JP2928337B2 - Cyclic olefin polymer, polymerization catalyst for cyclic olefin, and method for producing cyclic olefin polymer - Google Patents

Description

The present invention relates to a cyclic olefin or a cyclic olefin polymer having a cyclic olefin having an exocyclic unsaturated bond as a monomer component, a cyclic olefin polymerization catalyst, and a cyclic olefin. The present invention relates to a method for producing a polymer.

[Prior Art and Problems to be Solved by the Invention] Conventionally, a cyclic olefin polymer having excellent alkali resistance is a titanium-based catalyst comprising a titanium compound and an organoaluminum compound, and a vanadium-based catalyst comprising a vanadium compound and an organoaluminum compound. Is produced by polymerizing a cyclic olefin in the presence of

However, these catalyst systems have low catalytic activity, and it is difficult to increase the polymerization reactivity of cyclic olefin. When a large amount of cyclic olefin is used, the catalytic activity is impaired. Further, side reactions such as a ring-opening polymerization reaction and an isomerization reaction are likely to occur. In particular, the vanadium-based catalyst has extremely low polymerization activity as compared with the titanium-based catalyst. Therefore, it is difficult to obtain a high molecular weight cyclic olefin homopolymer, and many copolymers with ethylene have been reported (JP-A-59-16995 and JP-A-61-120816). And JP-A-61-272216).

Further, as a polymerization catalyst for a copolymerization reaction between an α-olefin and a cyclic olefin, a catalyst comprising a transition metal compound and an aluminoxane has been proposed [JP-A-61-221206, JP-A-1-156308, Journal Of Polymer Science Chemistry Edition (J.
Polym. Sci. Chem. Ed.) (23) 2151-2164 (1985)), Macromolecular Chemie (Makromol. Chem. (190), 51)
5-526 (1989)].

However, all of these prior arts relate to copolymerization of an α-olefin and a cyclic olefin, and these prior art documents include cyclic olefins and polymers of cyclic olefins having an exocyclic unsaturated bond. Is not disclosed at all. Further, the copolymer of α-olefin and cyclic olefin produced using the above catalyst has excellent heat resistance as compared to polyolefin, but contains α-olefin units, so that the heat resistance is increased. Has a limit. Further, since the content of α-olefin is large and insoluble in general-purpose organic solvents, processability such as film formation is also inferior. Furthermore, copolymers of α-olefins and cyclic olefins are difficult to modify by introducing various functional groups, and their uses are limited.

On the other hand, as a method for producing a cyclic olefin polymer having an exocyclic unsaturated bond, a method based on cation polymerization by Kennedy et al. [Journal of Macromolecules Science Chemistry Edition (J. Macromol. Sci (Chem. ) A1 (3) 345 (196
7)]; A method using a palladium compound as a catalyst [Journal of Polymer Science (J. Polym. Sc)
i.) B4 541 (1966) and U.S. Pat.
It has been known.

However, in the method by cationic polymerization, isomerization reaction, ring-opening reaction and side reactions such as cross-linking are likely to occur.
It is necessary to carry out the polymerization at a low temperature of not more than ℃, not only the production workability is lowered but also the yield of the cyclic olefin polymer is low. On the other hand, in the method using a palladium compound as the catalyst, the yield of the cyclic olefin polymer is low because the monomer forms a complex with the catalyst and is stabilized, and the polymerization activity is low. Therefore, when producing a cyclic olefin or a polymer of a cyclic olefin having an exocyclic unsaturated bond by these methods, it is difficult to efficiently produce a polymer having a film-forming ability.

As described above, cyclic olefins and cyclic olefins having an exocyclic unsaturated bond are liable to undergo side reactions such as ring-opening reaction, isomerization reaction, and cross-linking during polymerization, and therefore, the molecular weight distribution of the obtained polymer is low. There is a special feature that it is easy to spread. Therefore, a catalyst system having an excellent polymerization activity for selectively and smoothly proceeding a polymerization reaction at an unsaturated ring outside or inside a ring; a high molecular weight cyclic olefin polymer; a high yield of a high molecular weight cyclic olefin polymer Is strongly desired.

Therefore, an object of the present invention is to provide a high molecular weight cyclic olefin polymer using a cyclic olefin which may have an exocyclic unsaturated bond as a monomer component.

It is another object of the present invention to provide a high molecular weight cyclic olefin polymer having a narrow molecular weight distribution.

Still another object of the present invention is to provide a cyclic olefin polymer which has excellent heat resistance, transparency and strong alkali resistance, is soluble in an organic solvent, has a film forming ability, and can be modified by introducing various functional groups. To provide.

Another object of the present invention is to provide a cyclic olefin polymerization catalyst capable of selectively and highly advancing a polymerization reaction while suppressing a side reaction with a cyclic olefin which may have an exocyclic unsaturated bond. Is to provide.

Still another object of the present invention is to promote the polymerization reaction of a cyclic olefin and / or a cyclic olefin having an exocyclic unsaturated bond selectively and smoothly while suppressing a side reaction, and to obtain a high molecular weight cyclic An object of the present invention is to provide a production method capable of obtaining an olein polymer.

[Constitution of the Invention] In order to achieve the above object, the present invention provides a compound represented by the following formula [I]
[II] or [III] (Wherein, R ^{1 to} R ¹² are the same or different and each represent a hydrogen atom, a halogen atom, a saturated or unsaturated hydrocarbon group, and in formula [I], at least one of R ¹ and R ² , I
I], at least one of R ^{3 to} R ¹² , or a compound of the formula [II
In I], at least one of R ^{1 to} R ¹⁰ is an unsaturated hydrocarbon group. k and p are integers of 3 or more, m and n
Is an integer of 0 or more.) A cyclic olefin polymer comprising a cyclic olefin repeating unit represented by at least one unit and having a polystyrene equivalent number average molecular weight of 700 to 200,000 is provided.

Further, the present invention relates to the following formula [Ia] [IIa] or [III
a] (Wherein, R ^{1 to} R ¹² are the same or different and each represent a hydrogen atom, a halogen atom, a saturated or unsaturated hydrocarbon group,
(1) At least one of R ¹ and R ² in the formula [Ia]
In the formula [IIa], at least one of R ^{3 to} R ¹²
Or at least one of R ^{1 to} R ¹⁰ in the formula [IIIa] is an unsaturated hydrocarbon group, or (2) a compound represented by the formula [I
a] In [IIa] or [IIIa], R ^{1 to} R ¹² are the same or different and are a hydrogen atom, a halogen atom or a saturated hydrocarbon group. k and p are integers of 3 or more, and m and n are 0
Is a polymerization catalyst for polymerizing at least one cyclic olefin represented by the following formula (1) by an addition reaction of a double bond in the ring, and comprises a combination of a metal compound of Group VIII of the periodic table and an aluminoxane. Provided by the present invention.

Further, the present invention provides the cyclic olefin,
Provided is a method for producing a cyclic olefin polymer in which a cyclic olefin is polymerized by an addition reaction of a double bond in a ring in the presence of a polymerization catalyst comprising a combination of a group VIII metal compound and an aluminoxane.

 Hereinafter, the present invention will be described in detail.

The repeating unit of the cyclic olefin polymer of the present invention is composed of at least one unit represented by the following formulas [I], [II] and [III].

(Wherein, R ^{1 to} R ¹² are the same or different and each represent a hydrogen atom, a halogen atom, a saturated or unsaturated hydrocarbon group. K and p are integers of 3 or more, and m and n are integers of 0 or more. Shown) The halogen atoms of R ^{1 to} R ¹² include fluorine, chlorine, bromine and iodine atoms. The saturated hydrocarbon group includes, for example, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group and the like. Examples of the unsaturated hydrocarbon group include vinyl and ethylidene groups.

Among the cyclic olefins corresponding to the unit represented by the formula [I], examples of the cyclic olefin having an unsaturated bond in the ring include cyclopropene, cyclobutene, cyclopentene, 3-methylcyclopentene, 4-methylcyclopentene And monochloroalkenes such as 3-chlorocyclopentene, cyclohexene, 3-methylcyclohexene, 4-methylcyclohexene, 3,4-dimethylcyclohexene, 3-chlorocyclohexene, cycloheptene, cyclooctene, cyclodecene and cyclododecene.

Among the cyclic olefins corresponding to the unit represented by the formula [I], examples of the cyclic olefin having an exocyclic unsaturated bond include vinylcyclopentene, vinylcycloheptene, 4-vinyl-1-cyclohexene and the like. Is mentioned.

Among the cyclic olefins corresponding to the unit represented by the formula [II], examples of the cyclic olefin having an unsaturated bond in the ring include norbornene, 5-methyl-2-norbornene, 5-ethyl-2- Bicycloalkenes such as norbornene, 5-isobutyl-2-norbornene and 5,6-dimethyl-2-norbornene; 1,4,5,8-dimethano-1,
2,3,4,4a, 5,8,8a-octahydronaphthalene, 2-methyl-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydro Naphthalene, 2-ethyl-1,4,5,8-dimethano-1,
2,3,4,4a, 5,8,8a-octahydronaphthalene, 2-propyl-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydro Naphthalene, 2-n-butyl-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2
-Isobutyl-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a
-Octahydronaphthalene, 2-hexyl-1,4,5,8-
Dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2-stearyl-1,4,5,8-dimethano-1,2,3,4,4a,
5,8,8a-octahydronaphthalene, 2,3-dimethyl-1,1,
4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2-methyl-3-ethyl-1,4,5,8-dimethano-1,2, 3,4,4a, 5,8,8a-octahydronaphthalene, 2
-Cyclohexyl-1,4,5,8-dimethano-1,2,3,4,4a, 5,
8,8a-octahydronaphthalene, 2-chloro-1,4,5,8
-Dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2-bromo-1,4,5,8-dimethano-1,2,3,4,4a, 5,
8,8a-octahydronaphthalene, 2-fluoro-1,4,5,
8-Dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2,3-dichloro-1,4,5,8-dimethano-1,2,3,4,4
a, 5,8,8a-tetra cycloalkenes such octahydronaphthalene; hexacyclo [6,6,1,1 ^3,6, 1 ^10,13, 0 ^2,7, 0
^9,14] heptadecene -4 pentacyclo [8,8,1 ^2,9, 1
^4,7, 1 ^{11, 18,} 0, 0 ^3,8, 0 ^12,17] henicosenoic -5, octacyclo [8,8,1 ^2,9, 1 ^4,7, 1 ^{11, 18,} 1 ^{13, 16} , 0,0 ^3,8 ,
0 ^12,17 ] dococene-5 and the like.

Among the cyclic olefins corresponding to the unit represented by the formula [II], examples of the cyclic olefin having an exocyclic unsaturated bond include 5-vinyl-2-norbornene and 8-
Vinyl tetracyclo [4,4,0,1 ^2,5, 1 ^7,10] -3-dodecene, 5-ethylidene-2-norbornene, 5-methylene-2-norbornene, and the like.

Examples of the cyclic olefin corresponding to the unit represented by the formula [III] include, for example, 2,3,3a, 7a-tetrahydro-4,7
-Methano-1H-indene, 3a, 5,6,7a-tetrahydro-
Tricycloalkenes such as 4,7-methano-1H-indene; dicyclopentadiene, dicyclopentadienylheptene, alkylidenetetrahydroindene, 3a, 4,7,7
cyclic polyene such as a-tetrahydroindene;

One or more of these cyclic olefins can be used.

The molecular weight of the cyclic olefin polymer is, in terms of polystyrene, a number average molecular weight of 700 to 200,000, preferably 1,000 to 15,000.
0, more preferably 10,000 to 100,000.

The cyclic olefin polymer of the present invention has excellent transparency and heat resistance. For example, the following formula [IV] A polymer comprising a repeating unit represented by the formula: poly (5-vinyl-2-norbornene) has high transparency,
The pyrolysis onset temperature is usually 250 ° C. or higher, preferably 3 ° C.
It is about 00 to 500 ° C. The cyclic olefin polymer of the present invention is different from a copolymer of an α-olefin and a cyclic olefin, and has high solubility in an organic solvent and high film-forming ability. For example, a polymer comprising a repeating unit represented by the formula [IV] has excellent solubility at room temperature in various organic solvents such as chloroform, dichloromethane, tetrahydrofuran, and decalin. Further, the cyclic olefin polymer of the present invention, particularly poly (5-vinyl-2-norbornene), has a characteristic that it is not attacked by a strong alkali.

In the cyclic olefin polymer, an exocyclic unsaturated bond,
In particular, a polymer containing a cyclic olefin unit having a vinyl group, in particular, a polymer consisting of a repeating unit represented by the formula [IV], various known reactions, for example, halogenation,
Various functional groups can be introduced into an unsaturated bond to modify it by utilizing epoxidation, alcoholization, hydroformylation, or the like.

The cyclic olefin polymer of the present invention is obtained by polymerizing a cyclic olefin and / or a cyclic olefin having an exocyclic unsaturated bond in the presence of a catalyst comprising (a) a metal compound and (b) an aluminoxane.

In the present invention, a polymerization catalyst comprising a combination of a metal compound of Group VIII of the periodic table and an aluminoxane is used as the polymerization catalyst.

The metal compound (a) as a catalyst component is represented by VIII in the periodic table.
It is a metal compound selected from the group. Examples of the metal of Group VIII of the periodic table include cobalt, nickel, palladium, platinum, and rhodium. These Group VIII metal compounds may be used in combination with, for example, compounds of transition metals of Group IVB and VB of the periodic table such as titanium, zirconium, hafnium, vanadium and iron.

The metal compound is not particularly limited as long as it is a compound containing the Group VIII metal of the periodic table, and examples thereof include a metal compound having a halogen atom, a metal compound having a hydrocarbon group, an organic acid salt, an alcoholate, a complex, and an oxide. It may be.

Among the metal compounds of Group VIII of the periodic table, examples of the palladium compound include palladium (II) acetate, palladium (II) acetylacetonate, and palladium (O)
Bis (dibenzylideneacetone), palladium (II) bromide, palladium (II) chloride, palladium (II) iodide, palladium (II) oxide, monoacetonitrile tris (triphenylphosphine) palladium (II) tetrafluoroborate [Pd ( CH ₃ CN)
(PPh ₃ ) ₃ ] (BF ₄ ) ₂ , tetrakis (acetonitrile) palladium (II) tetrafluoroborate, dichlorobis (acetonitrile) palladium (II), dichlorobis (triphenylphosphine) palladium (II), dichlorobis (benzonitrile) Palladium (II) and the like are exemplified.

Examples of the nickel compound include nickelocene, nickel (II) acetate, nickel (II) acetylacetonate, nickel bromide, nickel chloride, nickel 4-cyclohexylbutyrate, nickel lactate, nickel oxide, nickel tetrafluoroborate, and the like. Is done.

Examples of the cobalt compound include cobalt acetate (I
I), cobalt (II) acetylacetonate, cobalt (III) acetylacetonate, cobalt benzoate (I
I), cobalt chloride, cobalt bromide, cobalt 4-cyclohexyl butyrate, cobalt (II) stearate, cobalt (II) tetrafluoroborate and the like.

Examples of the rhodium compound include rhodium chloride, rhodium bromide, rhodium acetate, rhodium (III) acetylacetonate, chlorotris (triphenylphosphine) rhodium (I) and the like.

Examples of iron compounds include ferrous chloride, ferric chloride, ferrous bromide, ferric bromide, ferric acetate, and iron (III).
Acetyl acetonate, ferrocene and the like are exemplified.

Examples of the titanium compound include titanium tetrachloride, titanium trichloride, bis (cyclopentadienyl) dimethyltitanium, bis (cyclopentadienyl) diethyltitanium, bis (cyclopentadienyl) diisopropyltitanium, bis (methylcyclopentane) Dienyl) dimethyl titanium, bis (cyclopentadienyl) methyl titanium monochloride, bis (cyclopentadienyl) ethyl titanium monochloride, bis (cyclopentadienyl) isopropyl titanium monochloride, bis (cyclopentadienyl) methyl Titanium monobromide, bis (cyclopentadienyl)
Methyl titanium monoiodide, bis (cyclopentadienyl) methyl titanium monofluoride, bis (indenyl) methyl titanium monochloride, bis (indenyl) methyl titanium monobromide, bis (cyclopentadienyl) titanium dichloride, bis (cyclo Pentadienyl)
Titanium dibromide, bis (cyclopentadienyl) titanium diiodide, bis (cyclopentadienyl) titanium difluoride, bis (indenyl) titanium dichloride, bis (indenyl) titanium dichloride, bis (indenyl) titanium dibromide, ethylene Bis (indenyl) titanium dichloride, ethylenebis (indenyl) titanium, tetramethoxytitanium, tetraethoxytitanium, tetra-n-propoxytitanium, tetraisopropoxytitanium, tetra-n-butoxytitanium, tetraisobutoxytitanium, tetra-sec- Butoxytitanium, tetra-tert-butoxytitanium, tetramentoxytitanium and the like are exemplified.

Examples of the zirconium compound include zirconium tetrachloride, bis (cyclopentadienyl) dimethyl zirconium, bis (cyclopentadienyl) diethyl zirconium, bis (cyclopentadienyl) diisopropyl zirconium, and bis (methylcyclopentadienyl) dimethyl Zirconium, bis (cyclopentadienyl) methyl zirconium monochloride, bis (cyclopentadienyl) ethyl zirconium monochloride, bis (cyclopentadienyl) isopropyl zirconium monochloride, bis (cyclopentadienyl) methyl zirconium monobromide, Bis (cyclopentadienyl) methyl zirconium monoiodide, bis (cyclopentadienyl) zirconium dichloride, bis (cyclopentadienyl) zirconium Difluoride, bis (cyclopentadienyl) zirconium dibromide, bis (cyclopentadienyl) zirconium monochloride hydride, bis (indenyl) zirconium dichloride, bis (indenyl) zirconium dibromide, ethylenebis (indenyl) zirconium dichloride, ethylenebis (Indenyl) zirconium dibromide, tetramethoxy zirconium, tetraethoxy zirconium, tetra-n-propoxy zirconium, tetraisopropoxy zirconium, tetra-n-butoxy zirconium, tetraisobutoxy zirconium, tetra-sec-butoxy zirconium, tetra-tret- Butoxyzirconium, tetramentoxyzirconium and the like can be exemplified.

Examples of the hafnium compound include hafnium tetrachloride, bis (cyclopentadienyl) dimethylhafnium, bis (cyclopentadienyl) methylhafnium monochloride, bis (cyclopentadienyl) ethylhafnium monochloride, and bis (cyclopentadiene) (Enyl) hafnium dichloride, bis (cyclopentadienyl) hafnium dibromide, bis (cyclopentadienyl) hafnium monochloride hydride, bis (indenyl) hafnium dichloride, ethylenebis (indenyl) hafnium dichloride, tetraethoxyhafnium, tetra-n -Propoxyhafnium, tetraisopropoxyhafnium, tetra-n-butoxyhafnium, tetra-tert-butoxyhafnium, tetramenthoxyhafnium and the like are exemplified. .

Examples of the vanadium compound include bis (cyclopentadienyl) vanadium dichloride and bis (cyclopentadienyl) vanadium monochloride.

These metal compounds can be used alone or in combination of two or more.

Among the group VIII metal compounds of the periodic table, compounds of highly active metals, for example, compounds of palladium, cobalt and nickel are preferred.

Examples of the aluminoxane (b) include organoaluminum compounds represented by the following general formulas [V] and / or [VI].

(Wherein, R ^{14 to} R ¹⁸ each represent a hydrocarbon group, and n is 1
Examples of the hydrocarbon group of aluminoxane include straight-chain or branched-chain alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, and t-butyl groups. Preferred alkyl groups are methyl and ethyl, especially methyl. n is an integer of 1 or more, preferably 5 or more, more preferably an integer of 10 to 100. The molecular weight of aluminoxane, that is, n, can be determined by a conventional method, for example, a molecular weight measurement method using freezing point depression.

These aluminoxanes can be used as one kind or as a mixture of two or more kinds.

Aluminoxane can be produced, for example, by the following method.

(1) A compound containing adsorbed water, a compound containing water of crystallization, for example, copper sulfate hydrate, aluminum sulfate hydrate, and the like are suspended in an organic solvent such as benzene and toluene, and trialkylaluminum is added. (2) a method in which water is directly added to a trialkylaluminum in an organic solvent to cause a reaction.

Among these methods, the method (1) is preferable.
The aluminoxane may contain a small amount of an organic metal component as long as the catalyst activity is not reduced.

The group VIII metal compound and / or aluminoxane of the periodic table may be supported on a conventional carrier such as silica or alumina.

The amounts and proportions of the Group VIII metal compound and aluminoxane in the periodic table can be selected in a wide range. When performing a polymerization reaction in a liquid phase polymerization reaction system, the amount of the metal compound of Group VIII of the periodic table is, as the concentration of metal atoms, usually 10 ^-8 to 10 ^-1 g atom / L, preferably 10 ^-7 to It is in the range of 10 ^-2 gram atoms / L. The amount of aluminoxane used is usually 10 ⁻⁶ to 10 g atom / L as the concentration of aluminum atoms,
Preferably it is in the range of 10 ^-5 to 10 ^-1 gram atom / L. The ratio of the aluminum atom to the Periodic Table VIII group metal in the polymerization reaction system is usually 1 to 10 ^7, preferably 5 to 10 ⁶
Range.

The polymerization reaction may be carried out in the absence of an organic solvent, but is usually carried out in an inert organic solvent which does not adversely influence the reaction, preferably in a hydrocarbon medium. Examples of the hydrocarbon medium include aliphatic hydrocarbons such as butane, isobutane, pentane, hexane, heptane, and octane; alicyclic hydrocarbons such as cyclohexane; aromatic hydrocarbons such as benzene, toluene, and xylene; Petroleum fractions such as gasoline, kerosene and light oil; mixed solvents thereof; Among these solvents, aromatic hydrocarbons are preferred.

The polymerization method is not particularly limited, and can be selected from conventional polymerization types such as suspension polymerization and solution polymerization. The temperature of the polymerization reaction is usually -50 to 230 ° C, preferably -30 to 200 ° C.
° C, more preferably in the range of 0 to 150 ° C.

After the completion of the polymerization reaction, the polymerization reaction is stopped by pouring the mixture into a mixed solvent of methanol / hydrochloric acid and the like, and a cyclic olefin polymer can be obtained by treating with a conventional method.

The cyclic olefin polymer of the present invention is used in various fields as, for example, paints, adhesives, compatibilizers, resin modifiers, modifiers, photocurable polymers, electron beam curable polymers, and electronic materials. it can.

[Effect of the Invention] The cyclic olefin polymer of the present invention comprises a cyclic olefin,
In spite of using a cyclic olefin having an exocyclic unsaturated bond as a monomer component, it has a high molecular weight and generally has a narrow molecular weight distribution.

Furthermore, the cyclic olefin polymer of the present invention, particularly a cyclic olefin polymer having an exocyclic unsaturated bond, has heat resistance,
It has excellent transparency and strong alkali resistance, is soluble in organic solvents, has a film-forming ability, and can be modified by introducing various functional groups.

When using the cyclic olefin polymerization catalyst of the present invention, the cyclic olefin which may have an exocyclic unsaturated bond can be selectively and highly advanced while suppressing side reactions. it can.

In the production method of the present invention, the polymerization reaction of the cyclic olefin and / or the cyclic olefin having an exocyclic unsaturated bond is selectively and smoothly progressed while suppressing the side reaction, and the high molecular weight cyclic olein polymer is obtained in good yield. Coalescence can be obtained.

EXAMPLES Hereinafter, the present invention will be described in more detail based on examples and comparative examples.

Example 1 In a flask of 300mL substituted [Preparation aluminoxane] nitrogen, CuSO of 18.4 g ₄ · 5
Are suspended and toluene between H ₂ O and 67 mL, in a nitrogen gas atmosphere, trimethyl aluminum 2 diluted with toluene 150mL
4 mL was added dropwise at a temperature of -30 to -20C. After dropping, 0
After stirring at 6 ° C. for 6 hours, the temperature was gradually raised, and the reaction was carried out at 40 ° C. for 12 hours. Next, the reaction product was filtered to perform solid-liquid separation, and the separated liquid was used as an aluminoxane for the polymerization reaction.

[Polymerization reaction] In a 100-mL glass pressure-resistant flask purged with nitrogen gas, 25 mL of toluene, 2 mmol of the above-mentioned methylaluminoxane (6 × 10 ^-2 g atom / L) and palladium (II) chloride
0.1 mmol (3 × 10 ⁻³ gram atoms / L) was added.

Next, 5 mL of 5-vinyl-2-norbornene was added, and a polymerization reaction was performed at 80 ° C. for 8 hours. After completion of the reaction, the reaction was stopped by pouring the reaction product into a methanol / hydrochloric acid mixed solution, and the produced polymer was separated by filtration and dried.
1.62 g of poly (5-vinyl-2-norbornene) was obtained.

When the infrared absorption spectrum of the obtained polymer was measured (using IR-810, manufactured by JASCO Corporation), the wave numbers were 3070, 1630, 980 and 908 cm, as shown in FIG.
^{At -1} , absorption derived from a vinyl group was observed, and absorption at a wave number of 710 to 720 cm ^-1 derived from a double bond in the ring was not observed.

In addition, ¹ H-NMR spectrum (manufactured by JEOL Ltd., JNM-MH
-100) was measured and analyzed. As shown in FIG. 2, 4.8 to 5.2 ppm, 5.5
An absorption of 6.26.2 ppm was observed, but an absorption of 6.0 ppm derived from a proton of a double bond in the ring was not observed. Further, a ¹³ C-NMR spectrum (manufactured by JEOL Ltd., JNM-MH
As a result, the absorption derived from methine of the vinyl group was observed at 111 ppm and 114 ppm, and the absorption derived from methylene was observed at 141 ppm and 144 ppm, but the absorption at 130 to 140 ppm derived from the internal olefin was observed. Was not found.

The molecular weight of the obtained polymer was determined by gel permeation chromatography (manufactured by Shimadzu Corporation).
When measured in chloroform solvent, the number average molecular weight Mn
Is 55000 in terms of polystyrene, and the molecular weight distribution is Mw / Mn = 2.
It was 0.

From the above, in the presence of a catalyst comprising a metal compound of Group VIII of the periodic table and an aluminoxane, 5-vinyl-2-
When norbornene was polymerized, it was clarified that the exocyclic vinyl group did not participate in the polymerization reaction but was polymerized by the addition reaction of the intracyclic double bond.

The obtained polymer was subjected to gravimetric analysis (using TG / DTA200, manufactured by Seiko Instruments Inc.). As a result, the thermal decomposition onset temperature was 363 ° C.

Comparative Example 1 A polymerization reaction was carried out in the same manner as in Example 1 except that 0.4 mmol of triethylaluminum was used instead of methylaluminoxane.
No polymer of vinyl-2-norbornene was obtained.

Example 2 A polymerization reaction was performed in the same manner as in Example 1 except that 0.1 mmol of nickel (II) chloride was used instead of palladium chloride in the polymerization reaction of Example 1. Thus, poly (5-vinyl-2-norbornene) was obtained. ) 0.5 g was obtained.

The infrared absorption spectrum and ¹ H-
The NMR spectrum was measured and analyzed.
Similarly to the above, the polymerization reaction proceeded by the addition reaction of the intracyclic double bond, and the exocyclic vinyl group remained almost without participating in the polymerization reaction.

Example 3 In the polymerization reaction of Example 1, methylaluminoxane was used.
When a polymerization reaction was carried out in the same manner as in Example 1 except that 10 mmol was used, poly (5-vinyl-2-norbornene) was obtained.
2.5 g were obtained.

The infrared absorption spectrum and ¹ H-
The NMR spectrum was measured and analyzed.
Similarly to the above, the polymerization reaction proceeded by the addition reaction of the intra-ring double bond, and the exocyclic vinyl group remained without participating in the polymerization reaction.

The number average molecular weight Mn of the obtained polymer is 38,400,
The molecular weight distribution was Mw / Mn = 3.1.

Example 4 In the polymerization reaction of Example 1, 5-ethylidene-2-norbornene was used instead of 5-vinyl-2-norbornene.
When a polymerization reaction was carried out in the same manner as in Example 1 except that 5 mL was used, poly (5-ethylidene-2-norbornene) 2.
4 g were obtained.

The infrared absorption spectrum and ¹ H-
The NMR spectrum was measured and analyzed.
Similarly to the above, the polymerization reaction proceeded only by the addition reaction of the intra-ring double bond.

Example 5 A polymerization reaction was carried out in the same manner as in Example 1 except that 5 mL of norbornene was used instead of 5-vinyl-2-norbornene in the polymerization reaction of Example 1, and 3.5 g of poly-norbornene was obtained. .

The infrared absorption spectrum and ¹ H-
The NMR spectrum was measured and analyzed.
Similarly to the above, it was confirmed that the polymerization reaction proceeded only by the addition reaction of the intra-ring double bond, and the ring was not opened.

Example 6 In the polymerization reaction of Example 1, except that 0.1 mmol of palladium (II) acetate was used instead of palladium chloride.
When a polymerization reaction was carried out in the same manner as in Example 1, 1.5 g of poly (5-vinyl-2-norbornene) was obtained.

Infrared absorption spectrum and ¹ H-NM of the obtained polymer
From the R spectrum, it was confirmed that the polymerization reaction proceeded by an addition reaction of a double bond in the ring, and the exocyclic vinyl group remained without participating in the polymerization reaction. The number average molecular weight Mn of the obtained polymer was 42,500, and the molecular weight distribution Mw / Mn was 3.0.

Example 7 A polymerization reaction was performed in the same manner as in Example 1 except that palladium (II) acetylacetonate was used in an amount of 0.1 mmol instead of palladium chloride. Vinyl-2-norbornene) was obtained.

Infrared absorption spectrum and ¹ H-NM of the obtained polymer
From the R spectrum, it was confirmed that the polymerization reaction proceeded by an addition reaction of a double bond in the ring, and the exocyclic vinyl group remained without participating in the polymerization reaction. The number average molecular weight Mn of the obtained polymer was 40,100, and the molecular weight distribution Mw / Mn was 3.1.

[Brief description of the drawings]

FIG. 1 is an infrared absorption spectrum chart of the cyclic olefin polymer obtained in Example 1, and FIG. 2 is ¹ H of the cyclic olefin polymer obtained in Example 1.
FIG. 3 is a diagram showing the ¹³ olefin polymer of the cyclic olefin polymer obtained in Example 1.
It is a chart of C-NMR.

Claims (3)

(57) [Claims] [1] The following formula [I] [II] or [III] (Wherein, R ^{1 to} R ¹² are the same or different and each represent a hydrogen atom, a halogen atom, a saturated or unsaturated hydrocarbon group, and in formula [I], at least one of R ¹ and R ² , I
I], at least one of R ^{3 to} R ¹² , or a compound of the formula [II
In I], at least one of R ^{1 to} R ¹⁰ is an unsaturated hydrocarbon group. k and p are integers of 3 or more, m and n
Is an integer of 0 or more.) A cyclic olefin polymer comprising a cyclic olefin repeating unit represented by at least one unit and having a polystyrene equivalent number average molecular weight of 700 to 200,000. 2. A compound represented by the following formula [Ia] [IIa] or [IIIa] (Wherein, R ^{1 to} R ¹² are the same or different and each represent a hydrogen atom, a halogen atom, a saturated or unsaturated hydrocarbon group,
(1) At least one of R ¹ and R ² in the formula [Ia]
In the formula [IIa], at least one of R ^{3 to} R ¹²
Or at least one of R ^{1 to} R ¹⁰ in the formula [IIIa] is an unsaturated hydrocarbon group, or (2) a compound represented by the formula [I
a] In [IIa] or [IIIa], R ^{1 to} R ¹² are the same or different and are a hydrogen atom, a halogen atom or a saturated hydrocarbon group. k and p are integers of 3 or more, and m and n are 0
A polymerization catalyst for polymerizing at least one cyclic olefin represented by the following formula (1) by an addition reaction of a double bond in the ring, comprising a combination of a metal compound of Group VIII of the periodic table and an aluminoxane. A polymerization catalyst comprising 3. A cyclic olefin polymerizable by polymerizing the cyclic olefin according to claim 2 by an addition reaction of a double bond in the ring in the presence of a polymerization catalyst comprising a combination of a metal compound of Group VIII of the periodic table and an aluminoxane. Manufacturing method of coalescence.