JPS6043366B2 - Method for producing ring-opening polymer - Google Patents

Description

[Detailed description of the invention] The present invention relates to a method for producing a circular polymer.

More specifically, norbornene derivatives and/or norbornadiene derivatives, or mixtures thereof with cycloolefin compounds copolymerizable with them, are used in groups IA, ■Al■B, ■B, ■A, and ■B of the periodic table. Circular polymerization using an organometallic compound having at least one metal selected from the group consisting of metals and a catalyst system obtained from (B) "carpine complex of tungsten or molybdenum" (hereinafter referred to as "carpine complex") The present invention relates to a method for producing a circular polymer characterized by the following. Some of the present inventors have already reported on a method for producing the same circular ring polymer in Japanese Patent Publication No. 50-2372 and Japanese Patent Publication No. 49-67.
99, 49-7799, etc.

However, when producing circular polymers by the above-mentioned methods, the polymerization activity of these catalyst systems is not necessarily satisfactory.

Furthermore, as a result of various searches for obtaining a catalyst system with excellent catalytic activity, the present inventors have found that a catalyst system obtained from an organometallic compound and a carbon complex can be obtained by combining the above-mentioned norbornene derivatives or the norbornene derivatives with a small amount of cycloolefin. The inventors have discovered that a circular polymer can be obtained in high yield by carrying out circular polymerization with a system compound, and have arrived at the present invention.

Since the catalyst system used in the present invention has a very high polymerization activity (catalytic activity), it is possible not only to reduce the amount of catalyst used, but also to increase the production efficiency of the polymerization apparatus.

In addition, since the amount of catalyst used can be small, after the polymerization is completed,
It is relatively easy to remove catalyst residues remaining in the resulting ring-opened polymer. Furthermore, since the catalyst system used in the present invention exhibits little decrease in activity due to the polar groups of the monomers, ring-opening polymerization can be continued for a long time.
The norbornene derivative used in the present invention is a polar group or a hydrocarbon group having at most 2 carbon atoms substituted with 1 to m polar groups, or an aromatic hydrocarbon group having at most 2 carbon atoms. It is a norbornene derivative having a group.

The above polar groups include "chlorine atom, bromine atom, cyano group (nitrile group), ester group and ether group having at most 20 carbon atoms, amide group, 64 heterocycle containing at least one nitrogen atom" Aromatic
Haracterl Chemistry Dictionary Editorial Committee, ゜Chemistry Dictionary゛Volume 8, Page 601, 1962, Published by Kyoritsu Publishing Co., Ltd.
Reference) Groups having a heterocyclic ring (hereinafter referred to as 5 aromatic nitrogen-containing heterocyclic groups), N-substituted amide groups substituted with a hydrocarbon group having at most 5 carbon atoms, and aromatic groups "Nitrogen-containing heterocyclic group" (hereinafter referred to as "A group polar group")
, refers to acid anhydride groups as well as imide groups.

The general formula of typical norbornene derivatives is the following formula [(
1) Formula and (■) Formula].

In the formula, Wl, Xl, Yl and l and W2,
X2, Y2 and l may be the same or different, and may be hydrogen atoms, alkyl, alkenyl, cycloalkyl, cycloalkynole substituted with an alkyl group, arynole (A
ryl) and aranolequinole group, the above-mentioned A group polar group, the above-mentioned hydrocarbon group substituted with an A group polar group, or an imide group [general The formula is 1(CH2)n-
N [ ]R1 (However, R1 has at most 6 carbon atoms
Wl, Xl, Yl and l or W2, X2, Y2
and Z2, at least one is an A group polar group, a hydrocarbon group substituted with an A group polar group, an imide group, or an aromatic hydrocarbon group.

The general formulas of other typical norbornene derivatives are shown by the following formulas [formula (■) and formula (■)].

In the formula, W3 and l and W4 and Y4 may be the same or different, and are a hydrogen atom, the above hydrocarbon group, the above ester group or ether group, or a hydrocarbon group substituted by an ester group or ether group, and A
The general formula is -COOR2-R3-00C--COOR4
-R5OR6-, -R7O-,
or ') E [However, R3, R4, R5, R6, R7, R9 and Rl2 may be the same or different, and have at most 2 carbon atoms.
The alkylene group of the fence, R2, R8, RlO and R
ll may be the same or different types, and is the above hydrocarbon group,
The general formula of E is ゛? (However, B is a hydrocarbon having at most 20 carbon atoms, D is oxygen or "N-R (However, R is the above-mentioned hydrocarbon group), and I and m are independently 0. , 1 or 2, and q is 0 or 1)].

Representative examples of these ilbornene derivatives are
-23720, JP-A-49-67999, JP-A No. 49-
7799-gin, 50-7180-inch, 50-753 (g), 50-1531 (4), 50-11000-inch, 50-11250-inch, and 50-16040-inch, each publication specification and special It is described in Japanese Patent Application No. 129581/1981. Among these norbornene derivatives, particularly representative ones include 5-cyanobicyclo[2,2,1]-heptene-2, 5,5-dicyanobicyclo[2,2,1]-heptene-2, 5,6-dicyanobicyclo[2,2,1]heptene-2,5-cyano5-methyl-bicyclo[2,2,1]-heptene-2,5-cyano6-methyl-bicyclo[2,2,1 ]
-Heptene-2,5-cyano-5-ethylbicyclo [
2,2,1]Heptene-2,5-cyanomethyl-bicyclo[2,2,1]-heptene-2,5-methoxycarbonyl-bicyclo[2,2,1]-heptene-2,5-methyl-methoxycarbonyl Bicyclo[2,2,1]-
Heptene-2,5,6-dimethoxycarbonylbicyclo[2,2,1]-Heptene-2,5-acetoxybicyclo[2,2,1]-Heptene-2,5-methoxybicyclo[2,2,1] -Heptene-2,5-Chlorubicyclo[2,2,1]-Heptene-2,5-chloromethyl-Bicyclo[2,2,1]-Heptene-2,5,6
-bis(chloromethyl)-bicyclo[2,2,1]-heptene-2,5-chloro-5-cyanobicyclo[2,
2,1]-heptene-2,5-cyano5-methoxycarbonylrubicyclo[2,2,1]-heptene-2,N
, N-dimethyl-bicyclo[2,2,1]-heptene-2-carbonamide 5,5-(2!-pyridyl)-bicyclo[2,2,1]-heptene-2,2-(2″-pyridyl )-1,4;5,8-dimethanol 1,2,3,4
、． 4a,5,8,8a-octahydronaphthalene, 3
, 6-methylene-1,2,3,6-tetrahydrosis-phthalic anhydride, 1,45,8-dimethanol 1,2,
3,4,4a,5,8,&i-octahydronaphthalene-2,3-dicarboxylic anhydride, N-methyl-3,6-
Methylene-1,2,3,6-tetrahydrosis-phthalimide, N-n-butyl-3,6-methylene-1,2
, 3,6-tetrahydrosis-phthalimide, N-butyl-3,6-1-methyl-1,2,3,6-tetrahydrosis-phthalimide, 5-phenyl-bicyclo[
2,2,1]-heptene-2 and 2-phenyl-1,
4:5,8 - Dimethanol 1,2,3,4,4a,5,8
, 8a-octahydronaphthalene. Also,
Norbornadiene derivatives include those with the following formula [(
A typical example is a norbornadiene derivative represented by the following formula.

In the formula, X5 and Y5 may be the same or different,
A hydrogen atom, the above hydrocarbon group, an ester group, or a hydrocarbon group substituted by an ester group,
and Y5, at least one is an ester group or a hydrocarbon group substituted with an ester group.

Representative examples of these norbornadiene derivatives are disclosed in JP-A-5
It is described in each publication specification of No. 0-6150 Gin and No. 50-103600.

Among these norbornadiene derivatives, particularly representative ones include 1,4-dihydro-1,4-methano-naphthalene, 5,8-diacetoxy-1,4-dihydro-1,4-methanonaphthalene, and 2-methoxycarbonyl-bicyclo. [2,2,1]-hepter-2,5-diene is mentioned.

The cycloolefin compounds used for copolymerization in the present invention are monocyclic monoolefin compounds, non-conjugated cyclic polyene compounds, and polycyclic olefin compounds.

The general formula of monocyclic olefin compounds is the following formula [(■) formula]
It is expressed as

(However, n is an integer of 3 to 20.) Typical examples include cyclopentene, cycloheptene, cyclooctene, cyclodecene, cyclodecene, cyclododecene, and these monocyclic olefin compounds containing an alkyl group having one or more carbon atoms at most w basis,
Mention may be made of monocyclic olefinic compounds substituted with hydrocarbon groups selected from the group consisting of alkenyl groups and Aryl groups.

The general formula of the non-conjugated cyclic polyene compound is represented by the following formula [formula (■) and formula (■)].

(However, 1 is O or an integer of 1 to 20, and m and n are integers of 2 to 20.) Representative examples include 1,5 cyclooctadiene and 1,5,9-cyclododecatriene.

Furthermore, non-conjugated cyclic polyene compounds represented by the above formulas (■) and (■) are substituted with one or more of the above hydrocarbon groups and/or halogen atoms (for example, 1- Chloro-1,5-cyclooctadiene and 1-methyl-1,5-cyclooctadiene) can also be used. Polycyclic olefin compounds have 2 to 1 rings and 1 to 1 carbon-carbon double bond.
It is a compound having 5 molecules, and typical examples include bicyclo[2,2,1]-heptene-2 (norbornene), 5
-Methyl-bicyclo[2,2,1]-heptene-2,5
-vinylubicyclo[2,2,1]-heptene-2,5
-ethylidene-bicyclo[2,2,1]-heptene-2
, 5-isopropenylbicyclo[2,2,1]-heptene-2, dicyclopentadiene, bicyclo[2,2,
1]-hepter 2,5-diene (norbornadiene) and 1,4;5,8-dimethanol 1,2,3,4,4a
, 5,8,8a-octahydronaphthalene.

Furthermore, in carrying out the present invention, as other non-conjugated cyclic polyene compounds represented by the above formula (■), J chloride represented by the above formula (■) and (■) may be used. A cyclic oligomer (generally,
The degree of polymerization may be at most 100).

In carrying out the present invention, 1-norbornene derivatives,
Each of the norbornadiene derivatives and the cycloolefin compound J (hereinafter referred to as monomer) may be used alone, or two or more types may be used in combination.

Further, the copolymerization ratio of the cycloolefin compound as a copolymerization component is at most 50 mol%, preferably 45 mol% or less, and particularly preferably 40 mol% or less.

The organometallic compounds used to obtain the catalyst system used in the present invention are IA, ■A, ■B, and ■B of the periodic table.
, ■B, and ■B group metals, and some of them have the general formulas shown below. MRn [However, M is IA, ■A, ■B, ■B, ■ of the periodic table
It is a metal of group A or B, and R has at most 2 carbon atoms.
An organic group selected from the group consisting of an alkyl group, an alkenyl group, an allyl group, an aralkyl group, an alkoxide group, a phenoxy group, and a cyclopentadienyl group, or a hydrogen atom or a halogen atom, even if they are the same. They may be different types, but at least one of them is a hydrogen atom or the above-mentioned organic group, and n is the highest valence number of the metal 3 or less] Other organometallic compounds include the above-mentioned organometallic compounds. and equimolar amounts of pyridine, triphenylphosphine or diethyl ether and 1 mole of said organometallic compound and at most 2
．． Mention may be made of reactants with 0 mol of water as well as double salts of the two organometallic compounds mentioned above.

Typically, organometallic compounds containing lithium, sodium, potassium, magnesium, calcium, zinc, boron, aluminum, gallium, titanium, zirconium, silicon, germanium and tin are preferred, with particular preference given to lithium, sodium, , magnesium, zinc, aluminum, and tin are preferred, and organoaluminium-based compounds are particularly preferred.

Typical examples of the organoaluminum compounds include triethylaluminum, triisobutylaluminum, trihexylaluminum, diethylaluminum chloride, di-n-butylaluminum chloride, ethylaluminum sesquichloride, diethylaluminum butoxide, and the reaction product of triethylaluminum and water. (reaction ratio 1:0.5 (molar ratio)).
Other representative examples are JP-B-50-23720, JP-A-49-679, JP-A-49-77999, and JP-A-50.
-- No. 582 (1), No. 50-615 (4), No. 50
-71800 and 50-7530 inches. Examples of other organoaluminum compounds include aluminum/siloxsalene compounds, aluminum/amide compounds, dialmoxalene compounds, and double salts containing the above organoaluminum compounds. Representative examples of other organometallic compounds are
No. 0-112068, No. 50-112534, No. 50
-116324, 50-117664 and 5
No. 0-120317. Furthermore, the general formula of the carpin complex is shown by the following formula. In the above formula, X is a halogen atom, M is tungsten or molybdenum metal, and R is a saturated or unsaturated hydrocarbon group having at most 2 carbon atoms or an amino group having at most no more than 2 carbon atoms. Or is the number of carbon atoms substituted with this amino group at most 2? is a saturated or unsaturated hydrocarbon, and n is O or 1.

Representative examples of these carpin complexes are described in Ogiwara and Sonogashira, Volume 1 of Kagakucho, pages 570 to 573, (Misaki 197).

The chemical formula of the representative one among them is (CO)5W...C
-CH3, C1(CO)4W...C-CH3, C1(CO
)4W=C-C6H5, Cl(CO)4M0=C-CH
3, Cl(CO)4M0=C-C6H5, Br(CO)
4W...C-CH3, Br(CO)4W...C-C6H5,
1(CO)4W yoC-CH3, I (CO)4W=C-
C6H5, Br(CO)4W=C-C...C-C6H5,
Br(CO)4W=C-N(C2H5)2 and Br(
CO)4 is mentioned. In carrying out the present invention, the amount of the organometallic compound per atomic equivalent of tungsten or molybdenum in the above-mentioned carpine complex is generally 0.1 to 100 mol, and 0.5 to 50 mol from the viewpoint of polymerization activity. Preferably, especially 1.
0 to 30 mol is suitable.

In carrying out the present invention, a catalyst system obtained from an organometallic compound and a carpine complex may be used, but it is also possible to use a catalyst system obtained from these and another compound (third component). , a catalyst system with even better catalytic activity can be obtained. Examples of the third component include water, hydrogen peroxide, an oxygen-containing organic compound, a nitrogen-containing organic compound, a halogen-containing organic compound, a phosphorus-containing organic compound, a sulfur-containing organic compound, and a metal-containing organic compound.
Representative examples of these third components are described in the specification of JP-A-51-63(1). The organic compound, the carpine complex, and the third component may be used alone or in combination of two or more. When a third component is used in the present invention, the ratio of the third component to one atomic equivalent of tungsten or molybdenum in the carpine complex is generally at most 100 moles, and from the standpoint of polymerization activity, it is 50 moles or less. is preferable, and particularly preferably 30 mol or less.

Further, although the catalyst system used in the present invention differs depending on its type, the proportion of carpine complex used is 0.001 to 100j atomic equivalent as the metal of tungsten or molybdenum per 1000 moles of monomer. from the viewpoint of polymerization activity and catalyst removal, from 0.005 to 50
Atomic equivalents are preferred, particularly 0.01 to 10 atomic equivalents.

The above-mentioned organic compound, carpine complex, and third component may be added to the polymerization system without any pretreatment, but some or all of them may be pulverized or co-pulverized in advance or in the presence of a solvent. Alternatively, it may be used after performing a pretreatment such as a method of thermal formation by heating in its absence.

The present invention involves carrying out ring-opening monopolymerization or ring-opening copolymerization of a monomer or a monomer and a cycloolefin compound in the presence of the above catalyst system in the absence of an inert organic solvent.
Although that purpose can be achieved, the ring-opening polymerization may also be carried out in an inert organic solvent. Examples of inert organic solvents include aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, halogenated hydrocarbons, and ethers.

When carrying out the present invention in an inert organic solvent, these inert organic solvents may be used alone or as a mixture of two or more. When ring-opening polymerization is carried out in the organic solvent, the proportion of the organic solvent used per 1 part by volume of monomer is generally at most 2 parts by volume, and in particular, 1 part by volume or less. preferable. The polymerization temperature is generally -100 to +250°C, particularly -50 to +
The temperature is preferably 180°C, and particularly preferably 0 to 150°C.

If the polymerization temperature is -100° C. or lower, there is no sufficient polymerization activity, so the polymerization rate is very slow, and furthermore, the monomer or the mixture of the monomer and the inert-organic solvent may solidify. On the other hand, when the polymerization temperature is 250° C. or higher, it is often difficult to sufficiently control the polymerization. The ring-opening polymer targeted by the present invention can be obtained by ring-opening polymerization using the method described above. However, in addition, alpha-olefins with at most 1 carbon number (e.g., ethylene, hexene-1, octene-1), internal olefins with at most no more carbons (e.g., hexene-2, octene-2), Conjugated diolefins, ines or their halogen substitutions (e.g., butadiene, chloroprene), unconjugated diolefins with at most no more carbon atoms (
For example, 1,4-hexadiene) and
No. 56494, No. 50-56495, No. 50-564
The molecular weight of the resulting ring-opening polymer can be adjusted by adding the compounds described in the publications No. 96 and No. 50-56497 as molecular weight regulators to the ring-opening polymerization system.

The proportion of the molecular weight regulator added to 100 moles of the monomer is generally at most 20 moles, preferably 10 moles or less, particularly preferably 5 moles or less. In carrying out the present invention, it may be carried out in a homogeneous system, but it may also be carried out in a heterogeneous system. Moreover, a batch method or a continuous method may be used. Since the catalyst system of the present invention is unstable to oxygen and moisture, it is desirable to operate under an atmosphere of inert gas such as argon and nitrogen.

Although the object of the present invention can be achieved by ring-opening polymerization in the absence of an unsaturated polymer, it can also be carried out in the presence of an unsaturated polymer. Unsaturated polymers are polymers containing carbon-carbon double bonds, and include butadiene-based rubbers containing butadiene as a main component (for example, butadiene monopolymer rubber, styrene-butadiene copolymer rubber, acrylonitrile-based rubber). butadiene copolymer rubber), chloroprene rubber, isoprene rubber, natural rubber, ethylene-propylene-diene terpolymer (generally referred to as EPT or EPDM), and cycloolefin rubber. It will be done.

When carrying out the present invention in the presence of the unsaturated polymer,
Generally, its Mooney viscosity is between 10 and 200, with 2
A value of 0 to 150 is desirable, and a value of 30 to 130 is particularly preferred.

Further, it is preferable that there is at least one carbon-carbon double bond per 10(1) total carbon-carbon bonds, and more preferable that there is m or more carbon-carbon double bonds. The proportion of unsaturated polymer used per 1 part by weight of monomer is generally at most 1 part by weight, preferably 5 parts by weight or less, and particularly preferably 3 parts by weight or less.

If the amount is 1 part by weight or more per 1 part by weight of the monomer, a polymer exhibiting the characteristics of the monomer used in the present invention cannot be obtained. When carrying out ring-opening polymerization in the presence of an unsaturated polymer, the unsaturated polymer is generally dissolved or suspended (dispersed) in the monomer or the monomer and the inert organic solvent described below. It is used with Further, the ring-opening polymerization may be graft polymerization, block polymerization, or a combination of graft and block polymerization. The grafted product and block polymer obtained by the above method are as follows:
Since it has excellent impact resistance, it is particularly promising in fields where impact resistance is desired.

After completion of the ring-opening polymerization, the resulting polymer can be recovered by several methods.

Regarding the recovery method, the types of resinous rubber materials and additives to be blended with the obtained polymer, and the characteristics, processing methods, and uses of these polymers (including blends), see, for example, Japanese Patent Publication No. 50-23720. No. 49-679, No. 50-77999, No. 49-
13,050 inches and 50 Ichinoseki 20 gallons, 50-718
0gin, No. 50-75300, No. 50-103600, No. 50-153100, No. 50-159598, and No. 50-16040. According to the present invention, since the polymerization activity of the catalyst is very high, the production of ring-opened polymer per single catalyst position is high;
Therefore, not only can the amount of catalyst used be reduced, but also purification of the ring-opening polymer obtained after the ring-opening polymerization is completed can be very simple or can be omitted.

Hereinafter, the present invention will be explained in more detail with reference to Examples.

In the examples, the reduced viscosity was measured using dimethylformamide as a solvent at a concentration of 0.1 g/Dt and a temperature of 30°C.

Moreover, the polymerization activity was expressed with respect to a certain amount (g) of tungsten or molybdenum metal in the carpin complex used. Example 1 In a 500ml autoclave completely purged with nitrogen, 25
0 ml of 1,3-dichloroethane, 150 ml of 5-cyanobicyclo[2,2,1]-heptene-2 (as a monomer, 1.26 mol) and diethylaluminum chloride (as an organometallic compound) at a concentration of 0. 1.0 mL of 1.2-dichloroethane solution of 8 mol/f was charged and stirred at room temperature to become homogeneous.

Next, phenylcarpinetetracarbonyltungsten bromide [Br(CR)4W=C
1.0 ml of a toluene solution having a concentration of 0.1 mol/e of -C6H5 (hereinafter referred to as 1 complex AJ) was added. The reaction system is 8
After raising the temperature to 0'C, polymerization was carried out at this temperature while stirring the powder. After the polymerization is completed, about 1.6-di-tertiary-butyl-P-cresol is added. Polymerization was stopped by adding about 50 nL of a mixed solution of 1.2-dichloroethane and methyl alcohol (about 4:1 in volume) containing 1.2-dichloroethane and methyl alcohol (about 1 e) of the obtained polymer. After filtering the polymer, the polymer was thoroughly washed with methyl alcohol, and then heated at about 50°C.
Drying was carried out under reduced pressure for about 2 hours.

As a result, 86 g of polymer was obtained. Polymerization activity is 46
74 g/g-W·hr. Note that the reduced viscosity of this polymer was 1.30. Examples 2 to 8, Comparative Example 1 CI(CO)4W=C-C6H5 [hereinafter 1 complex B] was used instead of complex A used as the carpine complex in Example 1.
I (CO)4W=C-C6H5 [hereinafter 1
complex CJ], Br(CO)4WmiC-N(C2H
5) 2 [hereinafter referred to as 1 complex Do], Br(CO)4W=
C-C=C-C6H5 [hereinafter referred to as 1 complex EJ], Br
(CO)4W--C-CH-♂ [hereinafter 1 complex F
], C1(CO)4M0=C-C6H5 [hereinafter referred to as 1 complex GJ], C1(CO)4M0=C-CH3
[hereinafter referred to as 1 complex HJ] and tungsten hexachloride (
Polymerization was carried out in the same manner as in Example 1, except that WCI6) was used in the amount shown in Table 1.

The results are shown in Table 1. 1 g/g-M·hr (M: tungsten or molybdenum) Examples 9 to 15 Polymerization was carried out in the same manner as in Example 1, except that 150 g of each of the monomers shown in Table 2 was used.

The results are shown in Table 2. Example 16 Polymerization was carried out in the same manner as in Example 1, except that a mixture of 100 g of 5-cyanobicyclo[2,2,1]-heptene-2 and 50 g of cyclopentene was used.

As a result, 102 g of polymer was obtained. When this polymer was subjected to infrared absorption spectrum analysis and magnetic resonance spectrum analysis, it was found that 5-cyanobicyclo[2,2
,1]-heptene-2 and cyclopentene. The copolymerization ratio of cyclopentene in this copolymer was 37 mol%. Examples 17-2
1 Polymerization was carried out in the same manner as in Example 1, except that the organoaluminum compounds or reaction products thereof shown in Table 3 were used (however, the concentrations of the organoaluminum compounds used were the same as in Example 1 and the aluminum concentration, respectively). same number of moles).

The results are shown in Table 3. 1 g/g-W.hr 22 mol of triethylaluminum and 1 mol of water Reaction product 3 Reaction product of equimolar of trimethylsilanol and triethylaluminum 4 Reaction product of equimolar of diethylamine and triethylaluminum Example 22 ~
Copolymerization was carried out in the same manner as in Example 1, except that 80 g of 245-cyanobicyclo[2,2,1]-heptene-2 and 70 g of each of the monomers shown in Table 4 were used.

The results are shown in Table 4. 1 g/g-W・hr 25-cyano-5-methyl-bicyclo[2,2,1]-
Heptene-235-methoxymethyl-bicyclo[2,2
,1]-heptene-245-chloromethyl-bicyclo[
2,2,1]-heptene-2 Example 25s26 After adding diethylaluminum chloride, the fifth
1.0% of the molecular weight regulator shown in the table for each monomer.
Polymerization was carried out in the same manner as in Example 1, except that mol% was added.

The results are shown in Table 5. Example 27 Dried cis-1,4-polybutadiene [manufactured by Japan Synthetic Rubber Co., Ltd., trade name JSRBR-01, Mooney viscosity (ML
l+4100℃) 45, Sis-1.4 content 97.5%]
20.0 g was placed in a 1e glass autoclave purged with nitrogen, and 500 mt of 1,2-dichloroethane was added and stirred to completely dissolve.

Claims (1)

[Claims] 1 Norbornene derivatives and/or norbornadiene derivatives having at least one polar group or aromatic hydrocarbon group, or a mixture of these and at most 50 mol% of a cycloolefin compound containing a carbon-carbon double bond. (A) I A, IIA, IIB, II of the periodic table in the absence or presence of an unsaturated polymer that
A ring characterized by ring polymerization with a catalyst system obtained from an organometallic compound having at least one metal selected from the group consisting of metals of groups IB, IVA and IVB and (B) a carbine complex of tungsten or molybdenum. Method for producing ring polymer.