JP2002302518A - Cyclic olefin-based polymer and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method and the like for producing a cyclic olefin-based polymer having high transparency, high heat resistance and low water absorp tion. SOLUTION: This method for producing a cyclic olefin-based polymer is to (co)polymerize dicyclopentadien and/or 7, 8-dihydrodicyclopentadiene by using a catalyst system containing half metallocene. The cyclic olefin-based polymer obtained by this method and its hydrogenated product are also claimed.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a transparent conductive film, a liquid crystal display panel member such as a color filter, and a transparent, heat-resistant and low-absorbing material which can be used for a surface protective layer of a solar cell module. It relates to a method for producing an excellent resin.

[0002]

2. Description of the Related Art Conventionally, in the fields of active liquid crystal display members such as color filters and transparent conductive films, and solar cell members such as optoelectronic devices and surface protective sheet layers,
Glass is mainly used as a substrate because of its weather resistance, heat resistance, and optical isotropy. In recent years, in these fields, weight reduction,
High demands have been made such as large size, impact resistance, and freedom of shape.However, glass substrates are difficult to increase in area due to poor moldability, low mechanical strength, high specific gravity, etc. A transparent polymer film substrate is being studied instead of a glass substrate. Known films include polyester (PET) films and polycarbonate (PC) films, both of which have drawbacks such as low heat resistance, high birefringence, and high water absorption. The problem is poor chemical properties. In addition, polyarylate (P
AR) films and polyethersulfone (PES) films have very good heat resistance, but have the problem that they are highly colored and very expensive.

On the other hand, in recent years, polycyclic olefin-based polymers have been used for optical applications due to demands for high transparency, high heat resistance and low water absorption. Examples of such a polymer include a hydrogenated ring-opening polymer of a tetracyclododecene derivative as disclosed in JP-A-63-218726, and a polymer as disclosed in JP-A-7-188396. Copolymer of cyclic olefin and α-olefin, copolymer of norbornene and alkyl norbornene disclosed in US Pat. No. 5,468,819;
A hydrogenated cyclohexadiene polymer disclosed in JP-A-196737 is known. The heat-resistant temperature of the resins (1) and (2) is about 140 to 160 ° C., which does not reach the required properties for the above-mentioned applications. Further, although high heat resistance is expected, the resin itself has to be expensive because the raw material is expensive, and there are far from practical applications of the above-mentioned applications as a substitute for glass.

[0004] Dicyclopentadiene Among the cyclic olefin is a so-called low material obtained from C ₅ fraction, is very inexpensive cyclic olefins. In addition, the polymer and the polymer hydrogenated product have high transparency, high heat resistance, and low water absorption because the side chains are bulky, rigid and non-polar. H. It is known that Schnecko et al. Polymerized dicyclopentadiene using a vanadyl-based catalyst to obtain a polymer having extremely high heat resistance (Angew.
Macromol. Chem. 20, 141 (197
1)). However, since the polymerization activity is low, a large amount of catalyst must be used, and the catalyst itself is harmful, a catalyst system having high activity has been desired.

[0005]

The present inventors have conducted intensive studies on a method for producing a high heat-resistant polymer containing cyclic olefins and, among them, inexpensive raw materials such as dicyclopentadiene and norbornene. It has been found that a cyclic olefin polymer having high transparency, high heat resistance and low water absorption can be obtained by using a metallocene-containing catalyst system.

[0006]

Means for Solving the Problems That is, the present invention provides: The following formula (A)

[0007]

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(Wherein n represents 0 or 1, ¹ R to ⁸ R are the same or different and represent a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms (provided that ¹ R, ² R and ³ R may at least one of R and ⁴ R is to form an unsaturated bond, represented by at least one of ¹ R and ³ R and ² R and ⁴ R may form a ring).) The cyclic olefin compound is represented by the following formula (C)

[0009]

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(Wherein ⁹ R to ¹³ R are the same or different,
Hydrogen atom, 1 or more than 12 carbons in the alkyl groups, represents a substituent selected from aryl groups having 6 to 12 carbon atoms (however, ⁹ R~ ¹³ R adjacent substituents together one or more aliphatic ring Or an aromatic ring may be formed). ¹ X to ³ X are the same or different and represent a substituent selected from a hydrogen atom, a halogen atom, an alkyl group having 1 to 12 carbon atoms and an aryl group having 6 to 12 carbon atoms (provided that such a substituent is nitrogen, phosphorus, oxygen, sulfur, also contain atoms such as silicon Joik Further, the ^{9 R~ 13} at least one of R, represents a binding site bound to the ¹ X to ³ X To form a ring). M represents a Group 4 metal element. Wherein the (co) polymerization is carried out in the presence of a half metallocene-containing catalyst system represented by the following formula (B):

[0011]

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[0012] (In the formula, n represents 0 or ^1, 1 R'~ ⁸
R 'are the same or different, a hydrogen atom or having 1 or more carbon atoms represents the 12 following hydrocarbon group (provided that, ¹ R' and forming at least one unsaturated bond ² R 'and ³ R' and ⁴ R ' And at least one of ¹ R ′ and ³ R ′ and ² R ′ and ⁴ R ′ may form a ring). A method for producing a cyclic olefin polymer containing a repeating unit represented by the formula (1). It is.

The present invention also includes the following inventions. 2. 2. The method according to 1, wherein the half metallocene is dicyclopentadienyl titanium trichloride. 3. A cyclic olefin polymer obtained by the production method according to 1 or 2. 4. 4. The cyclic olefin polymer according to 3, wherein the cyclic olefin polymer is a norbornene-dicyclopentadiene copolymer, an ethylene-dicyclopentadiene copolymer, or an ethylene-7,8-dihydrodicyclopentadiene copolymer. . 5. 4. A hydrogenated cyclic olefin polymer obtained by hydrogenating the unsaturated bond when the cyclic olefin polymer according to 3 has an unsaturated bond. 6. The unsaturated cyclic olefin polymer is ethylene-
6. The hydrogenated product according to 5, which is a dicyclopentadiene copolymer.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION [Form of Monomer] The cyclic olefin compound in the present invention is represented by the following formula (A).

[0015]

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(In the formula, n represents 0 or 1, and ¹ R to ⁸ R are the same or different and represent a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms (provided that ¹ R, ² R and ³ R Any of R and ⁴ R may form an unsaturated bond, and ¹ R and ³ R
And ² at least one of R and ⁴ R may form a ring). ) Specifically ^{1 R~ 8} R hydrocarbon group having 1 to 12 carbon atoms
Examples thereof include a methyl group, an ethyl group, a normal propyl group, an isopropyl group, a normal butyl group, an isobutyl group, a tertiary butyl group, a cyclopentyl group, a cyclohexyl group, a phenyl group, a benzyl group, and a naphthyl group. .

Specific examples of such compounds include, for example, norbornene, 5-methylnorbornene, 5,5-dimethylnorbornene, 5,6-dimethylnorbornene,
-Ethyl norbornene, 5,5-diethylnorbornene, 5,6-diethylnorbornene, 5-ethylidene norbornene, dicyclopentadiene, 6,7-dihydrodicyclopentadiene, tetracyclododecene, 8-methyltetracyclododecene, 8 , 8-Dimethyltetracyclododecene, 8,9-dimethyltetracyclododecene, 8-ethyltetracyclododecene, 8,8-diethyltetracyclododecene, 8,9-diethyltetracyclododecene, 8-ethylidene Tetracyclododecene and the like are exemplified, and norbornene, ethylidene norbornene, dicyclopentadiene, 6,7-dihydrodicyclopentadiene, tetracyclododecene, and ethylidenetetracyclododecene are preferably used. One of these monomers may be used alone, or two or more thereof may be mixed at the beginning or added stepwise during polymerization.

"Form of Polymer" The cyclic olefin polymer of the present invention contains the following formula (B) as a repeating unit.

[0019]

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[0020] (wherein, n represents 0 or ^1, 1 R'~ ⁸
R 'are the same or different, a hydrogen atom or having 1 or more carbon atoms represents the 12 following hydrocarbon group (provided that, ¹ R' and forming at least one unsaturated bond ² R 'and ³ R' and ⁴ R ' And at least one of ¹ R ′ and ³ R ′ and ² R ′ and ⁴ R ′ may form a ring). ) More specifically, ¹ R 'to ^{1 to} 12 hydrocarbon groups
⁸ R The 'may include the same as those exemplified as the hydrocarbon group having 1 to 12 carbon atoms in the ¹ R～ ⁸ R.

The cyclic olefin polymer of the present invention is obtained by polymerizing or copolymerizing the cyclic olefin compound represented by the formula (A) without opening the unsaturated bond at the 2-position. This polymer may be a homopolymer containing only one type of the above formula (A) or a copolymer obtained by copolymerizing two or more types. Ethylene, propylene,
Α-olefins such as butene and 1-hexene, 1,5-
Non-conjugated dienes such as hexadiene, 1,3-butadiene,
Conjugated dienes such as isoprene and 2,3-dimethylbutadiene may be copolymerized.

The molecular weight of such a polymer is, when it is soluble in toluene, 0.1% using toluene as a solvent.
When the reduced viscosity at 30 ° C. of the solution having a concentration of 5 g / dL is 0.05 dL / g or more and 10 d
L / g or less, preferably 0.1 dL / g or more.
dL / g or less is more preferable, and 0.3 dL / g or more and 3d
L / g or less is more preferable. Reduced viscosity of 0.05 dL /
When the amount is not less than g, sufficient mechanical properties of a polymer as a resin are easily obtained, and when it is not more than 10 dL / g, an appropriate solution and melt viscosity are easily obtained in molding. If such a polymer does not dissolve in toluene, the reduced viscosity using a solvent that can be dissolved is used. If there is no solvent to dissolve, it is determined that the polymer has a sufficient molecular weight, and the polymer is included in a preferable range.

[Form of Catalyst System] The half metallocene in the present invention is represented by the following formula (C), wherein cyclopentadiene is one of transition metal elements and pentahapto (hereinafter referred to as η ⁵
) -Type coordinated metal complex.

[0024]

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(Wherein ⁹ R to ¹³ R are the same or different,
Hydrogen atom, 1 or more than 12 carbons in the alkyl groups, represents a substituent selected from aryl groups having 6 to 12 carbon atoms (however, ⁹ R~ ¹³ R adjacent substituents together one or more aliphatic ring Or an aromatic ring may be formed). ¹ X to ³ X are the same or different and represent a substituent selected from a hydrogen atom, a halogen atom, an alkyl group having 1 to 12 carbon atoms and an aryl group having 6 to 12 carbon atoms (provided that such a substituent is nitrogen, phosphorus, oxygen, sulfur, also contain atoms such as silicon Joik Further, the ^{9 R~ 13} at least one of R, represents a binding site bound to the ¹ X to ³ X To form a ring). M represents a Group 4 metal element. ) Where ^{9 R~ 13} R having 1 to 12 alkyl group carbon of the aryl group having 6 to 12 carbon atoms, such as methyl group, ethyl group, normal propyl group, an isopropyl group, normal butyl group, isobutyl Group, tertiary butyl group, cyclopentyl group, cyclohexyl group, phenyl group, benzyl group, naphthyl group, cyclopentadienyl group, methylcyclopentadienyl group, 1,2-dimethylcyclopentadienyl group, 1,3 -Dimethylcyclopentadienyl group, 1,2,3-trimethylcyclopentadienyl group, 1,2,4-trimethylcyclopentadienyl group, tetramethylcyclopentadienyl group, pentamethylcyclopentadienyl group, etc. Can be mentioned.

[0026] ^{9 R~ 13} when adjacent substituents among R form one or more aliphatic ring or aromatic ring, as such rings, for example indenyl group, 1-methylindenyl group A 4-methylindenyl group, a 5-methylindenyl group, a 1,2-dimethylindenyl group, a 1,3-dimethylindenyl group, a 1,4-dimethylindenyl group,
1,5-dimethylindenyl group, 1,6-dimethylindenyl group, 1,7-dimethylindenyl group, 2,4-dimethylindenyl group, 2,5-dimethylindenyl group,
1,2,3-trimethylindenyl group, heptamethylindenyl group, fluorene group, 1-methylfluorene group,
Examples thereof include a 2-methylfluorene group, a 9-methylfluorene group, and a nanomethylfluorene group.

Of these, a cyclopentadienyl group,
A methylcyclopentadienyl group and a pentamethylcyclopentadienyl group are preferably used.

Examples of ¹ X to ³ X include a hydrogen atom, a chlorine atom, a bromine atom, a methyl group, an ethyl group, a normal propyl group, an isopropyl group, a normal butyl group, an isobutyl group, a tertiary butyl group, and a methylamide-2. -Ethyl group, methylamidotrimethylsilyl group, ethylamido-2-ethyl group, ethylamidotrimethylsilyl group, isopropylamido-2-ethyl group and the like. Among them, chlorine atom and methyl group are preferably used.

When at least one of ⁹ R to ¹³ R simply represents a binding site instead of a substituent, even if such a binding site is bonded to ¹ X to ³ X to form a ring, well, for example, methyl amide [eta ⁵ - cyclopentadienyl] methylene group, ethylamide [eta ⁵ - cyclopentadienyl] methylene, secondary propyl amide [eta ⁵ - cyclopentadienyl] methylene group, tertiary butylamide [eta ⁵ - cyclopentadienyl] methylene, phenyl amide [eta ⁵ - cyclopentadienyl] methylene group, methylamide [eta ⁵ - cyclopentadienyl] -1,2
Ethanediyl group, ethylamide [eta ⁵ - cyclopentadienyl] 1,2-ethanediyl group, secondary propyl amide [eta ⁵ - cyclopentadienyl] 1,2-ethanediyl group, tertiary butylamide [eta ⁵ -Cyclopentadienyl] -1,2-ethanediyl group, phenylamide [η ⁵ -cyclopentadienyl] -1,2-ethanediyl group, methylamide [η ⁵ -cyclopentadienyl] dimethylsilylene group, ethylamide [η ⁵ - cyclopentadienyl] dimethylsilylene group, secondary propyl amide [eta ⁵ - cyclopentadienyl] dimethylsilylene group,
Tertiary butylamide [eta ⁵ - cyclopentadienyl] dimethylsilylene group, phenyl amide [eta ⁵ - cyclopentadienyl] dimethylsilylene group, methylamide [2-
Methyl eta ⁵ - cyclopentadienyl] methylene group, ethylamide [2-methyl eta ⁵ - cyclopentadienyl] methylene, secondary propyl amide [2-methyl -
eta ⁵ - cyclopentadienyl] methylene group, tertiary butylamide [2-methyl-eta ⁵ - cyclopentadienyl]
Methylene group, phenyl amide [2-methyl-eta ⁵ - cyclopentadienyl] methylene group, methylamide [2-methyl eta ⁵ - cyclopentadienyl] 1,2-ethanediyl group, ethylamide [2-methyl-eta ⁵ -cyclopentadienyl] -1,2-ethanediyl group, secondary propylamide [2-methyl-η ⁵ -cyclopentadienyl] -1,2-ethanediyl group, tertiary butylamide [2-methyl- eta ⁵ - cyclopentadienyl] 1,2
-Ethanediyl group, phenylamide [2-methyl-η ⁵
-Cyclopentadienyl] -1,2-ethanediyl group,
Methylamide [2-methyl-η ⁵ -cyclopentadienyl] dimethylsilylene group, ethylamide [2-methyl-
eta ⁵ - cyclopentadienyl] dimethylsilylene group, secondary propyl amide [2-methyl eta ⁵ - cyclopentadienyl] dimethylsilylene group, tertiary butylamide [2-methyl-eta ⁵ - cyclopentadienyl ] dimethylsilylene group, phenyl amide [2-methyl-eta ⁵ - cyclopentadienyl] dimethylsilylene group, methylamide [pentamethyl eta ⁵ - cyclopentadienyl] methylene group, ethylamide [pentamethyl eta ⁵ - cyclopentadienyl Methylene group, secondary propylamide [pentamethyl-η ⁵ -cyclopentadienyl] methylene group,
Tertiary butylamide [pentamethyl eta ⁵ - cyclopentadienyl] methylene, phenyl amide [pentamethyl eta ⁵ - cyclopentadienyl] methylene group, methylamide [pentamethyl eta ⁵ - cyclopentadienyl]
-1,2-ethanediyl group, ethylamide [pentamethyl-η ⁵ -cyclopentadienyl] -1,2-ethanediyl group, secondary propylamide [pentamethyl-η ⁵ −
Cyclopentadienyl] -1,2-ethanediyl group, tertiary butylamide [pentamethyl-η ⁵ -cyclopentadienyl] -1,2-ethanediyl group, phenylamide [pentamethyl-η ⁵ -cyclopentadienyl]- 1,
2-ethanediyl group, methylamide [pentamethyl-η
⁵ - cyclopentadienyl] dimethylsilylene group, ethylamide [pentamethyl eta ⁵ - cyclopentadienyl] dimethylsilylene group, secondary propyl amide [pentamethyl eta ⁵ - cyclopentadienyl] dimethylsilylene group, tertiary butyramide [pentamethyl eta ⁵ - cyclopentadienyl] dimethylsilylene group, phenyl amide [pentamethyl eta ⁵ - cyclopentadienyl] dimethylsilylene group, phenyl phosphide [pentamethyl eta ⁵ - cyclopentadienyl] methylene group, phenyl phosphide [2-methyl-eta ⁵ - cyclopentadienyl] methylene, phenyl phosphide [eta ⁵ - cyclopentadienyl] methylene, phenyl phosphide [pentamethyl eta ⁵ - cyclopentadienyl] -1 , 2-ethanediyl group, phenylphos I de [2-methyl--η ⁵
-Cyclopentadienyl] -1,2-ethanediyl group,
Phenyl phosphide [η ⁵ -cyclopentadienyl]-
1,2-ethanediyl group, phenyl phosphide [pentamethyl-η ⁵ -cyclopentadienyl] dimethylsilylene group, phenyl phosphide [2-methyl-η ⁵ -cyclopentadienyl] dimethylsilylene group, phenyl phosphide [η ^[5 -cyclopentadienyl] dimethylsilylene group.

Among them, (tertiary butylamide) (tetramethyl-η ⁵ -cyclopentadienyl) -1,2-ethanediyl group, (tertiary butylamide) (tetramethyl-
(? ⁵ -cyclopentadienyl) dimethylsilylene group is preferably used. M is a Group 4 metal element, for example, titanium and zirconium are preferably used.

As the half metallocene of the present invention, for example,
Clopentadienyl titanium trichloride, methylcyclo
Pentadienyl titanium trichloride, isopropylcyclo
Lopentadienyl titanium trichloride, 1,3-dimethyl
Rucyclopentadienyl titanium trichloride, pentame
Tylcyclopentadienyl titanium trichloride, cyclo
Pentadienyl titanium tribromide, methylcyclopen
Tadienyl titanium tribromide, isopropyl cyclope
Nantadienyl titanium tribromide, 1,3-dimethyl
Clopentadienyl titanium tribromide, pentamethyl
Cyclopentadienyl titanium tribromide, (tertiary butyl
Tylamide) (tetramethyl-η^Five-Cyclopentadie
Nyl) -1,2-ethanediylzirconium dichloride
, (Tertiary butylamide) (tetramethyl-η^Five−
Clopentadienyl) -1,2-ethanediyl titaniumdi
Chloride), (methylamide) (tetramethyl-η)^FiveShi
Clopentadienyl) -1,2-ethanediyl zirconi
Um dichloride, (methylamide) (tetramethyl-η
^Five-Cyclopentadienyl) -1,2-ethanediylthio
Tandichloride, (ethylamide) (tetramethyl-η
^Five-Cyclopentadienyl) methylene titanium dichloride
, (Tertiary butylamide) (tetramethyl-η ^Five−
Clopentadienyl) dimethylsilylene titanium dichloride
, (Tert-butylamido) dimethylsilylene (tetra
Methyl-η^Five-Cyclopentadienyl) zirconiumdi
Benzyl, (benzylamide) (tetramethyl-η^Five−
Cyclopentadienyl) dimethylsilylene titanium dichloro
Lido, (phenyl phosphide) (tetramethyl-η^Five−
Cyclopentadienyl) dimethylsilylene diconium
Dibenzyl and the like; cyclopentadienyl tita
Trichloride, methylcyclopentadienyl titanate
Lichloride, pentamethylcyclopentadienyl titanium
Trichloride, (tertiary butylamide) (tetramethyl
−η^Five-Cyclopentadienyl) dimethylsilentilenta
Dichloride is preferably used, and cyclopentadienyl
Trititanium trichloride, methylcyclopentadienylthi
Tantric chloride, pentamethylcyclopentadienyl
Titanium trichloride, (tertiary butylamide) (tetra
Methyl-η^Five-Cyclopentadienyl) dimethylsilyl
Titanium dichloride is more preferably used. Also,
In order to improve the activity and facilitate the removal of the catalyst, etc.
-The metallocene component is magnesium chloride, silica,
Mina, silica alumina, molecular sieve, diatomaceous earth
For example, it may be used by being supported on a porous solid.

The half metallocenes of the present invention can be prepared by contacting a metal reagent with a Group 1 metal derivative or a Grignard derivative of a cyclopentadienyl compound in a solvent and then separating off the salt by-product.

The solvent used for producing such a half metallocene is a liquid containing an aliphatic or aromatic compound at room temperature, such as cyclohexane, methylcyclohexane, or the like.
Pentane, hexane, heptane, tetrahydrofuran,
Diethyl ether, alkyl ethers having 1 to 4 carbon atoms of mono- or di-ethylene glycol, alkyl ethers having 1 to 4 carbon atoms of mono- or di-propylene glycol, benzene, toluene, xylene, ethylbenzene and the like are preferably used. Can be Further, a mixture of these solvents may be used.

The concentration of the half-metallocene may be determined according to the polymerization activity, and is preferably 10 ^-6 to 10 ^-2 mol, and more preferably 1 to ⁶ mol per mol of the monomer added to the polymerization reaction system.
It is used at a concentration of 0 ^-5 to 10 ^-3 mol.

The catalyst system of the present invention preferably contains a cationizing agent and an alkylating agent in addition to the above half metallocene.

Such a cationizing agent is used to generate a cation which is a source of an active species from the half metallocene of the present invention, and an organic compound such as aluminoxane such as polymethylaluminoxane, ethylaluminum sesquichloride, diethylaluminum chloride and the like. Aluminum compounds, ionic boron compounds represented by the following formulas (I) to (IV), heteropoly acids, silica, alumina, and compounds having acid points such as lattice defects on magnesium chloride crystals are preferably used. ^{[14 RC] + [B 14} R 3] - ··· (I) [14 R x NH 4-x] + [B 15 R 4] - ··· (II) [14 R x PH 4-x] _{^{+ [B 15 R 4] -}} ··· (III) Li + [B 15 R 4] - in ··· (IV) [formula (I) ~ (IV), 14 R are identical or different, carbon atoms 1 To 8 aliphatic hydrocarbon groups or 6 to 1 carbon atoms
And 8 aromatic hydrocarbon groups. ¹⁵ R are the same or different and are an aromatic hydrocarbon group having 6 to 18 carbon atoms. x is 1, 2,
3 or 4. In the ionic boron compounds represented by the above (I) to (IV), ¹⁴ R is preferably the same, for example, an alkyl group such as a methyl group, an ethyl group, a propyl group or a butyl group, or an aryl group such as a phenyl group. Groups are preferred. ¹⁵ R are preferably the same, preferably a fluorinated or partially fluorinated aromatic hydrocarbon group, particularly preferably a pentafluorophenyl group. x is preferably 3.

Specific compounds include, for example, N, N-dimethylanilinium-tetrakis (pentafluorophenyl) borate, trityl- (pentafluorophenyl) borate, and lithium-tetrakis (pentafluorophenyl) borate.

As the cationizing agent of the present invention, polymethylaluminoxane and tritylpentafluorophenylborate are more preferably used. These may be used alone or in combinations of several types.

The ratio of the cationizing agent to the half metallocene is 0.5 to 10000 mol, preferably 0.8 to 3 mol of the cationizing agent per 1 mol of the half metallocene.
000 mol, more preferably 0.9-1500 mol
Is used. When the cationizing agent is an ionic boron compound, the efficiency of cationization is high, so that the ionic boron compound is 0.5 to 1 mol per half metallocene.
10 mol, preferably 0.8 to 3 mol, more preferably 0.9 to 1.5 mol is used.

The cationizing agent reacts with the half metallocene to form the half metallocene into a cationic complex and also functions to stabilize the half metallocene. In the reaction with the half metallocene, the alkylating agent described later is used simultaneously. Is preferred. Such an alkyl aluminum compound acts as an alkylating agent for half metallocene,
This has the effect of facilitating the reaction between the metallocene and the cationizing agent.

The alkylating agent activates the half metallocene by alkylating it. Alkylating aluminum compounds such as trimethylaluminum, triethylaluminum, triisobutylaluminum, ethylaluminum sesquichloride and diethylaluminum chloride, polymethylaluminoxane and the like Aluminoxane,
Organic zinc compounds such as dimethyl zinc, diethyl zinc, and diphenyl zinc are preferably used, and triethyl aluminum, triisobutyl aluminum, and polymethyl aluminoxane are more preferably used. These may be used alone or in combinations of several types.

Alkylating agent for half metallocene
The ratio indicates the number of moles of half metallocene [M₁], Archi
[AL]₁]
[AL ₁] / [M₁Is 1 or more and 1000 or less, preferably
Is 2 or more and 500 or less, more preferably 10 or more and 300 or less
The range is below. [AL₁] / [M₁Is less than 1
Sufficient polymerization activity was not obtained due to insufficient killing.
₁] / [M₁] Is more than 1000, half metallocene
Not only reduces the core metal and impairs the polymerization activity, but also
Problems with the surface and catalyst removal, both of which are preferred.
I don't.

The method of using the catalyst system of the present invention is not particularly limited. The alkylating agent may be added to the mixture of the half metallocene and the cationizing agent, or the half metallocene and the alkylaluminum compound may be reacted in advance, and the cationizing agent may be added thereto. The activation of the half metallocene may be performed in the polymerization solution, or may be separately performed to prepare a polymerization catalyst solution, which may be added to the polymerization solution or the monomer solution.

[Formation of Polymerization Method] In the production of the polymer of the present invention, a monomer having the above formula (A) and a catalyst system are mixed under an atmosphere of dehydration and inert gas, and a (co) polymerization reaction is carried out. This is done by: If the production of the present invention is carried out in the presence of water and / or in the presence of an active gas such as oxygen or the like, the catalyst system is altered and the polymerization activity is lost, which is not preferable. Nitrogen, argon gas and the like can be used as the inert gas, but it is preferable to use nitrogen gas from the viewpoint of economy.

As described above, the monomer represented by the formula (A) may be used for homopolymerization using only one kind, or may be used for copolymerization using two or more kinds. Α-olefins such as 1-butene and 1-hexene;
Non-conjugated dienes such as 1,5-hexadiene; conjugated dienes such as 1,3-butadiene, isoprene, and 2,3-dimethylbutadiene may be copolymerized.

It is preferable to use a solvent in the production of the present invention. Examples of such a solvent include aliphatic hydrocarbons having 5 to 20 carbon atoms such as hexane, heptane, octane, decane, dodecane, cyclohexane, cycloheptane, cyclodecane, methylcyclohexane, and tetralin, and carbons such as benzene, toluene, xylene, and ethylbenzene. Aromatic hydrocarbons having a number of from 6 to 20 are preferable, and toluene and xylene are more preferably used.

The reaction temperature exceeds the temperature at which the system begins to freeze,
And it is 100 ° C or less, -20 ° C or more and 70 ° C or less are preferred, and -10 ° C or more and 50 ° C or less are more preferred. The reaction does not proceed below the temperature at which the system freezes, and the temperature is 100 ° C.
If the ratio exceeds the above range, the catalyst deteriorates and loses the polymerization activity, which is not preferable. The reaction time is not particularly limited, but is, for example, 10 minutes to 24 hours, preferably 30 minutes to 15 hours, more preferably 1 hour to 10 hours. If the reaction time is less than 10 minutes, the reaction is so rapid that the temperature of the system cannot be controlled due to the heat of the reaction, which is not preferable. If the reaction time exceeds 24 hours, the catalyst is denatured and loses its activity, which is not preferable. The polymer or the polymer solution thus obtained can be obtained as a solution as it is, or only the polymer can be obtained by reprecipitation or desolvation.

[Mode of Hydrogenation Method] When unsaturated bonds such as chain-carbon double bonds and aromatic bonds remain in the polymer obtained by the above-mentioned production method, the polymer is used for improving weather resistance and the like. Can be hydrogenated. Examples of the catalyst used for hydrogenation include a homogeneous catalyst comprising a combination of a transition metal compound and an alkylating agent; and a heterogeneous catalyst in which a transition metal is supported on a carrier such as silica or alumina.

The transition metal compound in the homogeneous catalyst includes, for example, halides of transition metals such as vanadium, chromium, manganese, iron, ruthenium, cobalt, rhodium, nickel, palladium, acetylacetonate complexes,
Examples include a carboxylate complex, a naphthate complex, a trifluoroacetate complex, and a stearate complex. Specific examples include triethylvanadate, tris (acetylacetonato) chromium, tris (acetylacetonato) manganese, cobalt acetate, and tris (acetyl). Acetonate)
Cobalt, cobalt octenoate, bis (acetylacetonato) nickel and the like can be mentioned.

Examples of the alkylating agent used for such a catalyst include lithium, magnesium, aluminum and the like.
Examples include zinc compounds, and specific examples include butyllithium, dimethylmagnesium, triethylaluminum, triisobutylaluminum, methylaluminoxane, diethylzinc and the like.

Among these, from the viewpoint of catalytic activity, a combination of cobalt, a nickel compound and an alkylaluminum compound or an alkyllithium compound is preferable, and tris (acetylacetonato) cobalt or bis (acetylacetonato) nickel, triethylaluminum, Combinations of alkyl aluminum compounds such as triisobutyl aluminum or methyl aluminoxane are particularly preferred.

As the transition metal in the heterogeneous catalyst, for example, iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium and platinum are used, and nickel, palladium, rhodium and platinum are preferably used. As a carrier in such a catalyst, for example, silica,
Metal oxides such as alumina, silica alumina, magnesia, titania, and zirconia are used.

The concentration of the transition metal compound in the hydrogenation catalyst used in the hydrogenation reaction may be determined according to the polymerization activity. Is usually used at a concentration of 10 ^-6 g or more and 10 ^-2 g or less, preferably 10 ^-5 g or more and 10 ^-3 g or less with respect to 1 g of the polymer. In the case of a heterogeneous catalyst, it is usually 10 ^-5 g. g
It is used at a concentration of at least ¹ g and preferably at most 10 ^-4 g and at most 10 ^-1 g.

In the present invention, the hydrogenation reaction is usually carried out with an aliphatic hydrocarbon having 5 to 20 carbon atoms,
0 or less aromatic hydrocarbon solvent is used, for example, pentane, hexane, octane, decane, cyclopentane,
Cyclohexane, cyclooctane, benzene, toluene, xylene and the like are used, and cyclohexane, methylcyclohexane, toluene and xylene are preferably used. These solvents may be used alone or as a mixture of two or more.

The temperature, hydrogen pressure and reaction time for the hydrogenation reaction of the copolymer may be determined according to the type of the monomer used for the addition copolymerization and the type of the hydrogenation catalyst. Usually, the temperature is 0 ° C or higher and 250 ° C or lower, preferably 20 ° C or higher,
00 ° C or less, hydrogen pressure is 0.01MPa or more, 20MPa
a, preferably 0.1 to 10 MPa, and the reaction time is 0.1 to 10 hours.

The hydrogenation rate (hydrogenation rate of carbon-carbon double bond) of such a copolymer is preferably 99% or more, more preferably 99.5% or more, and still more preferably 99.9%.
% Or more. It is preferable that the hydrogenation rate be 99% or more, since sufficient thermal stability and weather resistance can be obtained.

The use form of the homogeneous hydrogenation catalyst in the present invention is not particularly limited, but a transition metal compound is reacted with an alkylating agent to prepare a preactivated catalyst solution, which is added to the polymerization solution. A method can be preferably mentioned. Such pre-activation is -40 ° C or higher and 100 ° C or lower,
The reaction is preferably performed at a temperature of 0 ° C to 80 ° C, and the reaction time is 0.5 minutes to 3 hours, preferably 1 minute to 1 hour.

Examples of the hydrogenation catalyst used for hydrogenating the copolymer include, in addition to the above, a catalyst comprising only a transition metal compound. Specifically, carbonylchlorohydridotris (triphenylphosphine) ruthenium, dihydridocarbonyltris (triphenylphosphine)
Examples thereof include ruthenium, dihydridotetrakis (triphenylphosphine) ruthenium, tetrahydridotris (triphenylphosphine) ruthenium, chlorotris (triphenylphosphine) rhodium, and hydridecarbonyltris (triphenylphosphine) rhodium. These catalysts dissolve very stably in the system,
Since removal of the catalyst tends to be difficult, it is desirable to add an operation for appropriately removing the catalyst as described below.

The hydrogenated cyclic olefin polymer solution thus obtained can be used as a solution as it is, or only the desired product can be obtained by reprecipitation, desolvation, etc., but the polymerization catalyst remaining in the solution, After the catalyst is analyzed by adding a chelating agent or acid to the hydrogenation catalyst, it can be removed by filtration, centrifugation, an adsorbent, or the like.

If necessary, additives such as an antioxidant, an ultraviolet absorber, a release agent, a plasticizer, and an antistatic agent may be added to the cyclic olefin polymer and the hydrogenated cyclic olefin polymer. can do.

The obtained cyclic olefin polymer and hydrogenated cyclic olefin polymer have high transparency from amorphous to high transparency, high heat resistance due to high glass transition temperature, and low water absorption due to the absence of polar groups. Shows sex.

[0062]

According to the present invention, a cyclic olefin polymer and a hydrogenated product of a cyclic olefin polymer excellent in optical properties such as transparency and optical isotropy, heat resistance and water resistance can be efficiently produced. The polymer and the hydrogenated product thereof can be used in the fields of transparent conductive films, liquid crystal display panel members such as color filters, surface protective layers of solar cell modules, and the like. .

[0063]

The present invention will be described below with reference to examples.

The items measured in Examples, Reference Examples and Comparative Examples were measured by the following methods.

IR: FT made by PERKIN ELMER
Using -IR 1760X, a tablet was molded together with KBr as a sample, and measurement was performed at room temperature.

¹ H-NMR: EX-270 manufactured by JEOL
The measurement was carried out at room temperature using deuterated chloroform as a solvent and chloroform contained in a trace amount of deuterated chloroform as an internal standard. Glass transition temperature (Tg): TA Instruments
The temperature was raised at a rate of 20 ° C./min using Model 2920 DSC.

Reduced viscosity: The reduced viscosity ηsp / C at 30 ° C. of a 0.5 g / dL toluene solution was measured.

Example 1 50 g of dicyclopentadiene, 100 g of toluene, 0.066 g of cyclopentadienyl titanium trichloride were placed in a 300 mL glass reaction vessel.
0.23 g of trityltetrakispentafluorophenylborate and 2.8 g of triisobutylaluminum were charged and reacted at 40 ° C. About 10 minutes after the start of the reaction, the inside of the system became turbid, and the degree of turbidity became constant in about 30 minutes. 40 minutes after the start of the reaction, 500 g of the mixture
In 2-propanol to precipitate polydicyclopentadiene. The precipitate was filtered, washed with clean 2-propanol, and dried under reduced pressure at 60 ° C. to obtain 11 g of dried powdery polydicyclopentadiene. The obtained polydicyclopentadiene is used for 1 hour at 1 g / g of catalyst.
6.2 g.

This polydicyclopentadiene did not dissolve in any of hot toluene, hot xylene, and hot orthodichlorobenzene. From DSC measurement, Tg was not observed up to 300 ° C.

[0070] When this powder was IR measured tablet with KBr, 1450 cm ^-1 derived from two different methylene group deformation vibration as shown in FIG. 1, of the polymer from the two absorption of 1470 cm ^-1 Since the unsaturated bond is at the 7-position, it is presumed that this polymer was polymerized by cleavage of the 2-position unsaturated bond of dicyclopentadiene.

Comparative Example 1 A 300 mL glass reaction vessel was charged with 66 g of dicyclopentadiene, 100 g of toluene, 0.8 g of vanadyl trichloride and 3.4 g of diethylaluminum chloride, and reacted at 40 ° C. Reaction start 1
After 3.5 hours, the mixture was poured into 500 g of 2-propanol to precipitate polydicyclopentadiene, and the precipitate was filtered, washed with clean 2-propanol, dried at 60 ° C. under reduced pressure, and dried at 4 g. A powdered polydicyclopentadiene was obtained. The obtained polydicyclopentadiene was 0.4 g per 1 g of the catalyst for 1 hour. From DSC measurement, Tg was not observed up to 300 ° C.

Example 2 22 g of dicyclopentadiene, 5 g of norbornene, 50 g of toluene, 0.066 g of cyclopentadienyltitanium trichloride, 0.24 g of trityltetrakispentafluorophenylborate, 0.24 g of triisobutylaluminum were placed in a 300 mL glass reaction vessel. 0.8 g was charged and reacted at 40 ° C. During the reaction, the inside of the system did not become cloudy. 120 minutes after the start of the reaction, this mixture was reprecipitated in 500 g of 2-propanol to obtain a dicyclopentadiene-norbornene copolymer. The precipitate was filtered, washed with clean 2-propanol, dried at 60 ° C. under reduced pressure, and the weight of the copolymer was measured to be 5 g. The reduced viscosity of 0.5 g / dL in toluene at 30 ° C. was 0.2 dL / g. Tg is 300 from DSC measurement.
Not observed by ° C. When this powder was IR measured tablet with KBr, 1450 cm ^-1 derived from two different methylene group deformation vibration observed in homopolymerization of dicyclopentadiene, 2 1470 cm ^-1
Since the absorption of the book disappeared and an IR spectrum different from that of the norbornene homopolymer was shown, it is presumed that this polymer was a copolymer of norbornene and dicyclopentadiene.

Example 3 In a 1 L stainless steel pressure vessel
128 g of dicyclopentadiene, 131 g of toluene,
Clopentadienyl titanium trichloride 0.058 g,
Trityltetrakispentafluorophenylborate
0.22 g and 2.4 g of triisobutylaluminum
And charged with 0.5 MPa of ethylene, and reacted at 20 ° C.
went. Ethylene is connected at 0.5MPa and flows about 8L
At that point, the ethylene supply was cut off. 120 minutes after the start of the reaction
Later, the mixture was taken up in 1500 g of 2-propanol.
Reprecipitate to obtain dicyclopentadiene-ethylene copolymer
Was. The precipitate is filtered, washed with clean 2-propanol, 6
After drying under reduced pressure at 0 ° C., the weight of the copolymer was measured and found to be 1
30 g. Polymerization activity per hour, per g of catalyst
It was 145 g. The obtained dicyclopentadiene-d
0.5 g / dL of toluene copolymer at 30 ° C. in toluene
Has a reduced viscosity of 0.66 dL / g and deuterated chloroform.
Measured at medium room temperature ¹Dish determined from H-NMR (FIG. 2)
The ratio of units derived from clopentadiene is 46 mo
1%, glass transition temperature was 165 ° C.

Example 4 30 g of the dicyclopentadiene-ethylene copolymer obtained in Example 3 and 120 g of cyclohexane were dissolved in a 1 L stainless steel autoclave equipped with a stirring function, and tris (acetylacetylacetonato) cobalt was dissolved. A mixture of 3 g and 0.5 g of triisobutylaluminum was added. 4.5 MPa of hydrogen was introduced, and a hydrogenation reaction was performed at 120 ° C. for 120 minutes. After the reaction, the reaction solution was poured into 1 L of methanol, and the obtained precipitate was filtered, washed with clean methanol, and dried at 60 ° C. under reduced pressure. ^{From the 1} H-NMR spectrum, the hydrogenation rate of this polymer was 99.9 or more. 0.5%
The reduced viscosity (ηsp) measured at 30 ° C. using a toluene solution
/ C) was 0.63 dL / g. The Tg measured using DSC was 168 ° C.

[Brief description of the drawings]

FIG. 1 shows the NMR of the polymer obtained in Example 1.

FIG. 2 shows an NMR of the polymer obtained in Example 3.

 ──────────────────────────────────────────────────の Continued on the front page F-term (reference) 4J028 AA01A AB01A AC08A AC10A AC26A AC28A BA00A BA01B BB00A BB00B BB01B BC09B BC13B BC16B BC19B BC25B CA16B CA27B CA28B EB02 EB04 EB05 EB09 A04 A02B02A AR11P AR21P AR22P AR25P AS02Q AS03Q AS11Q CA01 CA04 DA22 DA62 FA10 FA19 HA04 HB29 HC25 HD22 JA32 4J128 AA01 AB01 AC08 AC10 AC26 AC28 AD00 AE00 BA00A BA01B BB00A BB00B BB01B BC09B BC13B BCEBBEB EBEB EBEB EB13 EB00 EC02 FA02 GA04

Claims (6)

[Claims] (1) The following formula (A): (In the formula, n represents 0 or 1, ¹ R to ⁸ R are the same or different and represent a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms (provided that ¹ R and ² R and ³ R and ⁴ R At least one of R may form an unsaturated bond, and at least one of ¹ R and ³ R and ² R and ⁴ R may form a ring). With the following formula (C): (In the formula, ⁹ R to ¹³ R are the same or different and represent a substituent selected from a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, and an aryl group having 6 to 12 carbon atoms (provided that ⁹ R
To ¹³ R may form one or more aliphatic rings or aromatic rings). ¹ X to ³ X are the same or different and each represent a hydrogen atom, a halogen atom,
Represents a substituent selected from the following alkyl groups and aryl groups having 6 to 12 carbon atoms (however, such substituents may include atoms such as nitrogen, phosphorus, oxygen, sulfur, and silicon; the ^{9 R~ 13} at least one of R, may form a ring with ¹ X to ³ X represents a binding site). M represents a Group 4 metal element. ) In the presence of a catalyst system containing half metallocene (co)
The following formula (B) characterized by being polymerized: (In the formula, n represents 0 or 1, ¹ R ′ to ⁸ R ′ are the same or different and represent a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms (provided that ¹ R ′ and ² R ′ and ³ R 'and ⁴ R'
May form an unsaturated bond, and at least one of ¹ R ′ and ³ R ′ and ² R ′ and ⁴ R ′ may form a ring). A method for producing a cyclic olefin polymer containing a repeating unit represented by the formula (1). 2. The method according to claim 1, wherein the half metallocene is dicyclopentadienyl titanium trichloride. 3. A cyclic olefin polymer obtained by the method according to claim 1. 4. The method according to claim 1, wherein the cyclic olefin polymer is a norbornene-dicyclopentadiene copolymer, an ethylene-dicyclopentadiene copolymer, or ethylene-7,8-
4. A dihydrodicyclopentadiene copolymer.
The cyclic olefin-based polymer according to the above. 5. A hydrogenated cyclic olefin polymer obtained by hydrogenating the unsaturated bond when the cyclic olefin polymer according to claim 3 has an unsaturated bond. 6. The unsaturated cyclic olefin polymer is an ethylene-dicyclopentadiene copolymer.
The described hydrogenated product.