JPH03205408A - Cycloolefin polymer, catalyst for polymerizing cycloolefin and production of the same polymer - Google Patents

Abstract

PURPOSE:To obtain a high-mol.wt. cycloolefin polymer in good yiedls by polymerizing a cycloolefin or a cycloolefin having an unsaturated bond outside the ring in the presence of a specified polymerization catalyst. CONSTITUTION:A polymerization catalyst is obtained by combining 10<-8>-10<-1>g atom/l (in terms of the metal) of a compound of a transition metal selected from among IVB, VB and VIII groups of the periodic table [e.g. palladium (II) acetate] with 10<-6>-10g atom/l (in terms of Al) of aluminoxanes of formulas I and/or II (wherein R<14> to R<18> are each a hydrocarbon group; and n>=1) in a ratio of the number of the Al atoms to that of the transition metal atoms of 1-10<7>. A cycloolefin (e.g. cyclopropene) or a cycloolefin having an unsaturated bond outside the ring (e.g. 5-vinyl-2-norbornene) is polymerized at -50 to 230 deg.C in the presence of said polymerization catalyst to obtain a cycloolefin polymer comprising at least one kind of repeating units of formulas III-V [wherein R<1> to R<12> are each H, halogen or an (un)saturated hydrocarbon group; l and p each >=3; and m and n each >=0) and having a number-average mol.wt. (in terms of PS) of 700-200000.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a cyclic olefin polymer containing a cyclic olefin or a cyclic olefin having an extracyclic unsaturated bond as a monomer, a polymerization catalyst for the cyclic olefin, and The present invention relates to a method for producing a cyclic olefin polymer.

[Prior art and problems to be solved by the invention] Conventionally, cyclic olefin polymers with excellent alkali resistance are titanium-based catalysts made of a titanium compound and an organoaluminum compound, and vanadium-based catalysts made of a vanadium compound and an organoaluminum compound. 7L: It is produced by polymerizing a cyclic olefin.

However, these catalyst systems have low catalytic activity, making it difficult to increase the polymerization reactivity of cyclic olefins, and when using a large amount of cyclic olefins, the catalytic activity is impaired. Furthermore, side reactions such as ring-opening polymerization reactions and isomerization reactions are likely to occur. In particular, vanadium-based catalysts have extremely low polymerization activity compared to titanium-based catalysts. Therefore, it is difficult to obtain a high-molecular-weight cyclic olefin homopolymer, and many copolymers with ethylene have been reported (Japanese Patent Laid-Open Nos. 59-16995 and 1981-120816). , and Japanese Patent Application Laid-Open No. 61-272216).

Additionally, a catalyst consisting of a transition metal compound and an aluminoxane has been proposed as a polymerization catalyst for the copolymerization reaction of an α-olefin and a cyclic olefin [JP-A-61-2212
No. 06, JP 1-15 [1308, Journal of Polymer Science Chemistry Edition (J. PolyrFl. Sci.
m. Ed. ) (23) 2151-21134 (
1985) ), Macromolecular Chemistry (Ma
kromol. Chem. ) (190), 5l5
~52B (1989) Ko.

However, all of these prior art documents relate to the copolymerization of α-olefins and cyclic olefins, and these prior art documents do not describe the copolymerization of cyclic olefins or cyclic olefins having an extracyclic unsaturated bond. has not been disclosed at all.

In addition, although the copolymer of α-olefin and cyclic olefin produced using the above catalyst has superior heat resistance compared to polyolefin, it contains α-olefin units, so it is difficult to improve heat resistance. There are limits. In addition, it has a high α-olefin content and is insoluble in general-purpose organic solvents, so
In addition, the properties of the film type are 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 extracyclic unsaturated bond, Kennedy (Mennedy)
[Journal of
Macromolecules Science Chemistry Edition (J. Macromol. Sci(chem)
．． ) At (3) 345 (19[i7) 'II
; Method using a palladium compound as a catalyst [Journal of Polymer Science (J. Polym
．． Set. ) B4 541 (19f3B), and US Pat. No. 3,494,897] are known.

However, methods using cationic polymerization tend to cause side reactions such as isomerization reactions, ring-opening reactions, and crosslinking.
It is necessary to carry out the polymerization at a low temperature of .degree. C. or lower, which not only reduces production efficiency but also lowers the yield of the cyclic olefin polymer. On the other hand, in the method using a palladium compound as a catalyst, the monomer forms a complex with the catalyst and is stabilized, and the polymerization activity is low, so the yield of the cyclic olefin polymer is also low. Therefore, when producing cyclic olefins or polymers of cyclic olefins having an extracyclic unsaturated bond by these methods, it is difficult to efficiently produce a polymer with film-forming ability. .

In this way, cyclic olefins and cyclic olefins having an unsaturated bond outside the ring tend to undergo side reactions such as ring-opening reactions, isomerization reactions, and crosslinking during polymerization, and therefore the molecular weight distribution of the obtained polymers is affected. It has the special feature of being easy to expand. Therefore, a catalyst system with excellent polymerization activity that allows the polymerization reaction to proceed selectively at endocyclic or exocyclic unsaturated bonds; a high-molecular-weight cyclic olefin polymer; There is a strong need for a method to obtain union.

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 extracyclic unsaturated bond as a monomer.

Another object of the present invention is to provide a high molecular weight cyclic olefin polymer with a narrow molecular weight distribution.

Still another object of the present invention is to provide a cyclic olefin polymer that has excellent heat resistance, transparency, and strong alkali resistance, is soluble in organic solvents, has film-forming ability, and can be modified by introducing various functional groups. It is about providing.

Another object of the present invention is to provide a cyclic olefin polymerization catalyst that can selectively and highly polymerize cyclic olefins that may have unsaturated bonds while suppressing side reactions. Our goal is to provide the following.

6 Still another object of the present invention is to selectively and smoothly proceed with the polymerization reaction of a cyclic olefin and/or a cyclic olefin having an unsaturated bond on the outside of the ring, while suppressing side reactions. The object of the present invention is to provide a production method capable of obtaining a high molecular weight cyclic olein polymer.

[Structure of the Invention] In order to achieve the above object, the present invention comprises a repeating unit of a cyclic olefin and/or a cyclic olefin having an unsaturated bond, and has a number average molecular weight in terms of boristyrene of 700 to 20. A cyclic olefin polymer having 0 0 C:l O is provided.

The present invention also provides a polymerization catalyst for a cyclic olefin or a cyclic olefin having an extracyclic unsaturated bond, which comprises a transition metal compound and aluminoxane.

Furthermore, the present invention provides a method for producing a cyclic olefin polymer, in which a cyclic olefin or a cyclic olefin having an extracyclic unsaturated bond is polymerized in the presence of a transition metal compound and aluminoxane.

The present invention will be explained in detail below.

Repeating the cyclic olefin polymer of the present invention! The ll-position is composed of at least one unit represented by the following formulas [I], [II] and [■].

(In the formula, R1 to RI2 are the same or different and represent a hydrogen atom, a halogen atom, or a saturated or unsaturated hydrocarbon group.

and p are integers of 3 or more, and m and n are integers of 0 or more.) The halogen atoms of R1 to R12 include fluorine, chlorine, bromine, and iodine atoms. Saturated hydrocarbon groups include
For example, alkyl groups having 1 to 20 carbon atoms, cycloalkyl groups, etc. are included. In addition, as unsaturated hydrocarbon groups,
Examples include vinyl and ethylidene groups.

Among the cyclic olefins corresponding to the unit represented by the formula [1], examples of cyclic olefins having an unsaturated bond in the ring include cyclopropene, cyclobutene, cyclopentene, 3-methylcyclopentene, and 4-methylcyclopentene. , 3-chlorocyclobentene, cyclohexene, 3-methylcyclohexene, 4-methylcyclohexene, 3,4-dimethylcyclohexene, 3-chlorocyclohexene, cycloheptene, cyclooctene, cyclodecene, and cyclododecene.

Among the cyclic olefins corresponding to the r-1i position represented by the formula [1], examples of the cyclic olefins having an unsaturated bond outside the ring include vinylcycloben9tene, vinylcycloheptene, and 4- vinyl-1cyclo5
Examples include xene.

Among the cyclic olefins corresponding to the unit represented by the formula [I1], examples of the cyclic olefins having an unsaturated bond in the ring include norbornene, 5-methyl-2-norbornene, 5-ethyl-2-norbornene, Bicycloalkenes such as 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 octahydronaphthanone, 2-Ethyl-145,8-dimethano-I+ 2.3,4.4a,58,8a-octahydronaphthalene, 2-probyl-1.4,5.8-dimethano-1.23.44a,5,8 .8a-octahyde naphthalene, 2-n-butyl-1,4,5.8-dimethano-12.3,4.4a,5 8 8a-octahyF
Naphthalene, 2-isobutyl-1.4,5,810 Dimethano-1.2,3,4,4a,5,8,8a-Octahydronaphthalene, 2-hexyl-1.4.5.8-
Dimethano-1+ 2+ 3,4,4 a,5,8,
8a-octahydronaphthalene, 2-stearyl 1.
4,5.8-dimethano-1,2,3.4.4a,5,8
．． 8a-octahydronaphthalene, 2,3-dimethyl-
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-dimethano1,2,3
,4,4a,5,8.8a-octahyde naphthalene,
2-chloro1.4.5.8-dimethano-1.2,3,
4.4g, 5,8,8a-octahyde naphthalene, 2
-bromo1.4.5.8-dimethano-1 + 2+
3 + 4 + 4 a *5.8.8a-octahydronaphthalene, 2-fluoro 1.4,5.8-dimethano 1,2.3,4,4a,5.8.8a-octahydronaphthalene 11 2,3-dichloro-1,4,5,8-dimethano-1
．． Tetracycloalkenes such as 2,3,4,4a,5,8,8a-octahydronaphthalene; 3,8 10
．． 13 Hexacyclo[6,6,1,1 . 12.7
9.14 0 0 ] hebutadecene-4, pentasic 2,9
4,7 11.18 b [8.8,1. ,1 ,1 ,0,L8
12,17 0 0 ] Henikosen-5, Octashi 2.9
4,7 11.18 Kuro [8.8,1 ,1 . 118,16
3,8 12.171 ,0,0.0
1. Polycycloalkenes such as docosene-5 and the like can be mentioned.

Among the cyclic olefins corresponding to the unit represented by the formula [I1], examples of cyclic olefins having an unsaturated bond outside the ring include 5-vinyl-2-norbornene, 8-vinyltetracyclo[4,4 ,2.5 7.10 0,1. 1]-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 [nI] include 2,3.3a,7atetrahydro4,7-methanol1H-indene, 3a. Tricycloalkenes such as 5,6,7a-tetrahydro-4,7methanol 1H-indene; dicyclopentadiene, dicyclopentadienylheptene, alkylidene tetrahydroindene, 3a,4,7,7a-
Examples include cyclic polyenes such as tetrahydroindene.

One or more types of these cyclic olefins can be used.

The molecular weight of the cyclic olefin polymer is a number average molecular weight of 700 to 200,000, preferably 100 in terms of polystyrene.
0 to 150,000, more preferably 10,000 to 10
It is 0000.

The cyclic olefin polymer of the present invention has excellent transparency and heat resistance. For example, the repetition represented by the following formula [IV]! The polymer consisting of the lt position, i.e., 13 poly(5-vinyl-2-norbornene), has high transparency and its thermal onset temperature is usually 250°C or higher, preferably about 300 to 500°C. .

The cyclic olefin polymer of the present invention is a copolymer of an α-olefin and a cyclic olefin, exhibits high solubility in organic solvents, and has a high film-forming ability. For example, a polymer composed of repeating units represented by the formula [IV] has excellent solubility in various organic solvents such as chloroform, dichloromethane, tetrahydrofuran, and decalin at room temperature.

Further, the cyclic olefin polymer of the present invention, particularly poly(5-vinyl-2-norbornene), has the characteristic that it is not attacked by strong alkalis.

In the cyclic olefin polymer, a polymer containing a cyclic olefin unit having an unsaturated bond, especially a vinyl group, on the outside of the ring,
Among these, the polymer consisting of the repeating unit represented by the formula [IV] can be prepared by various known reactions such as halogenation, epoxidation, alcoholization, and hydroformylation reactions to unsaturated bonds. can be modified by introducing functional groups.

14 The cyclic olefin polymer of the present invention, in the presence of a catalyst consisting of (a) a transition metal compound and (b) aluminoxane,
It is obtained by polymerizing a cyclic olefin and/or a cyclic olefin having an extracyclic unsaturated bond.

The transition metal compound (a) of the catalyst structure is I of the periodic table.
It is a transition metal compound selected from the group consisting of Group VB, Group VB, and Group II. Examples of the transition metals of Group IVB, Group VB, and Group II of the periodic table include titanium, zirconium, hafnium, vanadium, iron, cobalt, nickel, palladium, platinum, and rhodium.

The transition metal compound is not particularly limited as long as it is a compound containing the above transition metal, and includes, for example, a metal compound having a halogen atom, a metal compound having a hydrocarbon atom, an organic acid salt, an alcoholate, a complex, an oxide, etc. Good too.

Among transition metal compounds, palladium compounds include, for example, palladium (I [l acetate, palladium [1
) acetylacetonate, palladium(0)bis(dibenzylideneacetone), palladium(II) bromide, palladium(Illchloride, palladium(I[)iodide, palladium[I[)oxide, monoacetonitrile tris(triphenyl) phosphine) palladium [11tetrafluorobonite [Pd
(CH3 CN) (PPh3 )3 ] (BF4
)2, tetrakis(acetonitrile)palladium[1
] Te1-lafluoroborate, dichlorobis(acetonitrile)palladium [I[1], dichlorobis(triphenylphosphine)palladium [l], dichlorobis(penzonitrile)palladium (Ill), and the like.

Examples of iron compounds include ferrous chloride, ferric chloride,
Ferrous bromide, ferric bromide, ferric acetate, v. (I[l acetylacetate, ferrocene, etc. are exemplified.

As a cobalt compound, for example, cobalt acetate (1)
, cobalt [11 acetylacetonate, cobalt (
Auto) Acetyl acetate, cobal benzoate l- (
H), cobalt chloride, cobalt bromide 1-, cobalt 4-cyclohexylbutyrate, cobalt stearate [11]
, tetrafluoroborate, and the like.

Examples of the nickel compound include nickelosene, nickel acetate (Ill), nickel [II1 acetylacetonate, nickel bromide, nickel chloride, nickel 4-cyclohexylbutyrate, nickel lactate, nickel oxide, nickel tetrafluoroborate, etc. .

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

Examples of titanium compounds include titanium tetrachloride, titanium trichloride, bis(cyclopentadienyl)dimethyltitanium, bis(cyclopentadienyl)diethyltitanium, bis(cyclopendadienyl)diisopropyl titanium, bis(methyl cyclopentadienyl) dimethyl titanium, bis(cyclopentadienyl) methyl titanium monochloride,
Bis(cyclopentadienyl)ethyl titanium monochloride, bis(cyclopentadienyl)isoprobyl titanium 1
7 monochloride, bis(cyclopentadienyl)methyltitanium monobromide, bis(cyclopentadienyl)methyltitanium monoiodide, bis(cyclopendadienyl)methyltitanium monofluoride, bis(indenyl)
Methyl titanium monochloride, bis (indenyl) methyl titanium monobromide, bis (cyclopentadienyl) titanium dichloride, bis (cyclopentadienyl) titanium dibromide, bis (cyclopentadienyl) titanium diiodide, bis (cyclo pentadienyl) titanium difluoride, 'bis(indenyl) titanium dichloride,
Bis(indenyl)titanium dichloride, bis(indenyl)titanium dibromide, ethylenebis(indenyl)titanium dichloride, ethyl-nonbis(indenyl)titanium, tetramethoxytitanium, tetraethyl-oxytitanium, tetra-n-propoxytitanium, te-lyso Proboxy titanium, Tetra n-butoxy titanium, Te1.
Lysobutoxytitanium, Tetra terL-butoxytitanium, Tetra terL-butoxytitanium, Tetra 1
8 Menthoxytitanium and the like are exemplified.

Examples of zirconium compounds include zirconium tetrachloride, bis(cyclopentadienyl)dimethylzirconium, bis(cyclopentadienyl)diethylzirconium, bis(cyclopentadienyl)diisoprobylzirconium, and bis(methylcyclopentadienyl). ) dimethylzirconium, bis(cyclopentadienyl)methylzirconium monochloride, bis(cyclopentadienyl)ethylzirconium monochloride, bis(cyclopentadienyl)isoprobylzirconium monochloride, bis(cyclopentadienyl)methylzirconium Monobromide, bis(cyclopentadienyl)methylzirconium monoiodide, bis(cyclopentadienyl)zirconium dichloride, bis(cyclopentadienyl)zirconium difluoride, bis(cyclopentadienyl)zirconium dibromide, bis( cyclopentadienyl) zirconium mono”chloride hydride, bis(indenyl) zirconium dichloride, bis(indenyl) zirconium dibromide,
ethylene bis(indenyl) zirconium dichloride,
ethylene bis(indenyl) zirconium dibromide,
Tetramethoxyzirconium, Tetraethoxyzirconium, Tetra n-proboxyzirconium, Tetraisopropoxyzirconium, Tetra n-butoxyzirconium, Tetraisobutoxyzirconium, Tetra-
Examples include sec-butoxyzirconium, tetra-tert-butoxyzirconium, and tetramentoxyzirconium.

Examples of hafnium compounds include hafnium tetrachloride, bis(cyclopentadienyl)dimethyl hafnium,
Bis(cyclopentadienyl) methyl hafnium monochloride, bis(cyclopentadienyl) ethyl hafnium monochloride, bis(cyclopentadienyl) hafnium dichloride, bis(cyclopentadienyl) hafnium dibromide, bis(cyclopentadienyl) hafnium dibromide ethylene) hafnium monochloride hydride, bis(indenyl) hafnium dichloride, ethylene bis(indenyl) hafnium dichloride, tetraethoxy hafnium,
Examples include tetra-n-proboxy hafnium, tetra-isopropoxy hafnium, tetra-n-butoxy hafnium, tetra-tert-butoxy hafnium, and tetramentoxy hafnium.

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

Among these transition metal compounds, highly active metal compounds such as palladium, iron, cobalt, nickel, titanium, and zirconium compounds are preferred. These transition metal compounds can be used alone or in combination of two or more.

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

21 (In the formula, RI4 to R18 each represent a hydrocarbon group, and n represents an integer of 1 or more.) Examples of the hydrocarbon group of aluminoxane include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t - Straight chain or branched alkyl groups such as butyl groups are exemplified. Preferred alkyl groups are methyl and ethyl, especially methyl. n is an integer of 1 or more, preferably 5 or more, more preferably 10 to 100. The molecular weight of aluminoxane, that is, n, can be determined by a conventional method, for example, a molecular weight measuring method using freezing point depression.

These aluminoxanes can be used alone or as a mixture of two or more.

2 2 Aluminoxane can be produced, for example, by the following method.

(1) A compound containing adsorbed water, a compound containing crystal water, such as copper sulfate permanent, aluminum sulfate hydrate, etc., is suspended in an organic solvent such as benzene or toluene,
A method of adding and reacting trialkylaluminium;
(2) A method in which water is directly added to trialkylaluminium in an organic solvent to cause a reaction.

Among these methods, method (1) above is preferred. Note that the aluminoxane may contain a small amount of organometallic component within a range that does not reduce the catalytic activity.

The transition metal compound and/or aluminoxane may be supported on a conventional carrier such as silica, alumina, etc.

The amounts and proportions of transition metal compounds and aluminoxane used can be selected within a wide range. When the polymerization reaction is carried out in a liquid phase polymerization reaction system, the amount of the transition metal compound to be used is usually 10-8 to 2310-1 gram atoms/g, preferably 10-7 to 10-1, in terms of metal atom concentration.
2 grams atom/. l! is within the range of The amount of aluminosaquin used is usually 106 to 10 gram atoms/.in terms of aluminum atom concentration. Q, preferably 10
~10-1 gram atoms/. The range of Q is -5. The ratio of aluminum to transition metal in the heavy reaction system is usually 1 to 1. ．． 07, preferably in the range of 5 to 106.

Can the polymerization reaction be carried out in the absence of an organic solvent?
The reaction is usually carried out in an inert organic solvent, preferably a hydrocarbon medium, which does not adversely affect the reaction. Hydrocarbon media include, for example, aliphatic hydrocarbons such as butane, isobutane, pentane, hexane, heptane, octane;
Alicyclic hydrocarbons such as cyclohexane; aromatic hydrocarbons such as benzene, toluene, and xylene; gasoline,
Ishiura distillate of Torioki, Karuyu Nato: Examples include mixed solvents of these. Among these solvents, aromatic hydrocarbons are preferred.

The polymerization method is not particularly limited, and a conventional polymerization method, 24 For example, it can be selected from suspension polymerization, solution polymerization, etc.

The temperature of the polymerization reaction is usually in the range of -50 to 230°C, preferably -30 to 200°C, more preferably 0 to 150°C.

After the polymerization reaction is completed, the polymerization reaction is stopped by pouring the mixture into a methanol/hydrochloric acid mixed solvent or the like, and a cyclic olefin polymer can be obtained by processing in a conventional manner.

The cyclic olefin polymer of the present invention can be used in various fields, such as paints, adhesives, compatibilizers, resin modifiers, modification aids, photo-curable polymers, electron beam-curable polymers, and electronic materials. can.

[Effects of the Invention] The cyclic olefin polymer of the present invention has a high molecular weight and generally has a narrow molecular weight distribution, even though the monomer is a cyclic olefin or a cyclic olefin having an extracyclic unsaturated bond.

Furthermore, the cyclic olefin polymer of the present invention, particularly the cyclic olefin polymer having an extracyclic unsaturated bond, has excellent heat resistance, transparency, and strong alkali resistance, and has the ability to dissolve in organic solvents and form a film. , modification by introducing various functional groups is possible.

When using the cyclic olefin polymerization catalyst of the present invention,
It is possible to selectively and highly polymerize a cyclic olefin that may have an extracyclic unsaturated bond while suppressing side reactions.

In the production method of the present invention, the polymerization reaction of a cyclic olefin and/or a cyclic olefin having an extracyclic unsaturated bond proceeds selectively and smoothly while suppressing side reactions, thereby producing a high-molecular-weight cyclic olefin in good yield. Polymers can be obtained.

[Examples] The present invention will be described in more detail below based on Examples and Comparative Examples.

Example 1 [Preparation of aluminoxane] In a 300 ml flask purged with nitrogen, 18.
Suspend 4g of CuSO4 ◆5H20 and 67ml of toluene, and add 150ml of toluene under nitrogen gas atmosphere.
24ml of trimethylaluminum diluted with 126 ml of trimethylaluminum was added dropwise at a temperature of -30 to -20°C. After completion of dripping, 0
After stirring at ℃ for 6 hours, the temperature was gradually raised and the mixture was reacted at 40 ℃ for 12 hours. Next, the reaction product was filtered to perform solid-liquid separation, and the separated liquid was used as aluminoxane in a polymerization reaction.

[Polymerization reaction] In a 100 ml glass pressure flask purged with nitrogen gas, 25 ml of toluene, 2 mmol of the above methylaluminoxane (6 x 10-2 gram atoms/j?) and 0.1 mmol (3 mmol) of palladium (I) chloride were added. x 10-8 gram atoms/g) was added.

Next, 5 ml of 5-vinyl-2-norbornene was added, and a polymerization reaction was carried out at 80°C for 8 hours. After the reaction is complete, the reaction is stopped by pouring the reactant into a methanol/hydrochloric acid mixed solution, and the resulting polymer is filtered 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 an IR-810 instrument made by Nihon Bunko Co., Ltd.), as shown in Figure 1, wave numbers of 3.070, 27 1630, 980 and 908 cm-ll: Absorption originating from the hinyl group was observed, and absorption at a wave number of 710 to 720 cm-' originating from the double bond in the ring was not observed.

In addition, 'H-NMR spectrum (manufactured by ■ Hondenshi ■, JNM-
MH-100) was measured and analyzed, and as shown in Figure 2, 4.8~
Absorption at 5.2 ppm and 5.5 to 6.2 ppm was observed, but absorption at 6.0 ppm derived from the proton of the double bond in the ring was observed.
No absorption of PM was observed. Furthermore, “'C-NM
R spectrum (manufactured by JEOL Ltd., J NM-MH-1
When measured and analyzed, the absorption derived from methine in the vinyl group was 1 1 1 ppm and 1 i 4
ppm, the absorption derived from methylene is 1.4 1 pI
) m and 1 4 4 pl) m, but no absorption of 130 to 140 ppm derived from internal olefins was observed.

The molecular weight of the obtained polymer is determined by gel permeation.
When measured by chromatography (manufactured by Shimadzu Corporation) in chloroform solvent, the number average molecular weight Mn was 55,000 in terms of polystyrene.
The molecular weight distribution was Mw/Mn=2.0.

From the above, when 5-vinyl-2-norbornene is polymerized in the presence of a catalyst consisting of a transition metal compound and aluminoxane, the vinyl group outside the ring is not involved in the polymerization reaction, but the vinyl group inside the ring is It has become clear that polymerization occurs through the addition reaction of heavy bonds.

Further, when the obtained polymer was subjected to gravimetric thermal analysis (manufactured by Seiko Electronics Co., Ltd., using TG/DTA200), the thermal decomposition initiation temperature was 363°C.

Comparative Example 1 In the polymerization reaction of Example 1, 0.0% triethylaluminum was used instead of methylaluminoxane. A polymerization reaction was carried out in the same manner as in Example 1 except that 4 mmol was used.
A polymer of 5-vinyl-2-norbornene was not obtained.

Example 2 In the polymerization reaction of Example 1, a polymerization reaction was carried out in the same manner as in Example 1 except that 0.1 mmol of nickel (I) chloride was used instead of palladium chloride, and poly(5-vinyl -2-norbornene) 0.5 g was obtained.

Infrared absorption spectrum and 'H-
When the NMR spectrum was measured and analyzed, it was found that, as in Example 1, the polymerization reaction proceeded due to the addition reaction of the endocyclic double bond, and the exocyclic vinyl group remained without almost participating in the polymerization reaction. .

Example 3 In the polymerization reaction of Example 1, methylaluminoxane 1
A polymerization reaction was carried out in the same manner as in Example 1 except that 0 mmol was used, and poly(5-vinyl 2-norbornene) 2
．． 5g was obtained.

Infrared absorption spectrum and 'H-
When the NMR spectrum was measured and analyzed, it was found that, as in Example 1, the polymerization reaction proceeded due to the addition reaction of the endocyclic double bond, and the exocyclic vinyl group remained without participating in the polymerization reaction.

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

Example 4 In the polymerization reaction of Example 1, 5-ethylidene-2-norporene 5 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 ml was used, poly(5-ethylidene-2-norbornene) 2
．． 4g was obtained.

Infrared absorption spectrum and 'H-
When the NMR spectrum was measured and analyzed, it was found that, as in Example 1, the polymerization reaction proceeded only by the addition reaction of the endocyclic double bond.

Example 5 In the polymerization reaction of Example 2, the 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, and 3.5 g of polynorbornene was obtained. .

Infrared absorption spectrum and 'H-
When the NMR spectrum was measured and analyzed, it was confirmed that, as in Example 1, the polymerization reaction proceeded only by the addition reaction of the intracyclic double bond, and no ring opening occurred.

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

The infrared absorption of the obtained polymer is
It was confirmed from NMR spectrum that the polymerization reaction proceeded by an addition reaction of the double bond within the ring, and the vinyl group outside the ring remained without participating in the polymerization reaction. The number average molecular weight Mn of the obtained polymer was 42,500, and the molecular weight (I
JMw/Mn=3. It was 0.

Example 7 In the polymerization reaction of Example 1, the polymerization reaction was carried out in the same manner as in Example 1, except that 0.1 mmol of palladium (ml acetylacetonate) was used instead of palladium chloride. (5-vinyl-2-norbornene) was obtained.

32 Infrared absorption spectrum and 1H-N of the obtained polymer
From the MR spectrum, it was confirmed that the polymerization reaction proceeded as an addition reaction of the double bond within the ring, and that the vinyl group outside the ring remained without participating in the polymerization reaction. The number average molecule l of the obtained polymer! lilM n was 40,100, and the molecular weight distribution Mw/Mn was 3.1.

[Brief explanation of drawings]

Figure 1 is an infrared absorption spectrum chart of the cyclic olefin composite obtained in Example 1, Figure 2 is an H-NMR chart of the cyclic olefin composite obtained in Example 1, and Figure 3 is an H-NMR chart of the cyclic olefin composite obtained in Example 1. 13C of the cyclic olefin compound
-NMR chart. heavy heavy heavy heavy

Claims (1)

[Scope of Claims] 1. A cyclic olefin polymer consisting of repeating units of a cyclic olefin and/or a cyclic olefin having an extracyclic unsaturated bond, and having a number average molecular weight in terms of polystyrene of 700 to 200,000. 2. A polymerization catalyst for a cyclic olefin or a cyclic olefin having an extracyclic unsaturated bond, which comprises a transition metal compound and aluminoxane. 3. A method for producing a cyclic olefin polymer, which comprises polymerizing a cyclic olefin or a cyclic olefin having an extracyclic unsaturated bond in the presence of a transition metal compound and aluminoxane. 4. A cyclic olefin having an extracyclic unsaturated bond is 5-
4. The method for producing a cyclic olefin polymer according to claim 3, wherein the cyclic olefin polymer is vinyl-2-norbornene.