JP6547484B2 - Method for producing ethylene-based polymer having unsaturated bond - Google Patents

Description

  The present invention relates to a method for producing an ethylene-based polymer having an unsaturated bond.

  As global environmental issues such as the increase of carbon dioxide are getting close up, solar power generation has come to be refocused together with effective use of water power, wind power and geothermal heat. Although solar power generation is smaller than hydropower, wind power, etc., it can be distributed to places where power is needed, so research and development aimed at improving performance such as power generation efficiency and lowering prices are being promoted . In addition, with the adoption of measures to assist the installation costs as a project to introduce solar power generation systems for homes in the country and local governments, its diffusion is gradually advancing. However, further cost reduction is necessary for further diffusion, and therefore, not only development of a solar cell element using a new material replacing conventional silicon or gallium-arsenic, but also the manufacturing cost of a solar cell module Efforts are underway to further reduce the

  In solar power generation, generally, solar cell elements such as silicon, gallium-arsenic and copper-indium-selenium are protected by an upper transparent protective material and a lower substrate protective material, and the solar cell element and the protective material are sealed by resin. A solar cell module fixed with materials and packaged is used.

  As a condition of the sealing material which comprises a solar cell module, in order to ensure the incident amount of sunlight so that the power generation efficiency of a solar cell may not be reduced, it is calculated | required that transparency is favorable. Moreover, since a solar cell module is usually installed outdoors, it is exposed to sunlight for a long time and temperature rises. Thus, the resin sealing material must be heat resistant in order to avoid problems such as fluidization and deformation of the module.

  Conventionally, ethylene / vinyl acetate copolymer (EVA) with a high vinyl acetate content has been used as a resin material for a sealing material, but ethylene / α-olefin copolymer excellent in transparency, moisture resistance, etc. It has been proposed to use For example, Patent Document 1 discloses a sealing material using an amorphous or low crystalline α-olefin copolymer having a crystallinity of 40% or less, and mainly ethylene as the α-olefin copolymer. It is described that a crosslinking agent is blended in the copolymer as a component.

  In recent years, with the increase in demand for solar cell modules, improvement in the production efficiency of solar cell modules is required, and there is a tendency to shorten the crosslinking step of the sealing material. In general, ethylene / α-olefin copolymers are not easy to crosslink with organic peroxide compared to EVA, and it is difficult to obtain a high gel fraction in short time heating, and crosslinks to the same degree as EVA It is difficult to get the efficiency. This is because the vinyl acetate moiety which is a comonomer can easily be a radical crosslinking point in EVA, whereas the α-olefin comonomer itself used in a general ethylene / α-olefin copolymer does not become a radical crosslinking point .

  Therefore, in order to improve the crosslinking efficiency of the ethylene α-olefin copolymer, the number of branches and the number of unsaturated bonds (vinyl, vinylidene, cis-vinylene, trans-vinylene, trisubstituted olefin) in the copolymer are large. It has been proposed to use an ethylene / α-olefin copolymer (Patent Documents 2 and 3). However, a sealing material using ethylene / α-olefin copolymer is required to further improve the crosslinking efficiency.

  Olefin polymerization catalysts generally adjust the molecular weight of the polymer produced by hydrogen. Non-Patent Document 1 shows that hydrogen is by-produced in olefin polymerization using a metallocene catalyst. As a device to reduce the concentration of by-produced hydrogen, it has been proposed to use a specific titanocene (Patent Documents 4 and 5), but in order to increase the amount of unsaturated bonds in the polymer to the extent of improving the crosslinking efficiency Further improvement is required.

JP, 2006-210906, A JP 2012-009688 A JP 2012-009691 A JP-A-2014-505771 JP, 2015-003952, A Organometallics, 1998, 17, p. 4997-5002.

  In view of the problems of the prior art, an object of the present invention relates to a method for producing an ethylene-based polymer having a large number of unsaturated bonds, and an object thereof is to provide a polymer having excellent crosslinking properties.

As a result of intensive studies to solve the above problems, the present inventors perform polymerization using a metallocene catalyst as a catalyst component in the state where the polymer is dissolved, and add a specific titanocene into a polymerization system including a circulatory system. It has been found that it is possible to produce an ethylene-based polymer having many unsaturated bonds, and the present invention has been completed.
The titanium compound represented by the general formula (1) has already been known to have the effect of reducing the hydrogen concentration in the polymerization system. On the other hand, it is known that titanium compounds are also effective in the hydrogenation reaction of olefin polymers. Therefore, it was expected to be unsuitable for the purpose of increasing unsaturated bonds in the ethylene-based polymer.
However, it has been found that by combining the olefin polymerization catalyst of the present invention with component (C) under specific polymerization conditions, it is possible to increase unsaturated bonds contrary to the expectation from conventional technical common sense .

That is, according to the first aspect of the present invention, in the polymerization of ethylene by the olefin polymerization catalyst containing the following components (A) and (B), the polymerization is carried out in the state where the polymer to be produced is dissolved. Provided is a method for producing an ethylenic polymer having unsaturated bonds.
Component (A) Metallocene compound having Ti, Zr, or Hf as a central metal Component (B) Compound which reacts with component (A) to form an ion pair or ion exchangeable layered silicate Component (C) General formula (1) A compound represented by)

[In general formula (1), R ^{1 to} R ¹⁰ are the same or different and each is a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 10 carbon atoms, 6 to 6 carbon atoms 20 carbon atoms substituted by 20 aryl groups, an alkoxy group having 1 to 10 carbon atoms, a silyl group having a hydrocarbon group having 1 to 6 carbon atoms, and a silyl group having a hydrocarbon group having 1 to 6 carbon atoms alkyl group, ^{-NR 30} ₂ group of, ^{-SR 30} groups, a -OSiR ³⁰ ₃ group or ^{-PR 30} ₂ radical (R ³⁰ represents a halogen atom, an alkyl group having 1 to 10 carbon atoms, 6 to 20 carbon atoms And R ^{1 to} R ¹⁰ may be taken together with the atoms linking them by adjacent substituents to form one or more aromatic rings or aliphatic rings;
X ¹ and X ² are the same or different and each is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aryloxy having 6 to 10 carbon atoms Group, alkenyl group having 2 to 10 carbon atoms, arylalkyl group having 7 to 40 carbon atoms, alkylaryl group having 7 to 40 carbon atoms, alkenyl aryl group having 8 to 40 carbon atoms, hydrocarbon group having 1 to 6 carbon atoms C 1 -C 20 alkyl group substituted by a silyl group having C 1, C 1 -C 10 amino group, OH group, halogen atom or neutral ligand capable of coordination, and X ¹ and X ² are , Together with the atoms connecting them, may form one ring. ]

  Further, according to a second aspect of the present invention, in the first aspect, an ethylene-based copolymer having an unsaturated bond characterized in that the ethylene-based copolymer is a copolymer of ethylene and an α-olefin. A method of making the combination is provided.

  Further, according to the third invention of the present invention, in the first invention, the at least one .alpha.-olefin is selected from propylene, 1-butene, 1-hexene, 1-octene or 1-decene. There is provided a process for producing an ethylene-based polymer having an unsaturated bond.

  Further, according to the fourth invention of the present invention, in any one of the first to third inventions, an ethylene system having an unsaturated bond characterized by polymerizing in a hydrocarbon solvent at a polymerization temperature of 90 ° C. or higher. A method of making a polymer is provided.

  Further, according to the fifth invention of the present invention, in any one of the first to third inventions, an ethylene polymer having an unsaturated bond characterized in that it is polymerized at a polymerization temperature equal to or higher than the melting point of the polymer to be produced. The manufacturing method of is provided.

  Further, according to the sixth invention of the present invention, in any of the first to fifth inventions, the metallocene complex of the component (A) is a compound represented by the general formula (2) A method of producing an ethylene-based polymer having unsaturated bonds is provided.

[In the general formula (2), M is Ti, Zr or Hf;
R ^{11 to} R ¹⁶ and R ^{17 to} R ²² are the same or different and each is a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 10 carbon atoms, or 6 to 20 carbon atoms An alkyl group substituted by an aryl group, an alkoxy group having 1 to 10 carbon atoms, a silyl group having a hydrocarbon group having 1 to 6 carbon atoms, or a silyl group having a hydrocarbon group having 1 to 6 carbon atoms group, ^{-NR 30} ₂ group, ^{-SR 30} group, an -OSiR ³⁰ ₃ group or ^{-PR 30} ₂ radical ^{(R 30} represents a halogen atom, an alkyl group having 1 to 10 carbon atoms, aryl having 6 to 20 carbon atoms And R ^{11 to} R ¹⁶ and R ^{17 to} R ²² may combine with the atoms connecting them together to form one or more aromatic rings or aliphatic rings. ,;
Y is Si or C;
R ²³ and R ²⁴ are the same or different and each is a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, a fluoroalkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or 6 to 6 carbon atoms 20 aryl groups, fluoroaryl groups having 6 to 10 carbon atoms, aryloxy groups having 6 to 10 carbon atoms, alkenyl groups having 2 to 10 carbon atoms, arylalkyl groups having 7 to 40 carbon atoms, 7 to 40 carbon atoms An alkylaryl group, an alkenylaryl group having 8 to 40 carbon atoms, and R ²³ and R ²⁴ are not simultaneously a hydrogen atom, and R ²³ and R ²⁴ together with the atoms connecting them together are one or more May form a ring;
X ³ and X ⁴ are the same or different and each is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aryloxy having 6 to 10 carbon atoms Group, alkenyl group having 2 to 10 carbon atoms, arylalkyl group having 7 to 40 carbon atoms, alkylaryl group having 7 to 40 carbon atoms, alkenyl aryl group having 8 to 40 carbon atoms, hydrocarbon group having 1 to 6 carbon atoms C 1 -C 20 alkyl group substituted by a silyl group having C 1, C 1 -C 10 amino group, OH group, halogen atom or neutral ligand capable of coordination, and X ³ and X ⁴ are , Together with the atoms connecting them, may form one ring. ]

Further, according to the seventh invention of the present invention, in any one of the first to fifth inventions, an unsaturated bond characterized in that at least one of R ¹¹ and R ¹⁷ in the general formula (2) is hydrogen. There is provided a process for producing an ethylene-based polymer having

Further, according to the eighth invention of the present invention, in any of the first to seventh inventions, R ¹³ and R ¹⁹ in the general formula (2) are a substituent represented by the following general formula (3) There is provided a process for producing an ethylene-based polymer having an unsaturated bond, characterized in that

[In general formula (3), R ^{25 to} R ²⁹ are the same or different and each is a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 10 carbon atoms, 6 to 6 carbon atoms 20 carbon atoms substituted by 20 aryl groups, an alkoxy group having 1 to 10 carbon atoms, a silyl group having a hydrocarbon group having 1 to 6 carbon atoms, and a silyl group having a hydrocarbon group having 1 to 6 carbon atoms alkyl group, ^{-NR 30} ₂ group of, ^{-SR 30} groups, a -OSiR ³⁰ ₃ group or ^{-PR 30} ₂ ^{radical, R 30} represents a halogen atom, an alkyl group having 1 to 10 carbon atoms, 6 to 20 carbon atoms The aryl groups may be combined with the atoms linking them together by adjacent substituents to form one or more aromatic or aliphatic rings. ]

  The present invention relates to a method for producing an ethylene-based polymer having an unsaturated bond. By increasing the unsaturated bond, the crosslinking rate of the polymer is improved, and it can be expected to be a material suitable for a solar cell encapsulant and the like.

The method for producing an ethylene-based polymer having an unsaturated bond according to the present invention is characterized in that, in the metallocene-catalyzed ethylene polymerization, the polymerization is carried out in the state where the produced polymer is dissolved, and a specific Ti compound is added.
Hereinafter, each component used in this invention, superposition | polymerization conditions, etc. are demonstrated in detail for every item.

1. Olefin Polymerization Catalyst The olefin polymerization catalyst used in the present invention contains the following components (A) and (B). Moreover, you may use a component (D) as needed.
Component (A) Metallocene compound having Ti, Zr or Hf as central metal Component (B) Compound which reacts with component (A) to form an ion pair or ion exchangeable layered silicate component (D) Organoaluminum compound

(1) Component (A)
The component (A) used in the present invention is a metallocene compound having Ti, Zr or Hf as a central metal.
Specifically, compounds represented by the following general formulas (I) to (VI) are used.

(C ₅ H _5-a R ³¹ _a ) (C ₅ H _5-b R ³² _b ) MXY (I)
Q (C ₅ H _4-c R ³¹ _c ) (C ₅ H _4-d R ³² _d ) MXY (II)
Q ′ (C ₅ H _4-e R ³³ _e ) ZMXY (III)
(C ₅ H _5-f R ³³ _f ) ZMXY (IV)
(C ₅ H _5-f R ³³ _f ) MXYW (V)
Q ′ ′ (C ₅ H _5-g R ³⁴ _g ) (C ₅ H _5-h R ³⁵ _h ) MXY (VI)

Here, Q is a bonding group that bridges two conjugated five-membered ring ligands, Q ′ is a bonding group that bridges a conjugated five-membered ring ligand and a Z group, and Q ′ ′ is R ³⁴ and R a binding group which crosslinks ^35, M is a groups 3 to 12 transition metal of the periodic table, X, Y and W are each independently hydrogen, halogen, hydrocarbon group having 1 to 20 carbon atoms, carbon atoms 1 to 20 oxygen-containing hydrocarbon group, nitrogen-containing hydrocarbon group having 1 to 20 carbon atoms, phosphorus-containing hydrocarbon group having 1 to 20 carbon atoms or silicon-containing hydrocarbon group having 1 to 20 carbon atoms, and Z is oxygen And a ligand containing sulfur, a silicon-containing hydrocarbon group having 1 to 40 carbon atoms, a nitrogen-containing hydrocarbon group having 1 to 40 carbon atoms or a phosphorus-containing hydrocarbon group having 1 to 40 carbon atoms, M represents Ti, It is a Group 4 transition metal such as Zr or Hf.

R ^{31 to} R ³⁵ each independently represent a hydrocarbon group having 1 to 20 carbon atoms, a halogen atom, a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group, an aryloxy group, an oxygen-containing hydrocarbon group, silicon It shows a containing hydrocarbon group, a phosphorus containing hydrocarbon group, a nitrogen containing hydrocarbon group or a boron containing hydrocarbon group. Among these, it is preferable that at least one of R ^{31 to} R ³⁵ is a heterocyclic aromatic group. Among heterocyclic aromatic groups, furyl group, benzofuryl group, thienyl group and benzothienyl group are preferable, and furyl group and benzofuryl group are more preferable. These heterocyclic aromatic groups include a hydrocarbon group having 1 to 20 carbon atoms, a halogen atom, a halogen containing hydrocarbon group having 1 to 20 carbon atoms, an oxygen containing hydrocarbon group, a silicon containing hydrocarbon group, and a phosphorus containing carbonized group. Although it may have a hydrogen group, a nitrogen-containing hydrocarbon group or a boron-containing hydrocarbon group, in that case, a hydrocarbon group having 1 to 20 carbon atoms and a silicon-containing hydrocarbon group are preferable. In addition, adjacent two R ³¹ , two R ³² , two R ³³ , two R ³⁴ , or two R ³⁵ are combined to form a ring having 4 to 10 carbon atoms. It may be done. a, b, c, d, e, f, g and h are respectively 0 ≦ a ≦ 5, 0 ≦ b ≦ 5, 0 ≦ c ≦ 4, 0 ≦ d ≦ 4, 0 ≦ e ≦ 4, 0 ≦ It is an integer that satisfies f ≦ 5, 0 ≦ g ≦ 5, and 0 ≦ h ≦ 5.

A linking group Q bridging between two conjugated five-membered ring ligands, a linking group Q ′ bridging between a conjugated five-membered ring ligand and a Z group, and bridging between R ³⁴ and R ³⁵ Specific examples of Q ′ ′ include the following: methylene, alkylene such as ethylene, ethylidene, propylidene, isopropylidene, phenylmethylidene and diphenylmethylidene Silicon such as alkylidene group, dimethylsilylene group, diethylsilylene group, dipropylsilylene group, diphenylsilylene group, methylethylsilylene group, methylphenylsilylene group, methyl-t-butylsilylene group, disilylene group, tetramethyldisilylene group Containing crosslinking groups, germanium-containing crosslinking groups, alkyl phosphines, amines, etc. Among these, alkylene groups, alkylidene groups, -Containing bridging groups, and germanium-containing crosslinking group are particularly preferably used.

  Specific Zr complexes represented by the above general formulas (I), (II), (III), (IV), (V) and (VI) are exemplified below, but Zr is replaced with Hf or Ti The same compounds can also be used. Further, the components (A) represented by the general formulas (I), (II), (III), (IV), (V) and (VI) are compounds represented by the same general formula, or It can be used as a mixture of two or more of the compounds shown.

Compounds of the general formula (I) Biscyclopentadienylzirconium dichloride, bis (n-butylcyclopentadienyl) zirconium dichloride, bis (2-methylindenyl) zirconium dichloride, bis (2-methyl-4,5-benzoin) (Denyl) zirconium dichloride, bisfluorenylzirconium dichloride, bis (4H-azulenyl) zirconium dichloride, bis (2-methyl-4H-azulenyl) zirconium dichloride, bis (2-methylcyclopentadienyl) zirconium dichloride, bis ( 2-Methyl-4-phenyl-4H-azulenyl) zirconium dichloride, bis (2-methyl-4- (4-chlorophenyl) -4H-azulenyl) zirconium dichloride, bis (2-furylcyclopentadienyl) zirco Sodium dichloride, bis (2-furylindenyl) zirconium dichloride, bis (2-furyl-4,5-benzoindenyl) zirconium dichloride.

Compounds of general formula (II) dimethylsilylene bis (1,1′-cyclopentadienyl) zirconium dichloride, dimethylsilylene bis [1,1 ′-(2-methylindenyl)] zirconium dichloride, dimethylsilylene bis [1,1 1 ′-(2-Methyl-4-phenyl-indenyl) zirconium dichloride, ethylene bis [1,1 ′-(2-methyl-4,5-benzoindenyl) zirconium dichloride, dimethylsilylene bis [1,1 '-(2-Methyl-4H-azulenyl) zirconium dichloride, dimethylsilylene bis [1,1'-(2-methyl-4-phenyl-4H-azulenyl)] zirconium dichloride, dimethylsilylene bis [1,1'- {2-Methyl-4- (4-chlorophenyl) -4H-azulenyl} zirconium di-k Lido, dimethylsilylene bis [1,1 '- (2-ethyl-4-phenyl -4H- azulenyl)] zirconium dichloride, ethylene bis [1,1' - (2-methyl -4H- azulenyl)] zirconium dichloride.

  Dimethylsilylene bis [1,1 ′-(2-furylcyclopentadienyl)] zirconium dichloride, dimethylsilylene bis [1,1 ′-{2- (2-furyl) -4,5-dimethyl-cyclopentadienyl }] Zirconium dichloride, dimethylsilylene bis [1,1 ′-{2- (2- (5-trimethylsilyl) furyl) -4,5-dimethyl-cyclopentadienyl} zirconium dichloride, dimethylsilylene bis [1,1 '-{2- (2-furyl) indenyl} zirconium dichloride, dimethylsilylene bis [1,1 ′-{2- (2-furyl) -4-phenyl-indenyl}] zirconium dichloride, dimethylsilylene bis [1,1 1 ′-{2- (2- (5-methyl) furyl) -4-phenyl-indenyl} zirconium dicloro Dimethylsilylene bis [1,1 ′-{2- (2- (5-methyl) furyl) -4- (4-isopropyl) phenyl-indenyl} zirconium dichloride, isopropylidene (cyclopentadienyl) (9) -Fluorenyl) zirconium dichloride, isopropylidene (cyclopentadienyl) [9- (2,7-t-butyl) fluorenyl] zirconium dichloride, diphenylmethylene (cyclopentadienyl) [9- (2,7-t-butyl ) Fluorenyl] zirconium dichloride, diphenylmethylene (cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl) [9- (2, 7-t-butyl) fluorenyl] zirconium dichloride, dimethylsilylene ( Cyclopen Dienyl) (9-fluorenyl) zirconium dichloride, diphenylsilylene (cyclopentadienyl) [9- (2, 7-t-butyl) fluorenyl] zirconium dichloride.

Compounds of the general formula (III) (t-butylamide) (tetramethyl-η ⁵ -cyclopentadienyl) -1,2-ethanediylzirconium dichloride, (methylamide)-(tetramethyl-− ⁵ -cyclopentadienyl) -1,2-ethanediyl-zirconium dichloride, (ethylamide) (tetramethyl-η ⁵ -cyclopentadienyl)-methylenezirconium dichloride, (t-butylamido) dimethyl- (tetramethyl-η ⁵ -cyclopentadienyl) silane Zirconium dichloride, (t-butylamido) dimethyl (tetramethyl-η ⁵ -cyclopentadienyl) silane zirconium dibenzyl, (benzylamide) dimethyl (tetramethyl-η ⁵ -cyclopentadienyl) silane zirconium dichloride, (phenyl Ruphosphide) dimethyl (tetramethyl-− ⁵ -cyclopentadienyl) silane zirconium dibenzyl.

Compounds of the general formula (IV) (Cyclopentadienyl) (phenoxy) zirconium dichloride, (2,3-dimethylcyclopentadienyl) (phenoxy) zirconium dichloride, (pentamethylcyclopentadienyl) (phenoxy) zirconium dichloride, (Cyclopentadienyl) (2,6-di-t-butylphenoxy) zirconium dichloride, (pentamethylcyclopentadienyl) (2,6-di-i-propylphenoxy) zirconium dichloride.

Compounds of the general formula (V) (cyclopentadienyl) zirconium trichloride, (2,3-dimethylcyclopentadienyl) zirconium trichloride, (pentamethylcyclopentadienyl) zirconium trichloride, (cyclopentadienyl) Zirconium triisopropoxide, (pentamethylcyclopentadienyl) zirconium triisopropoxide.

Compounds of the general formula (VI) Ethylenebis (7,7′-indenyl) zirconium dichloride, dimethylsilylene bis [7,7 ′-(1-methyl-3-phenylindenyl) zirconium dichloride, dimethylsilylene bis [7,7 7 ′-{1-methyl-4- (1-naphthyl) indenyl} zirconium dichloride, dimethylsilylene bis [7,7 ′-(1-ethyl-3-phenylindenyl) zirconium dichloride, dimethylsilylene bis [7 7 '-{1-isopropyl-3- (4-chlorophenyl) indenyl} zirconium dichloride.

In addition, the compound which substituted the silylene group of the compound of these specific examples to the germylene group is illustrated as a suitable compound.
As specific examples of metallocene compounds, JP-A-7-188335 and Journal of American Chemical Society, 1996, Vol. 118, p. 2291. Transition metal compounds having a ligand containing one or more elements other than carbon in the 5- or 6-membered ring disclosed in the above can also be used.
Moreover, as an example of the metallocene compound which has a heterocyclic hydrocarbon group as a substituent, it is disclosed by patent 3674509.

  In the present invention, among the metallocene compounds, the compounds of the general formula (II), the compounds of the general formula (III) and the compounds of the general formula (VI) are more preferably used, and among them, the compounds of the general formula (II) are preferable .

Furthermore, these components (A) can be used as a mixture of 2 or more types. Moreover, it can also be used together in combination with the metallocene compound mentioned above.
Among the compounds of the general formula (II), preferred are the compounds represented by the general formula (2).

In the general formula (2), M is Ti, Zr or Hf;
R ^{11 to} R ¹⁶ and R ^{17 to} R ²² are the same or different and each is a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 10 carbon atoms, or 6 to 20 carbon atoms An alkyl group substituted by an aryl group, an alkoxy group having 1 to 10 carbon atoms, a silyl group having a hydrocarbon group having 1 to 6 carbon atoms, or a silyl group having a hydrocarbon group having 1 to 6 carbon atoms group, ^{-NR 30} ₂ group, ^{-SR 30} group, an -OSiR ³⁰ ₃ group or ^{-PR 30} ₂ radical ^{(R 30} represents a halogen atom, an alkyl group having 1 to 10 carbon atoms, aryl having 6 to 20 carbon atoms And R ^{11 to} R ¹⁶ and R ^{17 to} R ²² may combine with the atoms connecting them together to form one or more aromatic rings or aliphatic rings. ,;
Y is Si or C;

R ²³ and R ²⁴ are the same or different and each is a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, a fluoroalkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or 6 to 6 carbon atoms 20 aryl groups, fluoroaryl groups having 6 to 10 carbon atoms, aryloxy groups having 6 to 10 carbon atoms, alkenyl groups having 2 to 10 carbon atoms, arylalkyl groups having 7 to 40 carbon atoms, 7 to 40 carbon atoms An alkylaryl group, an alkenylaryl group having 8 to 40 carbon atoms, and R ²³ and R ²⁴ are not simultaneously a hydrogen atom, and R ²³ and R ²⁴ together with the atoms connecting them together are one or more May form a ring;
X ³ and X ⁴ are the same or different and each is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aryloxy having 6 to 10 carbon atoms Group, alkenyl group having 2 to 10 carbon atoms, arylalkyl group having 7 to 40 carbon atoms, alkylaryl group having 7 to 40 carbon atoms, alkenyl aryl group having 8 to 40 carbon atoms, hydrocarbon group having 1 to 6 carbon atoms C 1 -C 20 alkyl group substituted by a silyl group having C 1, C 1 -C 10 amino group, OH group, halogen atom or neutral ligand capable of coordination, and X ³ and X ⁴ are , Together with the atoms connecting them, may form one ring.

Furthermore, ^{R 13, R 19} in the general formula (2) is preferably a substituent represented by the following general formula (3).

In the general formula (3), R ^{25 to} R ²⁹ are the same or different and each is a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 10 carbon atoms, 6 to 20 carbon atoms C 1-20 substituted with a silyl group having an aryl group, an alkoxy group having 1 to 10 carbon atoms, a silyl group having a hydrocarbon group having 1 to 6 carbon atoms, a silyl group having a hydrocarbon group having 1 to 6 carbon atoms alkyl group, ^{-NR 30} ₂ group, ^{-SR 30} group, an -OSiR ³⁰ ₃ group or ^{-PR 30} ₂ ^{radical, R 30} represents a halogen atom, an alkyl group having 1 to 10 carbon atoms, 6 to 20 carbon atoms An aryl group may form one or more aromatic rings or aliphatic rings together with the atoms connecting adjacent substituents to one another.

  In the general formula (2), M is Ti, Zr or Hf, preferably Zr or Hf, particularly preferably Hf.

Specifically, in the general formula (2), as X ³ and X ⁴ , a chlorine atom, a bromine atom, an iodine atom, a fluorine atom, a methyl group, an ethyl group, a propyl group, an n-butyl group, an i-butyl group, A phenyl group, a benzyl group, a dimethylamino group, a diethylamino group or a trimethylsilyl group etc. can be mentioned.
Among these, a chlorine atom, a methyl group, an i-butyl group, a phenyl group, a benzyl group and a trimethylsilyl group are preferable, and a chlorine atom, a methyl group, an i-butyl group, a benzyl group and a trimethylsilyl group are more preferable. .

In addition, X ³ and X ⁴ are neutral ligands that can be coordinated, and specifically, as an atomic group forming one ring together with the atoms connecting them, 1,3-butadiene 1,4-Diphenyl-1,3-butadiene, 3-methyl-1,3-pentadiene, 1,4-dibenzyl-1,3-butadiene, 2,4-hexadiene, 1,3-pentadiene, 1,4 -Ditolyl-1,3-butadiene, 1,4-bis (trimethylsilyl) -1,3-butadiene and the like can be mentioned.

In the general formula ^{(2), R} 11 ~R ¹⁶ and ^R 17 ^{to R 22} is preferably a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 10 carbon atoms, 6 to 10 carbon atoms An aryl group, a silyl group having a hydrocarbon group having 1 to 6 carbon atoms, an alkyl group having 1 to 20 carbon atoms substituted with a silyl group having a hydrocarbon group having 1 to 6 carbon atoms, and more preferably a hydrogen atom An alkyl group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 10 carbon atoms, and an aryl group having 6 to 10 carbon atoms.

  In the general formula (2), Y is preferably a carbon atom from the viewpoint of the number of unsaturated bonds of the produced ethylene / α-olefin copolymer.

In the general formula (2), Preferred ^{-R 30} group, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms.
In the general formula (2), preferable ^{-NR 30} ₂ group, can be exemplified dimethylamino group, diethylamino group, a diisopropyl amino group.

Specific examples of the —SR ³⁰ group in the general formula (2) include a methylsulfanyl group, an ethylsulfanyl group, an isopropylsulfanyl group, and a phenylsulfanyl group.

In the general formula (2), specifically as -OSiR ³⁰ ₃ group, trimethylsiloxy group, triethyl siloxane Shiki group, triisopropylsiloxy group, triphenylsiloxy group, and the like tert- butyl (dimethyl) siloxy group it can.

In the general formula (2), specifically as a -PR ³⁰ ₂ radical can be exemplified dimethylphosphino group, diethylphosphino group, diisopropylphosphino group, di-butyl phosphino group, and diphenylphosphino group.

In the general formula ^{(2), R 23, R} 24 is preferably an alkyl group having 1 to 10 carbon atoms, fluoroalkyl group having 1 to 10 carbon atoms, an aryl group having 7 to 10 carbon atoms, fluoroaryl group, carbon atoms It is an alkenyl group of 2 to 10, an arylalkyl group of 7 to 40 carbon atoms, an alkylaryl group of 7 to 40 carbon atoms, an alkenyl aryl group of 8 to 40 carbon atoms, and more preferably an alkyl of 1 to 10 carbon atoms A group, an aryl group having 7 to 10 carbon atoms, and an alkenyl group having 2 to 10 carbon atoms. In addition, preferably, the sum of carbon numbers contained in R ²³ and R ²⁴ is 3 or more.
R ²³ and R ²⁴ together with the linking atom (Y) preferably form one or more rings, more preferably form a 4- or 5-membered ring.

Hereinafter, the specific example of each functional group which may be contained in General formula (2) is shown.
Specific examples of the alkyl group having 1 to 10 carbon atoms include methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl, n-pentyl, n-hexyl and cyclo Propyl, cyclopentyl, cyclohexyl, n-heptyl, n-octyl, n-decyl and the like can be mentioned.

The halogen-containing alkyl group having 1 to 10 carbon atoms is one in which a hydrogen atom on the skeleton of the alkyl group having 1 to 10 carbon atoms is substituted with a halogen. As a halogen atom of a C1-C10 halogenated alkyl group, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are mentioned.
Specific examples of the halogenated alkyl group having 1 to 10 carbon atoms include fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, bromomethyl, dibromomethyl, tribromomethyl, iodomethyl, 2, 2, 2-trifluoroethyl, 2,2,1,1-tetrafluoroethyl, pentafluoroethyl, pentachloroethyl, pentafluoropropyl, nonafluorobutyl, 5-chloropentyl, 5,5,5-trichloropentyl, 5- There may be mentioned fluoropentyl, 5,5,5-trifluoropentyl, 6-chlorohexyl, 6,6,6-trichlorohexyl, 6-fluorohexyl, 6,6,6-trifluorohexyl.

  Specific examples of the aryl group having 6 to 20 carbon atoms include phenyl, 1-naphthyl, 2-naphthyl, acenaphthyl, phenanthryl, anthryl and the like.

A C1-C10 fluoroalkyl group is what the fluorine atom was substituted by the hydrogen atom on frame | skeleton of a C1-C10 alkyl group.
Specific examples thereof include fluoromethyl, difluoromethyl, trifluoromethyl, 2,2,2-trifluoroethyl, 2,2,1,1-tetrafluoroethyl, pentafluoroethyl, pentafluoropropyl, 5-fluoropentyl, Mention may be made of 5,5,5-trifluoropentyl, 6-fluorohexyl, 6,6,6-trifluorohexyl.

  Specific examples of the alkoxy group having 1 to 10 carbon atoms include methoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, i-butoxy, s-butoxy, t-butoxy, n-pentoxy, n-hexoxy and cyclo Propoxy, cyclopentoxy, cyclohexoxy, n-octoxy, n-deoxy and the like can be mentioned.

  The fluoroaryl group having 6 to 10 carbon atoms is one in which a hydrogen atom on the skeleton of the aryl group having 6 to 10 carbon atoms is substituted with a fluorine atom. Specific examples thereof include pentafluorophenyl, 2-fluorophenyl, 3-fluorophenyl, 4-fluorophenyl, di (trifluoromethyl) phenyl, pentafluoroethylphenyl, nonafluoro-t-butylphenyl, 1-perfluoronaphthyl, 2-perfluoronaphthyl etc. can be mentioned.

  The C 6-10 aryloxy group may be substituted with a C 1-4 hydrocarbon group, and specific examples thereof include phenoxy, trimethylphenoxy, dimethylphenoxy, ethylphenoxy, t-butylphenoxy, 1-naphthoxy, 2-naphthoxy etc. can be mentioned.

  As a specific example of a C2-C10 alkenyl group, vinyl, 1-propenyl, 2-propenyl, 3-butenyl, 5-hexenyl, 7-octenyl etc. can be mentioned.

  Specific examples of the arylalkyl group having 7 to 40 carbon atoms include benzyl, phenylethyl, (methylphenyl) methyl, (tert-butylphenyl) methyl and the like.

  Specific examples of the alkylaryl group having 7 to 40 carbon atoms include tolyl, dimethylphenyl, ethylphenyl, trimethylphenyl, t-butylphenyl and the like.

  Specific examples of the alkenylaryl group having 8 to 40 carbon atoms include vinylphenyl and (2-propenyl) phenyl group.

  Specifically, examples of the C1-C20 alkyl group substituted by a silyl group having a C1-C6 hydrocarbon group include a trimethylsilylmethyl group, a triethylsilylmethyl group and a triphenylsilylmethyl group. Can.

  Specific examples of the amino group having 1 to 10 carbon atoms include dimethylamino, diethylamino and diisopropylamino.

  As a silyl group which has a C1-C6 hydrocarbon group, a trimethylsilyl group, a triethyl silyl group, a tert- butyl (dimethyl) silyl group, a triphenyl silyl group etc. can be mentioned specifically ,.

(Specific examples of metallocene compounds)
Specific examples of the metallocene compound of the present invention represented by the general formula (2) are shown below. These are representative examples.

Isopropylidene Bridged Metallocene Compound:
Isopropylidenebis (4-phenyl-1-indenyl) dimethylhafnium, isopropylidenebis (4- (3-methylphenyl) -1-indenyl) dimethylhafnium, isopropylidenebis (4- (3-isopropylphenyl) -1-) Indenyl) dimethylhafnium, isopropylidenebis (4- (3-tert-butylphenyl) -1-indenyl) dimethylhafnium, isopropylidenebis (4- (4-methylphenyl) -1-indenyl) dimethylhafnium, isopropylidenebis (4- (4-isopropylphenyl) -1-indenyl) dimethylhafnium, isopropylidenebis (4- (4-tert-butylphenyl) -1-indenyl) dimethylhafnium, isopropylidenebis (4- (4-trifluoromethane) Rulphenyl) -1-indenyl) dimethylhafnium, isopropylidenebis (4- (4-methoxyphenyl) -1-indenyl) dimethylhafnium, isopropylidenebis (4- (4-isopropoxyphenyl) -1-indenyl) dimethylhafnium , Isopropylidenebis (4- (4-trimethylsilylphenyl) -1-indenyl) dimethylhafnium, isopropylidenebis (4- (4-fluorophenyl) -1-indenyl) dimethylhafnium, isopropylidenebis (4- (4- (4-fluorophenyl)) Chlorophenyl) -1-indenyl) dimethylhafnium, isopropylidenebis (4- (4-bromophenyl) -1-indenyl) dimethylhafnium, isopropylidenebis (4- (2-methylphenyl) -1-indenyl) dimethylha Sodium, isopropylidenebis (4- (2-ethylphenyl) -1-indenyl) dimethylhafnium, isopropylidenebis (4- (3,5-dimethylphenyl) -1-indenyl) dimethylhafnium, isopropylidenebis (4- (4) (3,5-diisopropylphenyl) -1-indenyl) dimethylhafnium, isopropylidenebis (4- (3,5-di-tert-butylphenyl) -1-indenyl) dimethylhafnium, isopropylidenebis (4- (3 5-Dimethoxyphenyl) -1-indenyl) dimethylhafnium, isopropylidenebis (4- (3,5-ditrimethylsilylphenyl) -1-indenyl) dimethylhafnium,
Isopropylidenebis (4- (3,5-ditrifluoromethylphenyl) -1-indenyl) dimethylhafnium, isopropylidenebis (4- (2,3-dimethylphenyl) -1-indenyl) dimethylhafnium, isopropylidenebis ( 4- (2,5-dimethylphenyl) -1-indenyl) dimethylhafnium, isopropylidenebis (4- (2,6-dimethylphenyl) -1-indenyl) dimethylhafnium, isopropylidenebis (4- (2,3 , 5,6-Tetramethylphenyl) -1-indenyl) dimethylhafnium, isopropylidenebis (4- (2,3,4,5,6-pentamethylphenyl) -1-indenyl) dimethylhafnium, isopropylidenebis ( 4- (4-tert-butyl-2-methyl-phenyl)- -Indenyl) dimethylhafnium, isopropylidenebis (4-biphenylyl 1-indenyl) dimethylhafnium, isopropylidenebis (4- (2,6-dimethylbiphenylyl) -1-indenyl) dimethylhafnium, isopropylidenebis (4- ( 2 ′, 6′-Dimethylbiphenylyl) -1-indenyl) dimethylhafnium, isopropylidenebis (4- (1-naphthyl) -1-indenyl) dimethylhafnium, isopropylidenebis (4- (2-naphthyl) -1 -Indenyl) dimethylhafnium, isopropylidenebis (4-phenanthryl-1-indenyl) dimethylhafnium

Dimethylsilylene bridged metallocene compound:
Dimethylsilylenebis (4-phenyl-1-indenyl) dimethylhafnium, dimethylsilylenebis (4- (3-methylphenyl) -1-indenyl) dimethylhafnium, dimethylsilylenebis (4- (3-isopropylphenyl) -1-) Indenyl) dimethylhafnium, dimethylsilylene bis (4- (3-tert-butylphenyl) -1-indenyl) dimethylhafnium, dimethylsilylene bis (4- (4-methylphenyl) -1-indenyl) dimethylhafnium, dimethylsilylene bis (4- (4-isopropylphenyl) -1-indenyl) dimethylhafnium, dimethylsilylene bis (4- (4-tert-butylphenyl) -1-indenyl) dimethylhafnium, dimethylsilylene bis (4- (4-trifluoromethane) Ruffyl) -1-indenyl) dimethylhafnium, dimethylsilylene bis (4- (4-methoxyphenyl) -1-indenyl) dimethylhafnium, dimethylsilylene bis (4- (4-isopropoxyphenyl) -1-indenyl) dimethylhafnium Dimethylsilylene bis (4- (4-trimethylsilylphenyl) -1-indenyl) dimethylhafnium, dimethylsilylene bis (4- (4-fluorophenyl) -1-indenyl) dimethylhafnium, dimethylsilylene bis (4- (4- (4-fluorophenyl)) Chlorophenyl) -1-indenyl) dimethylhafnium, dimethylsilylene bis (4- (4-bromophenyl) -1-indenyl) dimethylhafnium, dimethylsilylene bis (4- (2-methylphenyl) -1-indenyl) dimethylha Lithium, dimethylsilylene bis (4- (2-ethylphenyl) -1-indenyl) dimethylhafnium, dimethylsilylene bis (4- (3,5-dimethylphenyl) -1-indenyl) dimethylhafnium, dimethylsilylene bis (4- (3,5-diisopropylphenyl) -1-indenyl) dimethylhafnium, dimethylsilylene bis (4- (3,5-di-tert-butylphenyl) -1-indenyl) dimethylhafnium, dimethylsilylene bis (4- (3 5,5-Dimethoxyphenyl) -1-indenyl) dimethylhafnium, dimethylsilylene bis (4- (3,5-ditrimethylsilylphenyl) -1-indenyl) dimethylhafnium, dimethylsilylene bis (4- (3,5-ditrifluoro) Methylphenyl) -1-indenyl ) Dimethylhafnium, Dimethylsilylenebis (4- (2,3-dimethylphenyl) -1-indenyl) dimethylhafnium, Dimethylsilylenebis (4- (2,5-dimethylphenyl) -1-indenyl) dimethylhafnium, Dimethylsilylene Bis (4- (2,6-dimethylphenyl) -1-indenyl) dimethylhafnium, dimethylsilylene bis (4- (2,3,5,6-tetramethylphenyl) -1-indenyl) dimethylhafnium, dimethylsilylene bis (4- (2,3,4,5,6-pentamethylphenyl) -1-indenyl) dimethylhafnium, dimethylsilylene bis (4- (4-tert-butyl-2-methyl-phenyl) -1-indenyl) Dimethylhafnium, dimethylsilylene bis (4-biphenylyl-1-i Denyl) dimethylhafnium, dimethylsilylene bis (4- (2,6-dimethylbiphenylyl) -1-indenyl) dimethylhafnium, dimethylsilylene bis (4- (2 ′, 6′-dimethylbiphenylyl) -1-indenyl) Dimethyl hafnium, dimethyl silylene bis (4- (1-naphthyl) -1-indenyl) dimethyl hafnium, dimethyl silylene bis (4- (2-naphthyl) -1-indenyl) dimethyl hafnium, dimethyl silylene bis (4-phenanthryl-1 -Indenyl) dimethyl hafnium,

In the exemplified metallocene compounds, M is a compound replacing titanium and zirconium instead of hafnium, and X ³ and X ⁴ are a methyl group instead of one or both of a chlorine atom, a bromine atom, iodine Compounds substituted for atoms, phenyl group, benzyl group, dimethylamino group, diethylamino group, trimethylsilylmethyl group and the like can also be exemplified.

(2) Component (B)
The component (B) is a compound which reacts with the component (A) to form an ion pair, or an ion exchange layered silicate. Examples of the compound which forms an ion pair by reacting with the component (A) include organic aluminum oxy compounds, boron compounds and zinc compounds, preferably organic aluminum oxy compounds or boron compounds, more preferably boron compounds. It is. These components (B) may be used alone or in combination of two or more.

(I) Organoaluminum oxy compound The organoaluminum oxy compound which is one of the component (B) has an Al-O-Al bond in the molecule, and the number of bonds is usually 1 to 100, preferably 1 to 50. Range. Such organoaluminum oxy compounds are usually obtained by reacting an organoaluminum compound with water or an aromatic carboxylic acid.
The reaction of the organoaluminum with water is usually carried out in an inert hydrocarbon (solvent). As the inert hydrocarbon, aliphatic hydrocarbons such as pentane, hexane, heptane, cyclohexane, methylcyclohexane, benzene, toluene, xylene and the like, alicyclic hydrocarbons and aromatic hydrocarbons can be used, but aliphatic hydrocarbons or It is preferred to use aromatic hydrocarbons.

As the organoaluminum compound used for the preparation of the organoaluminum oxy compound, any compounds represented by the following general formula (A) can be used, but preferably trialkylaluminum is used.
^{_{R a t AlX a 3-t}} ··· ( A)
(Wherein, R ^a represents a hydrocarbon group such as an alkyl group having 1 to 18 carbon atoms, preferably 1 to 12 carbon atoms, an alkenyl group, an aryl group or an aralkyl group, and X ^a represents a hydrogen atom or a halogen atom , T represents an integer of 1 ≦ t ≦ 3)
The alkyl group of trialkylaluminum may be any of methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, pentyl group, hexyl group, octyl group, decyl group, dodecyl group, etc., preferably It is a methyl group or an isobutyl group, more preferably a methyl group.
The organoaluminum compounds may be used as a mixture of two or more.

The reaction ratio of water to the organoaluminum compound (water / Al molar ratio) is preferably 0.25 / 1 to 1.2 / 1, especially 0.5 / 1 to 1/1, and the reaction temperature is usually It is in the range of -70 to 100 ° C, preferably -20 to 20 ° C. The reaction time is usually in the range of 5 minutes to 24 hours, preferably 10 minutes to 5 hours. As water required for the reaction, not only simple water but also crystal water contained in copper sulfate hydrate, aluminum sulfate hydrate and the like, and components capable of producing water in the reaction system can also be used.
Among the above organoaluminum oxy compounds, those obtained by reacting alkylaluminum and water are usually called aluminoxanes, and in particular methylaluminoxanes (including those substantially consisting of methylaluminoxane (MAO)) Is preferred as the organoaluminum oxy compound.
Of course, two or more of the above-described organoaluminum oxy compounds can be used in combination as the organoaluminum oxy compound, and a solution in which the organoaluminum oxy compound is dissolved or dispersed in the above-mentioned inert hydrocarbon solvent. You may use what you did.

  Among the organoaluminum oxy compounds, those represented by the following general formula (I) can also be exemplified.

The compound represented by the general formula (I) comprises 10: 1 of one kind of trialkylaluminum or two or more kinds of trialkylaluminums and an alkylboronic acid represented by the general formula: R ^c B (OH) ₂ It can be obtained by the reaction of ̃1: 1 (molar ratio). In the general formula, R ^c represents a hydrocarbon group having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms.

(Ii) Boron Compound Examples of the boron compound which is one of the components (B) include boron compounds such as borane compounds and borate compounds.
Specific examples of the borane compound include triphenylborane, tri (o-tolyl) borane, tri (p-tolyl) borane, tri (m-tolyl) borane, tri (o-fluorophenyl) borane and tris (p-). Fluorophenyl) borane, tris (m-fluorophenyl) borane, tris (2,5-difluorophenyl) borane, tris (3,5-difluorophenyl) borane, tris (4-trifluoromethylphenyl) borane, tris (3 5-ditrifluoromethylphenyl) borane, tris (2,6-ditrifluoromethylphenyl) borane, tris (pentafluorophenyl) borane, tris (perfluoronaphthyl) borane, tris (perfluorobiphenylyl) borane, tris ( Perfluoroanthryl) Borane, Tris (Purf Oro binaphthyl) borane, and the like.
Among these, tris (3,5-ditrifluoromethylphenyl) borane, tris (2,6-ditrifluoromethylphenyl) borane, tris (pentafluorophenyl) borane, tris (perfluoronaphthyl) borane, tris (perfluoro) Biphenylyl) borane, tris (perfluoroanthryl) borane, tris (perfluoro binaphthyl) borane is more preferable, and tris (2, 6-ditrifluoromethylphenyl) borane, tris (pentafluorophenyl) borane, tris is more preferable. (Perfluoronaphthyl) borane and tris (perfluorobiphenylyl) borane are preferred.

Further, when the borate compound is specifically represented, the first example is a compound represented by the following general formula (c).
^{[L 1 -H] + [BR} d R e X b X c] - ··· ( c)
In formula (III), L ¹ is a neutral Lewis base, H is a hydrogen atom, and [L ¹ -H] is a Bronsted acid such as ammonium, anilinium, phosphonium and the like. Examples of ammonium include trialkyl ammonium such as trimethyl ammonium, triethyl ammonium, tripropyl ammonium, tributyl ammonium, trialkyl substituted ammonium such as tri (n-butyl) ammonium, and dialkyl ammonium such as di (n-propyl) ammonium and dicyclohexyl ammonium.
Further, as anilinium, N, N-dialkylanilinium such as N, N-dimethylanilinium, N, N-diethylanilinium, N, N-2,4,6-pentamethylanilinium can be exemplified.
Furthermore, examples of phosphonium include triarylphosphonium such as triphenylphosphonium, tributylphosphonium, tri (methylphenyl) phosphonium, tri (dimethylphenyl) phosphonium and the like, and trialkylphosphonium.

Further, in the formula (c), R ^d and R ^e are the same or different aromatic or substituted aromatic hydrocarbon groups containing 6 to 20, preferably 6 to 16 carbon atoms, which are linked to each other by a crosslinking group The substituent of the substituted aromatic hydrocarbon group is preferably an alkyl group represented by a methyl group, an ethyl group, a propyl group, an isopropyl group or the like, or a halogen such as fluorine, chlorine, bromine or iodine.
Furthermore, X ^b and X ^c are a hydride group, a halogen atom, a hydrocarbon group containing 1 to 20 carbon atoms, a substituted carbon containing 1 to 20 carbon atoms in which one or more hydrogen atoms are substituted by a halogen atom It is a hydrogen group.

  Specific examples of the compound represented by the above general formula (c) include tributylammonium tetra (pentafluorophenyl) borate, tributylammonium tetra (2,6-ditrifluoromethylphenyl) borate, tributylammonium tetra (3,5-) Ditrifluoromethylphenyl) borate, tributylammonium tetra (2,6-difluorophenyl) borate, tributylammonium tetra (perfluoronaphthyl) borate, dimethylanilinium tetra (pentafluorophenyl) borate, dimethylanilinium tetra (2,6-) Ditrifluoromethylphenyl) borate, dimethylanilinium tetra (3,5-ditrifluoromethylphenyl) borate, dimethylanilinium tetra (2,6-difluoropheny) B) Dimethylanilinium tetra (perfluoronaphthyl) borate, triphenylphosphonium tetra (pentafluorophenyl) borate, triphenylphosphonium tetra (2,6-ditrifluoromethylphenyl) borate, triphenylphosphonium tetra (3,5-) Ditrifluoromethylphenyl) borate, triphenylphosphonium tetra (2,6-difluorophenyl) borate, triphenylphosphonium tetra (perfluoronaphthyl) borate, trimethylammonium tetra (2,6-ditrifluoromethylphenyl) borate, triethylammonium tetrate (Pentafluorophenyl) borate, triethylammonium tetra (2,6-ditrifluoromethylphenyl) borate, triethyl alcohol Monium tetra (perfluoronaphthyl) borate, tripropylammonium tetra (pentafluorophenyl) borate, tripropylammonium tetra (2,6-ditrifluoromethylphenyl) borate, tripropylammonium tetra (perfluoronaphthyl) borate, di (1 -Propyl) ammonium tetra (pentafluorophenyl) borate, dicyclohexyl ammonium tetraphenyl borate and the like can be exemplified.

Among these, tributylammonium tetra (pentafluorophenyl) borate, tributylammonium tetra (2,6-ditrifluoromethylphenyl) borate, tributylammonium tetra (3,5-ditrifluoromethylphenyl) borate, tributylammonium tetra (perfluoro) Naphthyl) borate, dimethylanilinium tetra (pentafluorophenyl) borate, dimethylanilinium tetra (2,6-ditrifluoromethylphenyl) borate, dimethylanilinium tetra (3,5-ditrifluoromethylphenyl) borate, dimethylanilinium Tetra (perfluoronaphthyl) borate is preferred.
Among these, tributylammonium tetra (pentafluorophenyl) borate, tributylammonium tetra (2,6-ditrifluoromethylphenyl) borate, tributylammonium tetra (3,5-ditrifluoromethylphenyl) borate, and dimethylanil are most preferable. Sodium tetra (pentafluorophenyl) borate, dimethylanilinium tetra (2,6-ditrifluoromethylphenyl) borate, dimethylanilinium tetra (3,5-ditrifluoromethylphenyl) borate, dimethylanilinium tetra (perfluoronaphthyl) It is a borate.

In addition, a second example of the borate compound is represented by the following general formula (D).
^{[L 2] + [BR d} R e X b X c] - ··· ( d)
In the formula (D), L ² represents a carbocation, methyl cation, ethyl cation, propyl cation, isopropyl cation, butyl cation, isobutyl cation, tert-butyl cation, pentyl cation, tropinium cation, benzyl cation, trityl cation, sodium A cation, a proton, etc. are mentioned. Further, R ^d , R ^e , X ^b and X ^c are the same as the definition in the general formula (c).

  Specific examples of the above compounds include trityl tetraphenyl borate, trityl tetra (o-tolyl) borate, trityl tetra (p-tolyl) borate, trityl tetra (m-tolyl) borate, trityl tetra (o-fluorophenyl) borate, Trityltetra (p-fluorophenyl) borate, trityltetra (m-fluorophenyl) borate, trityltetra (3,5-difluorophenyl) borate, trityltetra (pentafluorophenyl) borate, trityltetra (2,6-ditrifluoro) Methylphenyl) borate, trityltetra (3,5-ditrifluoromethylphenyl) borate, trityltetra (perfluoronaphthyl) borate, tropinium tetraphenylborate, tropinium tetra (o-tolyl) , Tropinium tetra (p-tolyl) borate, tropinium tetra (m-tolyl) borate, tropinium tetra (o-fluorophenyl) borate, tropinium tetra (p-fluorophenyl) borate, tropinium tetra (m- Fluorophenyl) borate, Tropinium tetra (3,5-difluorophenyl) borate, Tropinium tetra (pentafluorophenyl) borate, Tropinium tetra (2,6-ditrifluoromethylphenyl) borate, Tropinium tetra (3,5 -Ditrifluoromethylphenyl) borate, tropinium tetra (perfluoronaphthyl) borate, sodium tetraphenylborate, sodium tetra (o-tolyl) borate, sodium tetra (p-tolyl) borate, sodium Tra (m-tolyl) borate, sodium tetra (o-fluorophenyl) borate, sodium tetra (p-fluorophenyl) borate, sodium tetra (m-fluorophenyl) borate, sodium tetra (3,5-difluorophenyl) borate, sodium tetra (pentafluoro) Phenyl) borate, sodium tetra (2,6-ditrifluoromethylphenyl) borate, sodium tetra (3,5-ditrifluoromethylphenyl) borate, sodium tetra (perfluoronaphthyl) borate, hydrogen tetraphenyl borate · diethyl ether, hydrogen tetra ( 3,5-Difluorophenyl) borate · 2 diethyl ether, hydrogen tetra (pentafluorophenyl) borate · 2 diethyl ether, hydride Logen tetra (2,6-ditrifluoromethylphenyl) borate · 2 diethyl ether, hydrogen tetra (3,5-ditrifluoromethylphenyl) borate · 2 diethyl ether, hydrogen tetra (perfluoronaphthyl) borate · 2 diethyl ether are exemplified be able to.

Among these, trityltetra (pentafluorophenyl) borate, trityltetra (2,6-ditrifluoromethylphenyl) borate, trityltetra (3,5-ditrifluoromethylphenyl) borate, trityltetra (perfluoronaphthyl) borate, Tropinium tetra (pentafluorophenyl) borate, tropinium tetra (2,6-ditrifluoromethylphenyl) borate, tropinium tetra (3,5-ditrifluoromethylphenyl) borate, tropinium tetra (perfluoronaphthyl) borate, Sodium tetra (pentafluorophenyl) borate, sodium tetra (2,6-ditrifluoromethylphenyl) borate, sodium tetra (3,5-ditrifluoromethylphenyl) borate, sodi Mutetra (perfluoronaphthyl) borate, hydrogen tetra (pentafluorophenyl) borate · 2 diethyl ether, hydrogen tetra (2,6-ditrifluoromethylphenyl) borate · 2 diethyl ether, hydrogen tetra (3,5-ditrifluoromethylphenyl) B) 2 Diethylether and hydrogen tetra (perfluoronaphthyl) borate 2 Diethylether are preferred.
More preferably, among these, trityltetra (pentafluorophenyl) borate, trityltetra (2,6-ditrifluoromethylphenyl) borate, tropinium tetra (pentafluorophenyl) borate, tropinium tetra (2,6-ditrifluoro) Methylphenyl) borate, Sodium tetra (pentafluorophenyl) borate, Sodium tetra (2,6-ditrifluoromethylphenyl) borate, Hydrogen tetra (pentafluorophenyl) borate · 2 diethyl ether, Hydrogen tetra (2,6-ditrifluoromethylphenyl) And 2) borate · 2 diethyl ether and hydrogen tetra (3,5-ditrifluoromethylphenyl) borate · 2 diethyl ether.

  Further, as the component (B), a mixture of the above-mentioned organoaluminum oxy compound and the above-mentioned borane compound or borate compound can also be used. Furthermore, the above borane compounds and borate compounds can be used as a mixture of two or more.

(Iii) Ion exchange layered silicate The ion exchange layered silicate which is the component (B) (hereinafter sometimes simply referred to simply as "silicate") has surfaces constituted by ionic bonds etc. bonded to each other It refers to a silicate compound that has a crystal structure stacked in parallel by force and whose contained ions are exchangeable. Various known silicates are known, and specifically, they are described in Haruo Shiramizu, "Clay Mineralogical Science" Asakura Shoten (1995).
In the present invention, those preferably used as the component (B) belong to the smectite group, and specific examples thereof include montmorillonite, saukonite, beidellite, nontronite, saponite, hectorite, and Stephenite. Among them, montmorillonite is preferable in terms of the activity of the rubber component and the molecular weight.
Most silicates are mainly produced as a main component of clay minerals in nature, so they often contain impurities (such as quartz and cristobalite) other than ion exchange layered silicates and are used in the present invention The smectite family of silicates may contain hybrids.

Ion exchange layered silicate granulation:
The silicate may be used in a dry state or may be used in a liquid slurry state. The shape of the ion exchange layered silicate is not particularly limited, and may be a naturally occurring shape or a shape at the time of artificial synthesis, or the shape may be obtained by operations such as grinding, granulation, classification, etc. Processed ion exchange layered silicate may be used. Among these, the use of granulated silicate is particularly preferable because it gives good polymer particle properties.
The shape processing of the ion exchange layered silicate such as granulation, pulverization and classification may be performed before the acid treatment, or the shape may be processed after the acid treatment.

Acid treatment:
Although the silicate used in the present invention is used after acid treatment, it may be treated by combining other chemical treatments. Other chemical treatments include alkali treatment, salt treatment, organic matter treatment and the like.
Acid treatment of the silicate can change the acid strength of the solid. The acid treatment also has the effect of eluting out part of cations such as Al, Fe, Mg, and Li of the crystal structure, in addition to the effect of removing ion exchange and impurities on the surface.
Examples of the acid used in the acid treatment include hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, acetic acid, oxalic acid, benzoic acid, stearic acid, propionic acid, acrylic acid, maleic acid, fumaric acid and phthalic acid. Two or more of these may be used simultaneously. Among them, inorganic acids are preferable, sulfuric acid, hydrochloric acid and nitric acid are preferable, and sulfuric acid is more preferable.
Moreover, the method of combining acid treatment and salt treatment is particularly preferable, a method of acid treatment after salt treatment, a method of salt treatment after acid treatment, a method of simultaneously treating salt treatment and acid treatment, salt treatment And salt treatment and acid treatment simultaneously.

Composition after acid treatment of silicate:
The acid-treated silicate which is the component (B) according to the present invention has an atomic ratio of Al / Si of 0.01 to 0.29, preferably 0.03 to 0.25, more preferably Is preferably from 0.05 to 0.23 in terms of the activity of the polymerization catalyst and the molecular weight of the olefin polymer.
The Al / Si atomic ratio is an index of the acid treatment strength of the clay portion, and as a method of controlling the Al / Si atomic ratio, control is carried out by adjusting the acid species to be acid treated, acid concentration, acid treatment time, and temperature. can do.
Aluminum and silicon in the silicate are measured by a method of preparing a calibration curve by a method of chemical analysis according to the JIS method and quantifying it by fluorescent X-ray.

(3) Component (D)
In ethylene polymerization, the component (D) shown below can be used as needed.
Component (D) is an organoaluminum compound.
An example of the organoaluminum compound is represented by the following general formula (E).
AlR _a X _3-a (E)
In the general formula, R represents a hydrocarbon group having 1 to 20 carbon atoms, X represents a hydrogen atom, a halogen, an alkoxy group or a siloxy group, and a represents a number greater than 0 and 3 or less.
Specific examples of the organoaluminum compound represented by the general formula (E) include trialkylaluminum such as trimethylaluminum, triethylaluminum, tripropylaluminum, triisobutylaluminum, trihexylaluminum, trioctylaluminum and the like, diethylaluminum monochloride, And halogen- or alkoxy-containing alkylaluminums such as diethylaluminum monomethoxide. Of these, trialkylaluminum is preferred, and most preferred is trihexylaluminum or trioctylaluminum. In addition, two or more of the above organoaluminum compounds may be used in combination.

(4) Preparation Method of Catalyst In the preparation method of the catalyst for olefin polymerization according to the present invention, the contact method of the component (A), the component (B) and the component (D) is not particularly limited. It can be used.

When component (B) is an organoaluminum oxy compound, the molar ratio of component (A) to component (B) is preferably 1: 0.1 to 1: 100,000.
When the component (B) is a boron compound, the molar ratio of the component (A) to the component (B) is preferably in the range of 1: 0.1 to 1: 100.
When component (D) is used, the molar ratio of component (A) to component (D) is preferably in the range of 1: 0.1 to 1: 10,000.

  When Component (B) is a silicate, the preferred amounts of Component (A) and Component (B) used are 0.001 to 10 mmol, more preferably 0, of the metallocene compound of Component (A) per 1 g of Component (B). It is in the range of .001 to 1 mmol. As a usage-amount of a component (C), the molar ratio of Al / metallocene compound is 0.1 or more and 100,000 or less, Preferably it is 1 or more and 10,000 or less. These use ratios show typical examples, and if the catalyst conforms to the object of the present invention, the present invention is limited by the range of the use ratios described above. It must not be.

2. Component (C)
Component (C) is a compound represented by the general formula (1).

[In general formula (1), R ^{1 to} R ¹⁰ are the same or different and each is a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 10 carbon atoms, 6 to 6 carbon atoms 20 carbon atoms substituted by 20 aryl groups, an alkoxy group having 1 to 10 carbon atoms, a silyl group having a hydrocarbon group having 1 to 6 carbon atoms, and a silyl group having a hydrocarbon group having 1 to 6 carbon atoms alkyl group, ^{-NR 30} ₂ group of, ^{-SR 30} groups, a -OSiR ³⁰ ₃ group or ^{-PR 30} ₂ radical (R ³⁰ represents a halogen atom, an alkyl group having 1 to 10 carbon atoms, 6 to 20 carbon atoms And R ^{1 to} R ¹⁰ may be taken together with the atoms linking them by adjacent substituents to form one or more aromatic rings or aliphatic rings;
X ¹ and X ² are the same or different and each is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aryloxy having 6 to 10 carbon atoms Group, alkenyl group having 2 to 10 carbon atoms, arylalkyl group having 7 to 40 carbon atoms, alkylaryl group having 7 to 40 carbon atoms, alkenyl aryl group having 8 to 40 carbon atoms, hydrocarbon group having 1 to 6 carbon atoms C 1 -C 20 alkyl group substituted by a silyl group having C 1, C 1 -C 10 amino group, OH group, halogen atom or neutral ligand capable of coordination, and X ¹ and X ² are , Together with the atoms connecting them, may form one ring. ]
Specific examples of component (C) include bis (cyclopentadienyl) titanium dichloride, bis (cyclopentadienyl) titanium dihydride, bis (cyclopentadienyl) titanium dimethoxide, bis (cyclopentadienyl) titanium Diphenoxide, dimethylbis (cyclopentadienyl) titanium, diphenylbis (cyclopentadienyl) titanium, dibenzylbis (cyclopentadienyl) titanium, dimethylbis (methylcyclopentadienyl) titanium, dimethylbis (ethylcyclopentadiethyl) Enyl) titanium, dimethyl bis (t-butyl cyclopentadienyl) titanium, dimethyl bis (1, 3- dimethyl cyclopentadienyl) titanium and the like. Further, titanium compounds described in JP-A-8-41081 and JP-A-9-27867 can also be used without limitation.

(1) Amount of Component (C) Used The amount of component (C) used can be arbitrarily determined according to the molecular weight and molecular weight distribution of the target ethylene polymer and the amount of hydrogen generated with polymerization. In general, the component (C) has a molar ratio [component (C) / component (A)] relative to the component (A) of 0.001 to 1000, preferably 0.01 to 100, more preferably 0. It is used in the range of 05 to 50.
When the amount of component (C) used is too small, the effect of generating unsaturated bonds is not sufficient, and a polymer of the target structure can not be obtained. On the other hand, when the amount used is large, the amount of unsaturated bonds may not increase due to hydrogenation reaction to the polymer, etc., and the polymerization activity of the olefin polymerization catalyst may be reduced.

(2) Addition of Component (C) Component (C) can be added from any position of the polymerization system including the circulation system. The polymerization system including the circulation system refers to a line for introducing the raw material into the polymerization reactor, a polymerization reactor, and a line for returning the raw material from the polymerization reactor back to the polymerization reactor. In the case of batch polymerization, it can be introduced from the line for introducing the raw materials into the polymerization reactor and from the polymerization reactor.

  The component (C) may be added as a solid, or may be added after being dissolved in an aliphatic hydrocarbon solvent such as hexane, heptane, toluene, xylene or the like or an aromatic hydrocarbon solvent. Moreover, it may be mixed with component (A) and component (B) and added in advance.

3. Polymerization Conditions of Ethylene The present invention is characterized in that the polymerization is carried out in the state where the polymer to be produced is dissolved. The state in which the polymer formed is in a dissolved state refers to a state in which the formed polymer is dissolved in a polymerization solvent or melted by applying a temperature higher than the melting point of the formed polymer. At this time, in the polymerization system, a polymer produced by normal polymerization does not exist as a solid whose shape is maintained.
Each polymerization condition is described below.
(1) Configuration of Monomer Ethylene polymerization in the present invention may be ethylene homopolymerization or ethylene / α-olefin copolymerization, but ethylene / α-olefin copolymerization is preferable.
The α-olefin used as a comonomer is an α-olefin having 3 to 20, preferably 3 to 12 carbon atoms. Specifically, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-heptene, 4-methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1 -Pentene etc. can be mentioned. Among these, propylene, 1-butene, 1-hexene, 1-octene and 1-decene are more preferable.
Specific examples of such ethylene / α-olefin copolymer include ethylene / propylene copolymer, ethylene / propylene / 1-butene terpolymer, ethylene / propylene / 1-hexene terpolymer, ethylene Propylene 1-octene terpolymer etc. are mentioned.
As comonomers other than α-olefin, 1,5-hexadiene, 1,6-heptadiene, 1,7-octadiene, 1,8-nonadiene, 1,9-decadiene, 5-vinyl-2-norbornene, and 5-ethylidene It is also possible to use small amounts of dienes such as -2-norbornene.

(2) Polymerization Method In the present invention, high pressure ion polymerization method and solution polymerization method can be used as the polymerization method.
The high pressure ion polymerization method refers to a polymerization method of obtaining an ethylene-based polymer by applying an ion polymerization catalyst such as a Ziegler catalyst or a metallocene catalyst to a process of high pressure method. When a Ziegler catalyst or a metallocene catalyst is applied, the produced polymer is characterized by being linear although under high pressure.
The solution polymerization method refers to a polymerization method carried out in a state where the polymer is dissolved in a hydrocarbon solvent.

  The polymerization temperature of solution polymerization is usually 50 to 200 ° C., preferably 50 to 170 ° C., more preferably 90 to 170 ° C., and the polymerization pressure is usually 0.1 to 20 MPa, preferably 0.1 to 10 MPa, more preferably It is 1 to 5 MPa.

The polymerization temperature of the high pressure ion polymerization method is usually 120 to 330 ° C., preferably 125 to 300 ° C., more preferably 160 to 280 ° C., still more preferably 180 to 280 ° C., and the polymerization pressure is usually 20 to 200 MPa. Preferably it is 40-150 Mpa, More preferably, it is 50-125 Mpa.
Among these, in order to obtain the ethylene-olefin copolymer which adjusted the unsaturated bond which concerns on this invention, since it is desirable to superpose | polymerize at high temperature, it is preferable to utilize a high voltage | pressure ion polymerization method. "Chapter 4, Matsuura Kazuo and Mikami Naotaka ed., 2001).

The following figure shows the reaction mechanism of unsaturated bond formation in the polymer.
In the upper part of the figure, an α-olefin such as 1-hexene or 1-octene is inserted into the polymer chain (P) in the polymerization reaction, and then the hydrogen of the β position of the complex metal (M) is extracted to obtain Intermediate 1 Indicates that it will occur. In this intermediate 1, the elimination reaction of (a) or (b) from hydrogen can be considered, but due to steric and electronic factors, the hydrogen of (a) is preferentially eliminated to give intermediate 2 It occurs. Furthermore, depending on the insertion position of intermediate 2 to the next monomer, trisubstituted olefin or vinylidene is generated, but the route for vinylidene is sterically to insert the next monomer between complex metal (M) and secondary carbon Is difficult. Therefore, from the intermediate 2, a trisubstituted olefin is preferentially formed through the insertion of the complex metal (M) and the primary carbon.
On the other hand, in the lower side of the figure, it is shown that when the propylene is inserted into the polymer chain (P) during the polymerization reaction and the hydrogen at the β position of the complex metal (M) is subsequently extracted, Intermediate 3 is generated. Also in this intermediate 31, elimination reaction from (a) or (b) is conceivable, but due to steric and electronic factors, the hydrogen in (b) is preferentially eliminated to obtain an intermediate 4 will occur. Furthermore, vinylidene is produced regardless of which of the following monomers is inserted from Intermediate 4 into any of them.

As shown in the following figures, it is considered effective to make the hydrogen abstraction reaction at the β-position frequent in order to increase the unsaturated bond in the polymer. From the viewpoint of frequent occurrence of hydrogen abstraction reaction at the β-position, the polymerization temperature is preferably higher, and it is more preferable to use high-pressure ion polymerization.
However, in the present invention, the mechanism of generation of unsaturated bond such as vinylidene is not limited to the following mechanism.

(3) Other conditions Moreover, even if it adds the component for the purpose of poisoning removal, so-called scavenger, in a polymerization system, it can carry out without any trouble.
In addition, as such a scavenger, organoaluminum compounds such as trimethylaluminum, triethylaluminum, triisobutylaluminum, trihexylaluminum, trioctylaluminum and the like, the organoaluminum oxy compounds, and the organoaluminum compounds modified with alcohols or phenols Organic aluminum compounds, organic zinc compounds such as diethyl zinc and dibutyl zinc, organic magnesium compounds such as diethyl magnesium, dibutyl magnesium and ethyl butyl magnesium, and Grignard compounds such as ethyl magnesium chloride and butyl magnesium chloride are used. Among these, triethylaluminum, triisobutylaluminum, trihexylaluminum and trioctylaluminum are preferable, and triisobutylaluminum, trihexylaluminum and trioctylaluminum are particularly preferable.

  The molecular weight of the formed polymer can be adjusted by changing the polymerization conditions such as the polymerization temperature, the concentration of the olefin monomer, and the molar ratio of the catalyst. Further, molecular weight control can be effectively performed by adding hydrogen or the above-mentioned scavengers as a chain transfer agent to the polymerization reaction system.

  The present invention can be applied to a multistage polymerization system of two or more stages having different polymerization conditions such as hydrogen concentration, amount of monomers, polymerization pressure, polymerization temperature and the like without any problem.

  As the polymerization method, a method of performing continuous polymerization, batch polymerization, or prepolymerization is also applied. Also, the combination of polymerization types is not particularly limited. A solution polymerization two-stage system is also possible, and furthermore, it is also possible to produce with more polymerization stages.

  EXAMPLES Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited by these examples. In addition, the evaluation method and resin which were used by the Example and the comparative example are as follows.

1. Evaluation method of resin physical properties (1) Melt flow rate (MFR):
The MFR of the ethylene / α-olefin copolymer was measured in accordance with JIS-K6922-2: 1997 Appendix (190 ° C., 21.18 N load).
(2) Density:
The density of the ethylene / α-olefin copolymer was measured in accordance with JIS-K6922-2: 1997 Appendix (23 ° C., in the case of low density polyethylene).
(3) Number of unsaturated bonds, number of comonomers:
The number of terminal vinyls, vinylidenes, vinylenes (including cis-vinylenes and trans-vinylenes) and trisubstituted olefins are determined by ¹ H-NMR and ¹³ C-NMR under the following conditions, and the amount of comonomers is Macromolecules, 1995 28, pp. 1739-1749. And Macromolecules, 2005, 38, p 69 88-6996. It calculated | required by the number of objects per 1000 principal chain carbon according to.
Device: Bruker Biospin KK AVANCE III cryo-400 MHz
Solvent: o-Dichlorobenzene / Heavy Bromobenzene = 8/2 Mixed Solution <Sample Amount>
460 mg / 2.3 ml
< ¹³ C-NMR>
・¹ H decoupling, NOE available ・ Number of integration: 256 scan
・ Flip angle: 90 °
・ Pulse interval 20 seconds ・ AQ (take-in time) = 5.45 s, D1 (waiting time) = 14.55 s
< ¹ H-NMR>
・ Number of times of accumulation: 1400 scan
・ Flip angle: 1.03 °
・ AQ (intake time) = 1.8 s, D1 (waiting time) = 0.01 s

2. Preparation of catalyst for olefin polymerization (1) Component (A): Synthesis of metallocene compound Metallocene compound: Synthesis of isopropylidene bis (4-phenyl-1-indenyl) dimethylhafnium

(I) Synthesis of 4-phenyl-indene It synthesize | combined according to the method of Unexamined-Japanese-Patent No. 2008-101034.
(Ii) Synthesis of 2,2-bis (4-phenyl-inden-1-yl) propane In a 100 mL glass reaction vessel, 1.00 g (5.21 mmol) of 4-phenyl-indene, 1,2-dimethoxyethane 10 mL of (DME) and 0.583 g (10.4 mmol) of potassium hydroxide were added, and the mixture was heated to reflux at 90 ° C. for 1 hour. The reaction solution was cooled to 0 ° C., and after adding 0.151 g (2.60 mmol) of acetone, the mixture was heated to reflux at 90 ° C. for 6 hours. The reaction solution was cooled to room temperature, 20 mL of distilled water was added, transferred to a separatory funnel, extracted three times with ethyl acetate, and dried over sodium sulfate. Sodium sulfate is filtered, the solvent is distilled off under reduced pressure, and the obtained crude product is purified by silica gel column chromatography (developing solvent, dichloromethane: petroleum ether = 1: 20) to obtain 2,2-bis 0.45 g of 4-phenyl-inden-1-yl) propane was obtained as a pale yellow solid (yield 41%).
¹ H-NMR (400 MHz, CDCl ₃ ): δ 7.52 (dd, 4 H), 7.44 (t, 4 H), 7.41 to 7.34 (m, 4 H), 7.16 (t, 2 H) , 7.11 (dd, 2H), 6.59 (t, 2H), 3.48 (d, 2H), 1.81 (s, 6H).
(Iii) Synthesis of isopropylidene bis (4-phenyl-1-indenyl) hafnium dichloride In a 200-ml three-necked flask fitted with a rotator and fitted with a three-way cock and a thermometer, 2,2-bis (4-phenyl-indene-1-one). 1.50 g (3.5 mmol) of propane) was added, and 70 ml of toluene and 15 ml of diethyl ether were added and dissolved. The mixture was cooled to -70 ° C in a dry ice-isopropyl alcohol bath, 4.7 ml (7.5 mmol) of n-butyllithium / hexane (1.59 M solution) was added, and the mixture was stirred for 40 minutes. The cooling bath was removed, the temperature was raised to 20 ° C., and after maintaining for 1 hour, the solvent was distilled off. To this, 70 ml of toluene and 3 ml of diethyl ether were added and dissolved, and the mixture was cooled to -70 ° C. Hafnium tetrachloride 1.25 g (3.9 mmol) was added, the cooling bath was immediately removed, and the temperature was gradually raised to room temperature. The steric composition of the obtained complex was racemic: meso = 33: 67 according to 1H NMR. The solvent was distilled off, 60 ml of DME was added, and the mixture was heated and stirred at 60 ° C. for 3 hours. By this operation, the steric composition of the complex became racemic: meso = 93: 7. The supernatant was decanted off, and the precipitate was dissolved in dichloromethane and filtered to remove insolubles. The filtrate is concentrated, and the solid obtained is washed with a small amount of toluene and then dried under reduced pressure to give isopropylidene bis (4-phenyl-1-indenyl) hafnium dichloride as a yellow powdery solid with 100% racemic purity, yield 1. Obtained in 25 g, 53% yield.
¹ H-NMR (400 MHz, CDCl ₃ ): δ 7.78 (d, J = 8.8 Hz, 2 H), 7.57 (dd, J = 8.3 Hz, 4 H), 7.42 (t, J = 7) .1 Hz, 4 H), 7.34 (t, J = 7.3 Hz, 2 H), 7. 26 (d, J = 6.3 Hz, 2 H), 7.13-7.09 (m, 2 H), 6 72 (dd, J = 3.6 Hz, 2 H), 6.18 (d, J = 3.6 Hz, 2 H), 2.41 (s, 6 H).

(Iv) Synthesis of isopropylidene bis (4-phenyl-1-indenyl) dimethylhafnium In a 100 ml branched flask equipped with a rotor, 0.51 g of isopropylidene bis (4-phenyl-1-indenyl) hafnium dichloride (0. 1%) was added. 76 mmol) and 40 ml of toluene were added and dissolved. The mixture was cooled to 0 ° C. with an ice bath, 1.8 ml (5.4 mmol) of methylmagnesium bromide / diethyl ether (3.0 M solution) was added, and the mixture was heated and stirred at 40 ° C. for 11 hours. After 0.47 ml (3.7 mmol) of trimethylsilyl chloride was added at room temperature and stirred for 30 minutes, 10 ml of dioxane was added and stirred for 30 minutes. The insolubles were removed by filtration and the filtrate was concentrated to give a yellow solid. The extract is washed with a small amount of hexane, and the supernatant is removed by decantation and dried under reduced pressure to give a light yellow powdered solid of isopropylidenebis (4-phenyl-1-indenyl) dimethylhafnium, racemic purity 100%, yield 0.32 g, Obtained in 66% yield.
¹ H-NMR (400 MHz, C ₆ D ₆ ): δ 7.69 (dd, J = 8.4 Hz, 4 H), 7. 35 (d, J = 9.0 Hz, 2 H), 7.22 (t, J = 7.6 Hz, 4 H), 7.15-7.09 (m, 4 H), 6.84-6. 80 (m, 4 H), 5.57 (d, J = 3.5 Hz, 2 H), 1 77 (s, 6 H),-0.99 (s, 6 H).

. Metallocene compounds: synthesis of dimethylsilylene bis (4-phenyl-1-indenyl) dimethylhafnium

(I) Synthesis of dimethylbis (4-phenylindene-1-yl) silane This compound was synthesized according to the method described in the literature (Oraganometallics, vol. 13, 1994, pp. 954-963).
(Ii) Synthesis of racemic-dimethylsilylene bis (4-phenyl-1-indenyl) hafnium dichloride 4.90 g (11.1 mmol) of dimethyl bis (4-phenyl inden-1-yl) silane in a 200 ml glass reaction vessel 110 ml of diethyl ether was added and cooled to -70 ° C with a dry ice-heptane bath. Here, 14.0 ml (22.7 mmol) of a 1.62 mol / L n-butyllithium-n-hexane solution was dropped, and the mixture was stirred at room temperature for 3.5 hours. The solvent of the reaction solution was distilled off under reduced pressure, 100 ml of toluene was added, and the mixture was cooled to -70 ° C with a dry ice-heptane bath. Thereto, 3.56 g (11.1 mmol) of hafnium tetrachloride was added. Then, it stirred for 17 hours, gradually returning to room temperature. The formation ratio of racemate to meso form at this time was 55:45.
After adding 200 mL of dichloromethane and filtering through Celite, recrystallization in toluene gave 2.23 g of a racemate of dimethylsilylene bis (4-phenyl-1-indenyl) hafnium dichloride as an orange solid (yield 29). %).
¹ H-NMR (400 MHz, CDCl ₃ ): δ 7.63 (d, 4 H), 7.53 (d, 2 H), 7.42 (t, 4 H), 7.38-7. 31 (m, 4 H) , 7.16 (dd, 2H), 7.01 (d, 2H), 6.10 (d, 2H), 1.18 (s, 6H).

(Iii) Synthesis of racemic-dimethylsilylene bis (4-phenyl-1-indenyl) dimethylhafnium In a 100 ml glass reaction vessel, 1.20 g (1.56 mmol) of dimethylsilylene bis (4-phenyl-1-indenyl) hafnium dichloride 50 mL of toluene was added, and 3.6 mL (10.8 mmol) of a 3.0 mol / L methylmagnesium bromide-diethyl ether solution was added dropwise thereto at room temperature, followed by stirring at 80 ° C. for 1 hour. The reaction solution is cooled to 0 ° C. with an ice bath, and then, 0.98 mL (7.76 mmol) of chlorotrimethylsilane is added, and the mixture is stirred at room temperature for 30 minutes, followed by 2.0 mL (23.4 mmol) of 1,4-dioxane. In addition, it was further stirred at room temperature for 30 minutes. The suspension was filtered through celite and the solvent was evaporated under reduced pressure. The resulting yellow solid is suspended in 10 mL of hexane, filtered through a glass frit, and the solid is further washed with 5 mL of hexane three times to obtain the racemate of dimethylsilylene bis (4-phenyl-1-indenyl) dimethylhafnium. 837 mg was obtained as a yellow solid (yield 85%).
¹ H-NMR (400 MHz, C ₆ D ₆ ): δ 7.70 (dd, 4 H), 7. 27-7. 18 (m, 8 H), 7. 15-7.0 7 (m, 4 H), 6. 90 (dd, 2H), 5.63 (d, 2H), 0.60 (s, 6H), -1.07 (s, 6H).

(2) Production of ethylene / α-olefin copolymer (2-1). Ethylene / Propylene Copolymerization by High-Pressure Ion Polymerization The polymerization reactions of Examples and Comparative Examples shown in Table 1 were carried out in a 5.0 L stainless steel reactor (with a stirrer) which was sufficiently dried and replaced with nitrogen. The The supply of the raw material was continuously performed so that the total amount of the raw material gas was 40 kg / hour while maintaining the ratio of ethylene and propylene shown in Table 1, and the pressure adjustment was maintained at about 80 MPa by the pressure adjustment valve on the discharge side. The polymerization temperature controlled the feed rate of the catalyst so that the internal temperature of the reactor was 217 ° C. Moreover, the tri (n-octyl) aluminum (component (D)) / heptane solution prepared to 30 mg / L as a scavenger was continuously supplied. Since the temperature of the reactor is above the melting point of the polymer, the polymerization reaction proceeded in a melted state.

Metallocene compounds (isopropylidenebis (4-phenyl-1-indenyl) dimethylhafnium, component (A)) and cocatalyst [Me ₂ N (H) C ₆ H ₅ ] [B (C ₆ F ₅ ) ₄ ] ( Component (B) separately prepares a toluene solution (20 to 50 mg / L, 37 to 120 mg / L, respectively) and mixed in piping so that the molar ratio of metallocene compound to cocatalyst is 1: 1.5. While continuously supplying to the polymerization system.
Dimethylbis (cyclopentadienyl) titanium (component (C)) is prepared in advance as a toluene solution (1 to 5 mg / L), and the molar ratio with the metallocene compound (component (A)) is as shown in Table 1. The flow rate was adjusted and continuously supplied.
Table 1 shows the feed ratio of component (C) / component (A), molar ratio of each monomer supplied, polymerization conditions such as polymerization temperature, and MFR of the obtained polymer in each of Examples 1 to 4 and Comparative Example 1. , Density, various olefin contents determined from NMR measurement were described.

(2-2). Ethylene / 1-Hexene Copolymerization by Solution Polymerization The polymerization reactions of the examples and comparative examples shown in Table 2 were carried out according to the following procedure.
1000 ml of toluene and 10 ml of 1-hexene were added to a sufficiently dried 2.4 L stainless steel reactor (with a stirrer) purged with nitrogen, and tri (n-octyl) aluminum (component (D)) / 3 ml of heptane solution (0.1 mmol / ml) was added and the temperature was raised to 100.degree. 0.5 MPa pressure increase with ethylene. Racemic-dimethylsilylene bis (4-phenyl-1-indenyl) dimethylhafnium (component (A)) in toluene solution (0.1 μmol / ml), [Me ₂ N (H) C ₆ H ₅ ] [B (C ₆₎ F ₅ ) ₄ ] (Component (B)) in toluene (0.1 μmol / ml), Dimethylbis (t-butylcyclopentadienyl) titanium (Component (C)) in toluene (0.1 μmol / ml) Were pre-mixed in the amounts described in Table 2 and, 5 minutes after mixing, polymerization was initiated by forcing nitrogen into the reactor. During the polymerization, ethylene was supplied to maintain a partial pressure of 0.5 MPa. After 5 minutes from the initiation of polymerization, ethanol was introduced to terminate the polymerization reaction, and the temperature in the reactor was lowered to 60 ° C., and then the reactor was opened. At this time, the produced polymer was in the state of being dissolved in the solvent toluene, and 1 L of acetone was added to precipitate the polymer and then recovered. The analytical values of the obtained polymer are described in Table 2.
The polymer was dissolved in the solvent at the opening temperature of the reactor (60 ° C.), and the polymer was in the dissolved state at the polymerization temperature (100 ° C.).

[Discussion of Comparative Results of Example and Comparative Example]
As is clear from Table 1, when comparing Examples 1 to 4 with Comparative Example 1 and Examples 5 to 6 with Comparative Examples 2 to 3 as the polymerization results of the same polymerization temperature, the component (C) becomes a polymerization system. It can be seen that feeding increases the amount of unsaturated bonds in the polymer.

  The method for producing an ethylene-based polymer of the present invention makes it possible to efficiently produce a copolymer having an increased amount of unsaturated bonds in the polymer, which is very useful industrially.

Claims (6)

In the polymerization of ethylene by the olefin polymerization catalyst containing the following components (A) and (B), the polymerization is carried out at a polymerization temperature above the melting point of the formed polymer in a melted state of the produced polymer, and the component (C) is added A process for producing an ethylene-based polymer having an unsaturated bond, characterized in that
Component (A) Compound Represented by General Formula (2) Component (B) Organoaluminum Oxy Compound or Boron Compound Component (C) Compound Represented by General Formula (1)

[In general formula (1), R ^{1 to} R ¹⁰ are the same or different and each is a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 10 carbon atoms, 6 to 6 carbon atoms 20 carbon atoms substituted by 20 aryl groups, an alkoxy group having 1 to 10 carbon atoms, a silyl group having a hydrocarbon group having 1 to 6 carbon atoms, and a silyl group having a hydrocarbon group having 1 to 6 carbon atoms alkyl group, ^{-NR 30} ₂ group of, ^{-SR 30} groups, a -OSiR ³⁰ ₃ group or ^{-PR 30} ₂ radical (R ³⁰ represents a halogen atom, an alkyl group having 1 to 10 carbon atoms, 6 to 20 carbon atoms And R ^{1 to} R ¹⁰ may be taken together with the atoms linking them by adjacent substituents to form one or more aromatic rings or aliphatic rings;
X ¹ and X ² are the same or different and each is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aryloxy having 6 to 10 carbon atoms Group, alkenyl group having 2 to 10 carbon atoms, arylalkyl group having 7 to 40 carbon atoms, alkylaryl group having 7 to 40 carbon atoms, alkenyl aryl group having 8 to 40 carbon atoms, hydrocarbon group having 1 to 6 carbon atoms C 1 -C 20 alkyl group substituted by a silyl group having C 1, C 1 -C 10 amino group, OH group, halogen atom or neutral ligand capable of coordination, and X ¹ and X ² are , Together with the atoms connecting them, may form one ring. ]

[In the general formula (2), M is Ti, Zr or Hf;
R ^{11 to} R ¹⁶ and R ^{17 to} R ²² are the same or different and each is a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 10 carbon atoms, or 6 to 20 carbon atoms An alkyl group substituted by an aryl group, an alkoxy group having 1 to 10 carbon atoms, a silyl group having a hydrocarbon group having 1 to 6 carbon atoms, or a silyl group having a hydrocarbon group having 1 to 6 carbon atoms group, ^{-NR 30} ₂ group, ^{-SR 30} group, an -OSiR ³⁰ ₃ group or ^{-PR 30} ₂ radical ^{(R 30} represents a halogen atom, an alkyl group having 1 to 10 carbon atoms, aryl having 6 to 20 carbon atoms And R ^{11 to} R ¹⁶ and R ^{17 to} R ²² may combine with the atoms connecting them together to form one or more aromatic rings or aliphatic rings. ,;
Y is Si or C;
R ²³ and R ²⁴ are the same or different and each is a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, a fluoroalkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or 6 to 6 carbon atoms 20 aryl groups, fluoroaryl groups having 6 to 10 carbon atoms, aryloxy groups having 6 to 10 carbon atoms, alkenyl groups having 2 to 10 carbon atoms, arylalkyl groups having 7 to 40 carbon atoms, 7 to 40 carbon atoms An alkylaryl group, an alkenylaryl group having 8 to 40 carbon atoms, and R ²³ and R ²⁴ are not simultaneously a hydrogen atom, and R ²³ and R ²⁴ together with the atoms connecting them together are one or more May form a ring;
X ³ and X ⁴ are the same or different and each is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aryloxy having 6 to 10 carbon atoms Group, alkenyl group having 2 to 10 carbon atoms, arylalkyl group having 7 to 40 carbon atoms, alkylaryl group having 7 to 40 carbon atoms, alkenyl aryl group having 8 to 40 carbon atoms, hydrocarbon group having 1 to 6 carbon atoms C 1 -C 20 alkyl group substituted by a silyl group having C 1, C 1 -C 10 amino group, OH group, halogen atom or neutral ligand capable of coordination, and X ³ and X ⁴ are , Together with the atoms connecting them, may form one ring. ]   The method for producing an ethylene-based polymer having an unsaturated bond according to claim 1, wherein the ethylene-based polymer is a copolymer of ethylene and an α-olefin. The unsaturated ethylene polymer according to claim 2 , characterized in that at least one α-olefin is selected from propylene, 1-butene, 1-hexene, 1-octene or 1-decene. Production method.   The method for producing an ethylene-based polymer having an unsaturated bond according to any one of claims 1 to 3, wherein the polymerization is carried out in a hydrocarbon solvent at a polymerization temperature of 90 ° C or higher. The method for producing an ethylene-based polymer having an unsaturated bond according to any one of claims 1 to 4 , wherein at least one of R ¹¹ and R ^{17 in} the general formula (2) is hydrogen. The unsaturated bond according to any one of claims 1 to 5 , wherein R ¹³ and R ^{19 in} the general formula (2) are a substituent represented by the following general formula (3) The manufacturing method of the ethylene polymer which has it.

[In general formula (3), R ^{25 to} R ²⁹ are the same or different and each is a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 10 carbon atoms, 6 to 6 carbon atoms 20 carbon atoms substituted by 20 aryl groups, an alkoxy group having 1 to 10 carbon atoms, a silyl group having a hydrocarbon group having 1 to 6 carbon atoms, and a silyl group having a hydrocarbon group having 1 to 6 carbon atoms alkyl group, ^{-NR 30} ₂ group of, ^{-SR 30} groups, a -OSiR ³⁰ ₃ group or ^{-PR 30} ₂ ^{radical, R 30} represents a halogen atom, an alkyl group having 1 to 10 carbon atoms, 6 to 20 carbon atoms The aryl groups may be combined with the atoms linking them together by adjacent substituents to form one or more aromatic or aliphatic rings. ]