n-hexyl group, and n— Alkyl groups such as decyl group, cyclopentyl group, cyclohexyl group or cycloalkyl group, phenyl group, aryl groups such as 1-naphthyl group, 2-naphthyl group, and aralkyl groups such as benzyl group.
  • a halogen-containing hydrocarbon group having 1 to 20 carbon atoms for example, a group in which at least one hydrogen atom of the above-mentioned hydrocarbon group such as a trifluoromethyl group is substituted with an appropriate halogen atom Is mentioned.
  • the silicon-containing group include a trimethylsilyl group and a dimethyl (tert-butyl) silyl group
  • the oxygen-containing group include an alkoxy group such as a methoxy group and an ethoxy group.
  • the thio-containing group include a thiol group and a sulfonate group.
  • Examples of the nitrogen-containing group include a dimethylamino group, and examples of the lin-containing group include phenylphosphine.
  • R 1 and R 3 an alkyl group ⁇ a cycloalkyl group is preferable, and a methyl group, an i-propyl group, a cyclopentyl group, and a cyclohexyl group are more preferable.
  • R 2 and R 4 are as described above, where a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, and a silicon-containing group.
  • oxygen-containing group is a specific example of Iou-containing group, a nitrogen-containing group, and Li down-containing group is as exemplified in the description of the R 1 and R 3.
  • R 2 and R 4 a hydrogen atom and an alkyl group having 6 or less carbon atoms are preferable. Particularly preferred are methyl, methyl, ethyl and isopropyl.
  • a 1 and A 2 represents a divalent group capable of forming a crosslinked structure in combination with two Sik Ropentajeniru group.
  • Examples of such a divalent group include a divalent hydrocarbon group having 1 to 20 carbon atoms, a divalent halogen-containing hydrocarbon group having 1 to 20 carbon atoms, and a divalent silicon-containing group.
  • Examples of such a crosslinking group include a methylene group, an ethylene group, an ethylidene group, a propylidene group, an isopropylidene group, a cyclohexylidene group, a 1,2-cyclohexylene group, a vinylidene group, and a dimethylsilylene group.
  • an ethylene group, an isopropylidene group and a dimethylsilylene group are preferred.
  • R 17 is a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group or a hetero atom-containing group, 17 can be the same or different, P may be an integer of 1 to 4, which may be linked to each other to form a ring structure.
  • R 18 2 S i, RG e , R 18 2 S n, R 18 A 1, R 18 P, R 18 P ( 0), R 18 N, oxygen (- 0-), sulfur (an S —), Selenium (1-Se)
  • R 18 is a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group containing 1 to 20 carbon atoms, a silicon-containing group Or a hetero atom-containing group, and when two R 18 s , they may be the same or different, or may be bonded to each other to form a ring structure.
  • R 18 is a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group containing 1 to 20 carbon atoms, a silicon-containing group Or a hetero atom-containing group, and when two R 18 s , they may be the same or different, or may be bonded to each other to form a ring structure.
  • 1,2-phenylene groups can also be mentioned.
  • at least one of A 1 and A 2 is a divalent group that forms a cross-linked structure by a gay atom.
  • X represents a ⁇ -binding ligand, and when there are a plurality of Xs, X may be the same or different, and may be cross-linked to another X or a cyclopentadienyl group or ⁇ .
  • Specific examples of X include a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an alkoxyl group having 1 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, C1 to C20 amide group, C1 to C20 silicon-containing group, C1 to C20 phosphide group, C1 to C20 sulfide group, C1 to C20 And the like.
  • Y represents a Lewis base, and when there are a plurality of Ys, the plurality of Ys may be the same or different, and may be cross-linked to another ⁇ or a cyclopentenyl group or X.
  • Specific examples of the Lewis base of Y include amines, ethers, phosphines, thioethers and the like.
  • Q is an integer of 1 to 5 and represents [(valency of M) —2];
  • transition metal compound represented by the general formula (I) examples include (1,1'-dimethylsilylene) (2,2 ''-dimethylsilylene)-(cyclopentagenenyl) (3, 5 —Dicyclopentylcyclopentagenenyl) zirconium dichloride, (1,1, -dimethylsilylene) (2,2'-dimethylsilylene)-(cyclopentyl genenyl) (3,5-dicyclohexylcyclopentagenenyl) Zirconium dichloride, (1,1'-dimethylsilylene) (2,2'-dimethylsilylene)-(cyclopentagenenyl) (3-cyclopentyl-5-cyclohexynolecyclopentageninole) zirconium Dichloride, (1,1'-dimethylsilylene) (2,2'-dimethylsilylene), (cyclopentene genil) (3,5- Diisopropyl lip mouth pen Jeny
  • (2,2, -dimethylsilylene) 1 (4—methylenocyclopentenyl) (3—cyclohexyl—5—isopropinoresic lopene genil) dinoreconidum chloride, (1 , 1 '
  • 1,1'-dimethylsilylene (2,2'-dimethylsilylene) (4-methylcyclopentene genyl) (3-cyclopropyl-1-isobutylcyclo) Lopenta-genyl) zirconium dichloride, (1,1'-dimethylsilylene) (2,2'-dimethylsilylene) -1 (4-methylcyclopentagen) (3-cyclopropyl-1-) t-Butylcyclopentadienyl) Zirconium dichloride and the like, and the bridging group in these compounds is replaced by (1,1'-dimethylsilylene) (2,2'-dimethylsilylene).
  • the transition metal compound as the component (a) may be used alone or in a combination of two or more.
  • the co-catalyst for activating the component (b) in the polymerization catalyst used in the present invention includes (b-1) a compound which reacts with the transition metal compound of the component (a) or a derivative thereof to form an ionizable compound. And at least one selected from (b-2) oxygen-containing organic aluminum compounds, (b-3) Lewis acids and (b-4) clay compounds. You.
  • (b-1) refers to the transition metal compound of the component (a).
  • any ionizing compound that forms an ionizing complex by reacting with a derivative thereof can be used.However, from the viewpoint of being able to efficiently form a polymerization active site, the following compounds can be used. Those represented by the general formulas (III) and (IV) can be suitably used.
  • M 3 represents an element in Groups 5 to 15 of the Periodic Table, preferably elements in Groups 13 to 15 of the Periodic Table.
  • G 1 to G f represent a hydrogen atom, a halogen atom, and a carbon atom, respectively.
  • Aryloxy group having 4 to 40 carbon atoms, alkylaryl group having 4 to 40 carbon atoms, arylalkyl group having 4 to 40 carbon atoms, halogen-substituted hydrocarbon group having 1 to 20 carbon atoms, 1 to 20 carbon atoms Represents an acyloxy group, an organic metalloid group, or a heteroatom-containing hydrocarbon group having 2 to 20 carbon atoms, wherein at least two of G 1 to G f may form a ring.
  • [Zeta 2] is the reciprocal of the acid dissociation constant log (p Ka) Gar 1 0 following Purensutetsu de acid Germany or Purensutetsu de acids and Lewis acids combinations conjugate base, or generally exhibit conjugate base which is defined as a superacid. Further, a Lewis base may be coordinated.
  • 'R 19 is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, and an aryl group having 6 to 20 carbon atoms.
  • R 2 ° and R 21 represent a cyclopentagenenyl group, a substituted cyclopentadienyl group, an indenyl group or a fluorenyl group, respectively, and R 22 represents a C 1 -C 1 -C 1 -C 1 -C 1 -C 1 -C 2 -C 2 -C 2 -C 2 -C 2 -C 1 20 represents a 3 alkyl group, aryl group, alkyl aryl group or aryl alkyl group.
  • R 23 represents Te Torafue two Ruporufi Li down, a macrocyclic ligand such as lid opening Shianin.
  • M 1 is the first to 3, 1 1-1 3, 1 7 group elements of the periodic table is Dressings containing, M 2 represents a periodic table seventh 1 Group 2 element. ]
  • specific examples include ammonia, methylamine, adiline, dimethylamine, getylamine, N-methylaniline, diphenylamine, N, N-dimethylaniline, and Limethylamine, triethylamine, tri-n-butylamine, methyldiphenylamine, pyridine, p-bromo_N, N_dimethylaniline, ⁇ -nitro-N, N— Amines such as dimethyl aniline; phosphines such as triethylphosphine, triphenylphosphine and diphenylphosphine; thioethers such as tetrahydrothiothiophene; esters such as ethyl benzoate; Nitriles such as cetonitrile and benzonitrile can be mentioned.
  • R 19 hydrogen, methyl, Echiru group, etc. can and Ageruko benzyl group, Application Benefits methyl group, R ", specific examples of R 21 are Shikuropen evening Jeniru group, main Chirushikuropen . evening Jeninore group, Echisore Shikuropen evening Jeniru group, and etc. Pentame chill cyclopentadienyl group as a specific example of R 22, Fuweniru group, p - DOO Lil group, 'p-menu Tokishifueniru group Specific examples of R 2 include tetrafenyl porphyrin, phthalocyanine, and ⁇ . Ril and methalyl can be mentioned. Further, specific examples of M 1 include Li, Na, K, Ag, Cu, Br, I, and I 3 , and specific examples of M 2 include , Mn, Fe, Co, Ni, Zn, and the like.
  • [Z 1 ] — that is, in [M 3 G 1 G 2 ⁇ G £ ], specific examples of M 3 include B, A 1, S i, P, As, S b, and the like. And preferably B and A 1.
  • Examples of G 1 , G 2 to G f include dialkylamino groups such as dimethylamino group and getylamino group, and alkoxy or aryloxy groups.
  • Methoxy, ethoxy, n-butoxy, phenoxy and other hydrocarbon groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isopropyl , N-octyl group, n-eicosyl group, phenyl group, p-tolyl group, benzyl group, 4_t-butylphenyl group, 3,5-dimethylphenyl group, etc.
  • Bromine, iodine, and heteroatom-containing hydrocarbon groups such as p-fluorophenyl group, 3,5-difluorophenyl group, chlorophenyl group, 3,4,5—trifluorophenyl group, and pentafluorophenyl group , 3, 5 — bis (trifluoromethyl) phenyl, bis (trimethylsilyl) methyl, and other organic methyl groups such as pentamethylantimony, trimethylsilyl, and trimethylsilyl.
  • Examples include a dimethylgermyl group, a diphenylarsine group, a dicyclohexylantimony group, and diphenylboron.
  • non-coordinating anion ie, the common base [Z 2 ] _, which is composed of a single presnsted acid having a pKa of ⁇ 10 or less or a combination of a bronsted acid and a Lewis acid.
  • the (b-1) component compound examples include triethylammonium tetrabutylborate, tri-n-butylammonium tetraphenylborate, trimethylammonium tetrabutylborate, and tetramethylammonium.
  • Methyl borate (2-phenylpyridinium), Tetrakis (pentafluorofluorophenyl) Benzyl borate (2—cyanopyridinium), Tetrakis (pentanofluorophenyl) methyl borate (4-1) Cyan Pyridinium), Tetrakis (pentafluorophenyl) Triphenyl borate borate, Tetrakis [bis
  • the component (b-1) may be used alone, or two or more kinds may be used in combination.
  • the oxygen-containing organic aluminum compound as the component (b-2) is represented by the general formula (V)
  • R 24 represents a hydrocarbon group or a halogen atom such as an alkyl group, alkenyl group, aryl group or arylalkyl group having 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms, and w represents It represents an average degree of polymerization, and is usually an integer of 2 to 50, preferably 2 to 40.
  • Each R 24 may be the same or different.
  • R 24 and w are the same as those in the above general formula (V). Further, n is a positive integer.).
  • Examples of the method for producing the aluminoxane include a method in which an alkylaluminum is brought into contact with a condensing agent such as water.However, the method is not particularly limited, and the reaction is carried out according to a known method. I just need. For example, a method in which an organic aluminum compound is dissolved in an organic solvent and then brought into contact with water, a method in which an organic aluminum compound is first added during polymerization, and water is added later, and a method in which metal salts are contained.
  • a method of reacting the water of crystallization and water adsorbed on inorganic and organic substances with an organic aluminum compound a method of reacting a trialkylaluminum with a tetraalkyldialuminoxane, and further reacting the water.
  • the aluminoxane may be toluene-insoluble.
  • the component (b-2) may be used alone or in a combination of two or more.
  • the Lewis acid of the component (b-3) is not particularly limited, and may be an organic compound or a solid inorganic compound.
  • a boron compound or an aluminum compound is preferably used, and as an inorganic compound, a magnesium compound, an aluminum compound, or the like is preferably used because an active site can be efficiently formed.
  • the aluminum compound include bis (2,6-di-tert-butyl-4-methylphenoxy) aluminum methyl, (1,1,1-bi-2-naphthoxy) aluminum methyl, and the like.
  • the compound include magnesium chloride and jetoxymagnesium, and examples of the aluminum compound include aluminum oxide and aluminum chloride.
  • boron compound examples include, for example, triphenyl boron and tris (pentafluorofluorophenyl).
  • ) Boron tris [3,5-bis (trifluoromethyl) phenyl] boron, tris [(4-fluoromethyl) phenyl] boron, trimethylboron, triethylboron, tri-n Butyl boron, tris (fluoromethyl) Boron, tris (pentafluorofluoroethyl) boron, tris (nonafluorobutyl) boron, tris (2,4,6-trifluorophenyl) boron, tris (3,5-difluoro) boron, tri Squirrel [3,5-bis (trifluoromethyl) phenyl] boron, bis (pentafluorophenyl) fluoroboron, diphenylfluoroboron, bis (pentafluoroflu
  • One of these Lewis acids may be used, or two or more may be used in combination.
  • the clay-based compound of the component (b_4) the following clay, clay mineral, or zion-exchangeable layered compound can be used.
  • Clay is an aggregate of fine hydrated maleate minerals, a substance that produces plasticity when kneaded with an appropriate amount of water, exhibits rigidity when dried, and sinters when baked at high temperatures.
  • Clay minerals are hydrated silicates that are the main component of clay. These are not limited to naturally occurring ones, and may be artificially synthesized ones.
  • the ion-exchangeable layered compound is a compound having a crystal structure in which planes formed by ion bonds and the like are stacked in parallel with weak bonding force to each other, and the contained ions are exchangeable.
  • Some clay minerals are ion-exchangeable layered compounds.
  • an ionic crystalline compound having a layered crystal structure such as a hexagonal close-packing type, an antimony type, a cadmium chloride type, a cadmium iodide type and the like can be given.
  • the ion-exchange layered compound is not limited to a naturally occurring compound, and may be an artificially synthesized compound.
  • the component (b-4) include kaolin, bentonite, kibushi clay, gairome clay, alofin, hesingelite, pyrophyllite, evening nolek, gem group, and montmorillonii. Group, basilikiuraite, ryokdi stone group, parigorskite, olizonite, nacreite, dickite, halloysite, etc.
  • the pore volume with a radius of 2 nm or more measured by the mercury intrusion method is 0.1 mil / litre or more, in particular, 0.3 to 5 mil. Those above Torr Z are preferred.
  • the preferred component (b-4) is clay or clay mineral, and the most preferred component is monmorillonite.
  • the component (b-4) may be used after removing impurities or changing its structure and function, and is preferably subjected to chemical treatment.
  • the chemical treatment means either a surface treatment for removing impurities adhering to the surface of the component (b-4) or a treatment that affects the surface and internal crystal structure.
  • Specific examples include acid treatment, alkali treatment, salt treatment, and organic substance treatment.
  • Acid treatment removes surface impurities and increases the surface area by eluting cations such as aluminum, iron, and magnesium in the crystal structure.
  • Alkali treatment destroys the crystal structure, causing a change in the structure.
  • an ionic complex, a molecular complex, an organic complex, and the like are formed, and the surface area, the interlayer distance, and the like can be changed. Utilizing ion exchange, separate exchangeable ions between layers By substituting with bulky ions, it is possible to obtain an interlayer material with an expanded interlayer.
  • component (b-4) may be used as it is, may be newly added and adsorbed water, or may be subjected to heat dehydration.
  • the clay-based compound as the component (b-4), one treated with an organic aluminum compound and / or an organic silane compound in the above-mentioned chemical treatment.
  • the linear aluminoxane represented, the cyclic aluminoxane represented by the general formula (VI) or an aggregate of the cyclic aluminoxane can be used.
  • R 25 and R 26 each represent an alkyl group having 1 to 8 carbon atoms, preferably 1 to 4 carbon atoms;
  • X 1 represents a hydrogen atom or a halogen atom; and
  • m represents 0 ⁇ m ⁇ 3, preferably 2 or 3, most preferably 3, and
  • n is 0 ⁇ n ⁇ 3, preferably 0 or 1.
  • trimethylaluminum Trimethylaluminum, Trialkylaluminum, dimethylaluminum chloride, dimethylaluminum chloride, dimethylaluminum methoxide, trialkylaluminum, tripropylaluminum, triisopropylaminoaluminum, trit-butylaluminum, etc.
  • Halo such as getyl aluminum methoxide And aluminoxane such as alkylaluminum, methylalumoxane, ethylalumoxane, and isobutylalumoxane containing a gen or alkoxy group. Of these, triisobutylaluminum is particularly preferred.
  • the molar ratio of the transition metal in the component (a) to the hydroxyl group in the clay-based compound and the aluminum atom in the organic aluminum compound is 1: 0.1 to 1: 1. It is preferred that the contact be made at 0. 00 to 0: 0 to 1 to 0 0 0 0 0 0, especially at 1 to 0.5 to 1 0 0 0 0 0: 0.5 to 1 0 0 0 0. New
  • organic silane compound for treating the clay compound as the component (b-4) examples include, for example, trimethylsilyl chloride, triethylsilyl chloride, triisopropylsilyl chloride, and tert-butylsilane.
  • Trialkylsilyl chlorides such as butyl dimethyl resilyl chloride, tert-butyl diphenyl silino chloride, phenethyl dimethyl silyl chloride, dimethyl silyl dichloride, getyl silino resyl chloride, diisopropyl chloride
  • Dialkylsilyl dichlorides such as lithoresyl chloride, bisdiphenethylsilyl dichloride, diphenylsilyl resilichloride, dimesityl silino resilichloride, ditrinoresilino reschloride, and methinoresilyl Trichloride, ethylsilyl trichloride, isopro Alkylsilyl trichlorides, such as rusilyl trichloride, phenylsilinolate trichloride, mesityl silinolate trichloride, trinolesilin
  • Triisopropylsilyl amide, bis (dimethylethylsilyl) Amid, bis (dimethylmethylsilyl) amide, bis (dimethylphenylsilyl) amide, bis (dimethyltrisilyl) amide, bisilazane such as bis (dimethylmethylsilylsilyl) amide, Tetraalkylsilanes such as polysilanols, dimethyldiphenylsilane, getyldiphenylsilane, and dimethyldiphenylsilane, which are commonly referred to by the common name of peralkylpolysiloxypolyol, trimethyl Tylsilane, triethylsilane, triisopropyl silane, tri-t-butyl silane, triphenyl silane, tritrisilane, trimesityl silane, methyl diphenyl silane, dinaphthyl methyl silane, Trialkylsilanes
  • the molar ratio of the transition metal in the component (a) to the hydroxyl group in the clay compound and the silicon atom in the organic silane compound is 1: 0.1 to 1 0 0 0 0 0: 0.1 ⁇
  • the contact be made at a value of 1: 0.5 to 100: 0: 0.5 to 1 000, in particular, so as to be 100 000 000.
  • At least one of the catalyst components can be used by being supported on a suitable carrier.
  • the type of the carrier is not particularly limited, and any of an inorganic oxide carrier, other inorganic carrier and an organic carrier can be used.
  • the inorganic oxide carrier or the other inorganic carrier may be used. Carriers are preferred.
  • the activation co-catalyst of the component (b) is Oxygen-containing organic aluminum compounds comprising aluminoxane are preferred.
  • organoaluminum compound of the component (c) an alkyl group-containing aluminum compound represented by the above general formulas (VII), (V) and (VI), a linear aluminoxane or a cyclic aluminoxane, An aggregate of cyclic aluminoxane can be mentioned.
  • the catalyst for polymerization in the present invention includes (a) a transition metal in which at least one of A 1 and A 2 in the above general formula (I) is a divalent group forming a crosslinked structure by a gayne atom.
  • At least one compound selected from the compounds is preferable.
  • a compound using a trialkylaluminum as the component (c) is preferable, and a compound using an aluminoxane as the component (b) is particularly preferable. Is suitable.
  • ethylene is copolymerized with cyclic olefin in the presence of the polymerization catalyst to produce an ethylene monoolefin copolymer.
  • ethylene may be ethylene alone or a mixture of ethylene and other one-year-old olefins having 3 to 25 carbon atoms, such as propylene, butene-1,1,4-methylpentene-11.
  • cyclic olefin examples include a monocyclic olefin such as cyclopentene and cyclohexene, a polycyclic olefin such as norbornene, Cyclic gens such as dicyclopentene genenyl can be mentioned.
  • One of these cyclic orientations may be used, or two or more thereof may be used in combination. Particularly preferred among these are the general formulas
  • R 5 to R 1 S are each a hydrogen atom, a hydrocarbon group or a halogen atom with carbon number 1-2 0, Wakashi oxygen atom Ku substituent n containing a nitrogen atom represents an integer of 0 or more, R 13 or R 14 and R 15 or R 18 and may form a ring bonded to each other is also, R 5 to R 16 may be the same or different.
  • a norbornene or a derivative thereof is particularly preferable.
  • Examples of the hydrocarbon group having 1 to 20 carbon atoms in the general formula (II) include, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, C1-C20 alkyl such as hexyl, C6-C20 aryl, alkylaryl or arylalkyl, methylidene, such as phenyl, tolyl, and benzyl; , Ethylidene group, propylidene group Examples thereof include an alkylidene group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms such as a vinyl group and an aryl group.
  • R 7 , R 8 , and R 11 to R 16 is an alkylidene group, the carbon atom to which it is bonded has no other substituent.
  • Examples of the substituent containing a halogen atom include a halogen group having 1 to 20 carbon atoms, such as a halogen group such as fluorine, chlorine bromine, and iodine, and a chloromethyl group, a bromomethyl group, and a cycloethyl group. Examples thereof include an alkyl group.
  • Examples of the substituent containing an oxygen atom include an alkoxy group having 1 to 20 carbon atoms such as a methoxy group, an ethoxy group, a propoxy group, and a phenoxy group, a methoxycarbonyl group, and an ethoxycarbonyl group. Examples thereof include an alkoxycarbonyl group having 1 to 20 carbon atoms.
  • Examples of the substituent containing a nitrogen atom include an alkylamino group having 1 to 20 carbon atoms, such as a dimethylamino group and a dimethylamino group, and a cyano group.
  • Examples of the cyclic olefin represented by the general formula (II) include norbornene, 5-methylnorbornene, 5-ethylnorbornene, 5-propylnorbornene, 5,6-dimethylnorbornene, and 1-methylnorbornene.
  • the polymerization method in the present invention is not particularly limited, and known methods such as slurry polymerization, gas-phase polymerization, high-pressure polymerization, and solution polymerization can be used. These polymerization methods can be used alone or in combination. Combined multistage polymerization and prepolymerization can also be used. Among them, solution polymerization is preferred.
  • the polymerization temperature is not particularly limited, but is usually from 20 to 250 ° C, preferably from 40 to 220 ° C, and more preferably from 60 to 190 ° C. .
  • the polymerization pressure is not particularly limited, but is preferably from 0.05 to 10 MPa, more preferably from 0.1 to 7 MPa.
  • the polymerization time is not particularly limited, but is usually 1 to 180 minutes.
  • the catalyst is used in an amount of 0.001 to 100 micromoles Z liter, preferably 0.01 to 100 micromoles / liter, in terms of the transition metal of component (a). Preferably it is between 0.02 and 50 micromol / liter. If the amount used is too large, it becomes difficult to remove the heat of the polymerization. On the other hand, if the amount is too small, sufficient activity is not exhibited.
  • the amount of the activating cocatalyst is usually 0.1 to 10 times (molar ratio), preferably 0.3 to 5 times, based on the transition metal. Particularly preferably, the amount is 0.5 to 3 times.
  • the amount is usually 1 to 1000 times (molar ratio), preferably 5 to 500 times the amount of the transition metal.
  • the component (b-3) is used, it is usually 0. ⁇ 10 times
  • component (b-4) is usually 0.0001 to 100 g, preferably 0.05 to 50 g, and particularly preferably 0.1 to 0.1 g per mol of the transition metal. 0 1 to 10 g.
  • chemically treated (b-4) usually 1 mole of transition metal
  • the amount used is too large, there are problems such as high cost and an increase in the residual amount in the copolymer, which deteriorates the physical properties of the polymer. Conversely, if the amount is too small, sufficient catalytic activity cannot be obtained, resulting in high cost and lowering of the physical properties of the polymer.
  • the organoaluminum compound of the component (c) When the organoaluminum compound of the component (c) is used, it is usually 1 to 1000 times (molar ratio) to the transition metal, preferably 5 to 100 times. The amount is 100 times, particularly preferably 100 to 500 times.
  • Methods for adjusting the molecular weight of the copolymer include selection of the type and amount of each catalyst component used, the polymerization temperature, and polymerization in the presence of hydrogen.
  • a polymerization solvent for example, aromatic hydrocarbons such as benzene, toluene, and xyleneethylbenzene, alicyclic hydrocarbons such as cyclopentane, cyclohexane, and methylcyclohexane, pentane, hexane, heptane , Octane and the like, and halogenated hydrocarbons such as chlorinated form and dioctene romene. These solvents may be used alone or in a combination of two or more.
  • a non-aromatic solvent it is advantageous to use a non-aromatic solvent.
  • a monomer such as cyclic or ⁇ -olefin may be used as the solvent.
  • it can be carried out without a solvent depending on the polymerization method.
  • preliminary polymerization can be performed using the polymerization catalyst.
  • the prepolymerization can be carried out by bringing a small amount of an olefin into contact with the catalyst component, but the method is not particularly limited, and a known method can be used.
  • the olefin used for the prepolymerization is not particularly limited, and is the same as that exemplified above.Examples include ethylene, monoolefin having 3 to 20 carbon atoms, cyclic olefin, and a mixture thereof. However, it is advantageous to use the same olefin used in the polymerization.
  • the prepolymerization temperature is usually from 120 to 200 ° C., preferably from ⁇ 10 to 130 ° C., and more preferably from 0 to 80 ° C.
  • an aliphatic hydrocarbon, an aromatic hydrocarbon, a monomer or the like can be used as a solvent. Of these, fat is particularly preferred. Group hydrocarbons.
  • the prepolymerization may be performed without a solvent.
  • the intrinsic viscosity of the pre-polymerized product [] (measured in a power line at 135) is ⁇ .2 deciliters / g or more, especially 0.5 deciliters or more g, in the catalyst. It is desirable to adjust the conditions so that the amount of the prepolymerized product per 1 mol of the transition metal component is 1 to 1000 g, particularly 10 to 100 g.
  • a linear alkyl group, a branched alkyl group, a halogen, an alkoxy group, etc. may be used for the purpose of removing catalyst poisoning substances in the system and alkylating the complex. It can also be carried out after treating the inside of the reactor or the catalyst in advance using an organic aluminum compound having a substituent selected from the groups.
  • the amount of the organic aluminum compound to be used is usually 0.01 to 10000 mol, preferably 0.01 to 500 mol, per 1 mol of the transition metal. Particularly preferred is 0.:! To 500,000 moles.
  • Anhydrous THF 20 milliliter and 0.2 g of lithium aluminum hydride were charged into a 100 milliliter three-neck flask equipped with a Dimroth tube and a dropping port.
  • a solution prepared by dissolving the product in THF 10 milliliters was added dropwise under ice-cooling and a nitrogen atmosphere.
  • 20 milliliters of water was added under ice cooling, and extraction was performed with 50 milliliters of Jetil ether.
  • the organic layer was dried over magnesium sulfate, filtered, and the oily product obtained by distilling off the solvent under reduced pressure was purified by a silica gel column using hexane as a solvent to obtain 1,3-dicyclohexane. Pentylcyclopentene was obtained.
  • a copolymer was obtained in the same manner as in Example 1 except that the polymerization conditions were changed as shown in Table 1. The results are shown in Table 1.
  • Example 1 (2) (1,1′-dimethylsilylylene) (22′-dimethylsilylene) (cyclohexene genil) (3,5-dicyclopentylenecycloyl)
  • the polymerization was carried out in the same manner except that 0.5 micromol of biscyclopentene genilzirco dimethyldichloride was used instead of 0.5 micromol of reconidium chloride.
  • the activity per transition metal and the 2-norbornene unit content determined by NMR were 500 kg / g Zr and 3 mol%, respectively. Table 1 shows the other results.
  • THF from 30 g of cyclopentene and 1.5 g (22.0 millimoles) of sodium and 0.51 g (22.0 millimoles) of sodium in THF Lopentagenide was prepared, and 4.1 g of (3,5-dimethylcyclopentagenenyl) dimethylchlorosilan synthesized above was added dropwise thereto, followed by stirring at room temperature overnight.
  • the solvent is distilled off, the residue is extracted with 60 ml of n-hexane, and then the n-hexane is distilled off to give (3,5-dimethylcyclopentagenenyl) (cyclopentagenenyl). 2.62 g (12.1 millimoles) of dimethylsilane was obtained.
  • This dilithium salt was dissolved in THF 20 milliliters, and dichlorodimethylsilyl 1.5 milliliters was added dropwise at 0 ° C, followed by stirring at room temperature overnight. After distilling off the solvent, 1,3,4,4,8,8-hexamethyl thiol trahydro-1,4,8_disilane is extracted by extracting with n-hexane 40 milliliters. s—Indacene 2.46 g (9.0 mimol) was obtained.
  • Example 1 (2) (1, 1'-dimethylsilylene) (2 ; 2'-dimethylsilylene) (cyclopentene genil) (3,5-dicyclopentylcyclopentyl) pentagenenyl )
  • zirconium dichloride (1,1'-dimethylsilylene) (2,2'-dimethylsilylene) 1-cyclopentagenenyl (3,5-dimethylcyclopentagenenyl)
  • a copolymer was obtained in the same manner as in Example 1 (2), except that zirconium dichloride was used and the polymerization conditions were changed as shown in Table 2. The measurement results for this copolymer are shown in Table 2 ( Example 5
  • pyrrolidine 36 milliliters was added dropwise at room temperature to synthesize 36.8 g of 3-isopropyl-16,6-dimethylfurfulvene 36.8 g.
  • To 9.4 g of lithium aluminum hydride was added 200 ml of ether, and under ice-cooling, 3 -isopropyl-1, 6,6 -dimethyltylfulvene 35.3 g (23.7.8) (Millimol) in 50 milliliters of ether was added dropwise.
  • This dilithium salt was dissolved in THF 20 milliliters, and dichloromethylethylsilane 1.0 milliliter was added dropwise at room temperature, followed by stirring for 5 hours. The solvent was distilled off under reduced pressure, and the residue was extracted with 20-milliliter of n-hexane to give 1,3-diisopropyl pill 1,4,4,8,8-tetramethyltetrahydro-4- There were obtained 2.39 g (7.27 mol) of, 8-disilas-indacene.
  • Example 1 (2) (1,1'-dimethylsilylene) (2,2'-dimethylsilylene) mono (cyclopentagenenyl) (3,5—dicyclopentylcyclopentenyl) Instead of zirconium dichloride, (1,1'-dimethylsilylene) (2,2'-dimethylsilylene)-(cyclopentagenenyl) (3,5-diisopropynolecyclopentane) Genyl) A copolymer was obtained in the same manner as in Example 1 (2), except that the polymerization conditions were changed as shown in Table 2 using zirconium dichloride. Table 2 shows the measurement results of the copolymer.
  • the amount of the polyethylene component that is, the amount of the crystalline component in which the cyclic olefin content in the copolymer is extremely small
  • the copolymer obtained by the production method of the present invention has no high melting point component of 110 ° C. or more in DSC measurement. This indicates that the composition of the copolymer is uniform. For this reason, molded articles produced using the copolymer of the present invention are expected to exhibit good mechanical and optical properties (eg, transparency).
  • an inexpensive and highly active polymerization catalyst is used, and in a non-aromatic solvent, a molecular weight is not reduced, a uniform composition, a narrow molecular weight distribution, and a high molecular weight ethylene is used.
  • a monocyclic copolymer can be efficiently produced.

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Abstract

Copolymères éthylène-cyclooléfines ayant des compositions uniformes, une répartition étroite des poids moléculaires et des poids moléculaires élevés, qui peuvent être produits même dans un solvant non aromatique par copolymérisation d'éthylène avec une cyclooléfine en présence d'un catalyseur de polymérisation contenant (a) un composé de métal de transition représenté par la formule générale (I) et (b) un cocatalyseur d'activation. Dans la formule (I), M est un élément choisi parmi des éléments métalliques du groupe 3 à 10 et de la série des lanthanides du tableau périodique, R1 à R3 représentent chacun indépendamment halogéno, hydrocarbyle C¿1-20?, halohydrocarbyle C1-20 ou un groupe contenant du silicium, de l'oxygène, du soufre, de l'azote ou du phosphore, ou bien R?2 et R4¿ peuvent représenter hydrogène, ou bien R?1 et R2 ou R2 et R3¿ peuvent être unis pour former un noyau, A1 et A2 représentent chacun un groupe de pontage bivalent, X représente un groupe à liaison σ, Y représente une base de Lewis, q est un nombre entier de 1 à 5 et r est un nombre entier de 0 à 3.
PCT/JP2002/004484 2001-05-15 2002-05-08 Procede de production de copolymeres ethylene-cycloolefines WO2002092641A1 (fr)

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