JPS5818370B2 - Norbornene dicarbonate composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing novel polymers from norbornene derivatives.

More specifically, it is an object of the present invention to provide a catalyst for producing a novel polymer or copolymer hitherto unknown from a cyclic acid anhydride derivative of norbornenes.

Detailed research has been carried out on ring-opening polymerization methods for cyclic olefin hydrocarbons having no polar groups, and in particular, cyclopentene polymers are attracting industrial attention as polypentenamers.

On the other hand, although the polymerization of cyclic olefins containing polar substituents such as ester groups and nitrile groups is attracting attention from various quarters as a method for producing new polymer materials, there are difficulties such as deactivation of the catalyst due to the polar substituents. For this reason, there have been extremely few examples of this in the past.

Examples of such polymerizations include the polymerization of carboxylic acids, esters, imides or alcohol derivatives of norbornene in alcohol or water emulsion using Ru, Ir, O8 compounds (French Patent No. 155,621).
No. 5, No. 1594934), and W, Mo or T
A method for polymerizing norbornene esters, nitrile, and halokene derivatives using a so-called Ziegler type catalyst containing the compound of a as a part (West German Published Patent Application No. 223199)
! No. 5) is known.

However, there have been no prior examples of polymerization of cyclic acid anhydride derivatives of norbornene, and much interest has been focused on polymers containing substituents with extremely diverse reactivity.

The present inventors have carried out extensive research aimed at developing polymers of cyclic acid anhydrides in particular during research into the polymerization of various norbornene derivatives having polar substituents.
Compounds of ゛, Re or Ta and the periodic table IA, ■A, I
We have discovered that these polymers can be obtained by contacting the above-mentioned cyclic acid anhydride derivatives with a catalyst containing an organometallic compound or hydride of a group IB, TIIA, or IVA metal, and based on this finding, we have arrived at the present invention. did.

The present invention not only provides a method for producing a novel polymer that has not been previously known, but also enables the production of an even wider variety of new polymers due to the diverse reactivity of the obtained polymer. be.

Next, the constituent elements of the present invention will be explained in detail.

The cyclic acid anhydride derivative of norbornene used as a monomer in the present invention is a compound represented by the general formula Σl2I''o, where A and B are H or C1-1o
hydrocarbon group or -(CH2)nY (n is O~10
Y is a norogen, an ester group, a nitrile group, or an amide group], and is preferably a (2) or a hydrocarbon group.

Specific examples include 5-norbornene-2,3-dicarboxylic anhydride (himic anhydride), 2-methyl-5
-Norbornene-2,3-dicarboxylic anhydride, 2-ethyl-5-norbornene-2,3-dicarboxylic anhydride, 2-n-butyl-5-norbornene-2,3-dicarboxylic anhydride, 2- n-octyl-5-norbornene-
2,3-dicarboxylic anhydride, 2,3-dimethyl-5-
norbornene-2,3-dicarboxylic anhydride, 2-methyl-3-ethyl-5-norbornene-2,3-dicarboxylic anhydride, 2-chloro-5-norbornene-2,3-
Dicarboxylic anhydride, 2,3-dichloro-5-norbornene-2,3-dicarboxylic anhydride, 2-methoxycarbonyl-5-norbornene-2,3-dicarboxylic anhydride, 2-(methoxycarbonylmethyl)- Examples include 5-norbornene-2,3-dicarboxylic anhydride.

A tetracyclic compound (A and B are the same as above) can also be used.

As a specific example, ■・4・5・8-dimethano-1・2・
Examples include 3,4,4a,5,8,8a-octahydronaphthalene-2,3-dicarboxylic acid anhydride.

Furthermore, compounds in which at least one of the hydrogen atoms other than the 2nd and 3rd positions of the above compounds are replaced with . . . rogene can also be used.

Examples of such compounds are 1, 4, 5, 6, 7,
Examples include 7-hexachloronorbornene-2,3-dicarboxylic acid anhydride (het acid anhydride).

Copolymers can be produced using mixtures of these acid anhydrides and as little as one comonomer.

Compounds suitable for use as comonomers are chosen among norbornenes and cycloalkenes containing polar substituents.

The norbornenes used as comonomers contain esters, nitriles, amides, imides and/or halogens as polar substituents; particularly suitable monomers include the following:

(1) Ester general formula 11)1 or 11)
1 [wherein R is a C1-2o hydrocarbon group, n is an integer of 0-10,
X is H-(CH2)mcOOR', (CH2)(yr
OCOR', C1-1 o hydrocarbon group, -(CH2
)mCN, -(CH2)rnCONR2R3 or...
igen (R1 is a hydrocarbon group of 01 to 2o, R2 and R
3 is H or a C1-1o hydrocarbon group, m is an integer of 0-10), A and B are H or a C1-1o hydrocarbon group].

Specific examples include methyl 5-norbornene-2-carboxylate, ethyl 5-norbornene-2-carboxylate,
Methyl 5-norbornene-2-carboxylate, octyl 5-norbornene-2-carboxylate, 5-norbornene-
lauryl 2-carboxylate, oleyl 5-norbornene-2-carboxylate, phenyl 5-norbornene-2-carboxylate, methyl 2-methyl-5-norbornene-2-carboxylate, 3-methyl-5-norbornene-2- Ethyl carboxylate, ethyl 3-phenyl-5-norbornene-2-carboxylate, ethyl 3,3-dimethyl-5-norbornene-2-carboxylate, cyclohexyl 5-norbornene-2-carboxylate, 5-norbornene-2- Allyl carboxylate, methyl 5-norbornene-2,3-dicarboxylate, allylethyl 5-norbornene-2,3-dicarboxylate, 5-norbornen-2-yl acetate, 2
-Methyl-5-norbornen-2-yl acetate, 5
-norbornene-2-inpropionate and the like.

Mapa general formula 1'') T) R4, N, ;o 6°1''117 to R8 (A and B are the same as above, R4 is an alkylene group), or 4 represented by the general formula 1
Cyclic compound (A, B, , R, X and n are the same as above)
You can also use

As a specific example, ■・4・5・8-dimethano-1・2・
3, 4, 4a, 5, 8, 8a-methyl octahydronaphthalene-2-carboxylate/Yanonaka (\(lI)Sat B-') is mentioned (2)
Nitriles general formula W2 ff? ---7'" compound [
In the formula, A, B and n are the same as above, and X is Hl-(CH
2) mCN, C1-1o hydrocarbon group, -(CH2)m
CONR2R3 or halogen (R2, R3 and m are the same as above)].

A specific example is 5-norbornene-2-nitrile, '2
-Mef-5-norbornene-2-nitrile, 3-methyl-5-norbornene-2-nitrile, 3-phenyl-
5-norbornene-2-nitrile, 3-ethyl-5-norbornene-2-nitrile, 3-butyl-5-norbornene-2-nitrile, 2,3-dimethyl-5-norbornene-2-nitrile, 3. Examples include 3-dimethyl-5-norbornene-2-nitrile, 5-norbornene-2,3-dinitrile, and 2-methyl-5-norbornene-2,3-dinitrile.

(3) Amides Compounds represented by the general formula [N] [wherein A, B and n are the same as above,
R1 and R2 are H or a C1-1o hydrocarbon group, X
represents Hl-(CH2)mCONR"R', a C1 to 1o hydrocarbon group or norogen (m is the same as above, R3 and R4 are H or a C1 to 1o hydrocarbon group).

Specific examples include 5-norbornene-2-carboxylic acid amide, N-methyl-5-norbornene-2-carboxylic acid amide, and N-N-dimethyl-5-norbornene-2-
Carboxylic acid amide, N-N-diethyl-5-norbornene-2-carboxylic acid amide, N-phenyl-5-norbornene-2-carboxylic acid amide, N-N~dicyclohexyl-5-norbornene-2-carboxylic acid Amide, N-
N dimethyl-2-methyl-5-norbornene-2-carboxylic acid amide, N・N-diethyl-3-phenyl-5
-Norbornene-2-carboxylic acid amide, 5-norbornene=2,3-dicarboxylic acid diamide, N-N-N'.
Examples include N'-tetramethyl-5-norbornene-2,3-dicarboxylic acid diamide.

Also, tricyclic compounds represented by the general formula (A and B are the same as above,
R7 may be an alkylene group, R5, R6 and R8 may be H or a C1-1o hydrocarbon group).

(4) Imides A compound represented by the general formula [1>, L, , >NR (wherein A and B are the same as above, and R represents H or a C1-1o hydrocarbon group).

Specific examples include 5-norbornene-2,3-dicarboxylic acid imide, N-methyl-5-norbornene-2,3-dicarboxylic acid imide, N-ethyl-5-norbornene-2
・3-dicarboxylic imide, N-n-propyl-5-norbornene-2,3-dicarboxylic imide, N-octyl-5-norbornene-2,3-dicarboxylic imide,
N-cyclohexyl-5-norbornene-2,3-dicarboxylic acid imide, N-phenyl-5-norbornene-2
-3-dicarboxylic acid imide, N-hexyl-2-methyl-5-norbornene-2,3-dicarboxylic acid imide, etc.

(5) Halogen compounds represented by the general formula N [
In the formula, A, B and n are the same as above, Y is a halogen, and X is Hl-(CH2)mYl or a C7-1o hydrocarbon group (m is an integer of O-10, Yl is a halogen)].

Specific examples include 5-chloro-2-norbornene, 5-
Methyl-5-chloro-2-norbornene, 6-methyl-
Examples include 5-chloro-2-norbornene and 5-bromo-2-norbornene.

On the other hand, various compounds can be used as the cycloalkenes used as comonomers, and particularly preferred monomers include the following compounds.

(1) Cycloolefins cyclopentene, cycloheptene, cyclooctene, cyclodecene, cyclododecene and other compounds represented by the general formula It (CH2)n (n≧3), and methylcyclopentene , methylcyclooctene, chlorocyclopentene and other alkyl, alkenyl or halogen substituted products.

Compounds represented by general formula 2, n≧2) such as ■・5-cyclooctadiene, ■・5,9-cyclododecatriene, and 12-vinylroot 5,9-cyclotetradecatriene, or their alkyls and alkenyls. , halogen substituted product.

≧) Bicycloolefin norbornene [bicyclo(2.2.1)hebutene-2]
, 5-methyl-2-norbornene, 5-phenyl-2-
norbornene, 5-vinyl-2-norbornene, 5-ethylidene-2-norbornene, dicyclopentadiene,
Dihydrodicyclopentadiene, turvonacien, 1.
4, 5, 8-Dimetanaut 2, 3, 4, 4a, 5, 8,
8a-Octahydronaphthalene There is no particular restriction on the mixing ratio of these comonomers and the norbornene dicarboxylic acid anhydride, but usually 99
:1 to o:ioo can be used.

The catalyst used in the present invention is (A) W and MO
(B) at least one selected from organometallic compounds and hydrides of metals of groups IA, I[A, I[B, IIIA and IVA of the periodic table; It is prepared from at least two components (8) and (B), (C) an activator added by.

Compounds of W or Mo suitable as component (A) include halides, oxyhalides, alkoxyhalides, alkoxides, carboxylates, (oxy)acetylacetonates, carbonyl complexes, acetonitrile complexes, hydride complexes, and derivatives thereof. , or a combination thereof, but compounds of W and MO, particularly halides, oxyhalides, and alkoxyhalides thereof, are preferred from the standpoint of polymerization activity and practicality.

Also included are mixtures of two or more compounds that produce the above compounds upon reaction.

Furthermore, these compounds can be combined with suitable complexing agents, such as P (C
It may be complexed with 6H5)3, C5H, N, etc.

Specific examples include WC16, WCl6, WC14,
WB r 6, H6, WN2, MoCl5, MoC14
, Mo113, TaBr3, WOCl4, M00C13
, W(QC6H5) a, WC12(0C6H5)4,
Mo (OC2H5) 2C13, Mo, (QC2H
5) 5,M00□(aCaC)2,W(OCOR)s
, W(C0)a, M o (CO) a, WCi s
・p (C6H3) 3, WCl6・C5H5N, W
(CO)5・P(C6H5)3, , □W(CO)
3(CH3CN)s and the like.

Compounds suitable as component (B) are IA and m of the periodic table.
A, JIB, HA, or IVA group metal compound having at least one metal-carbon bond, or a hydride thereof.

Specific examples include n-C4H9Li, n-C3H1
□Na, C3H5, NalCH3MgI, C2H5Mg
Br, CH3MgBr, n-C3H7MgCl, t-C
4H9MgC1, CH2=CH-CH2-MgC1, (
C2H5) 2 Zn, (C2Hs) 2 Cd, C
aZn (C2H5) 4, (CH3)3B, (C2H
5) 3B, (n-C4H9)3B, (CH3)3Al,
(CH3)2AICI, (CH3)3A12C13,C
H3AlCl2, (C2H5)aAl, LtAl
(C2H5)4, (C2n, ) 2 A l・0
(C2H5) 2, (02H5) 2A I CI,・
C2H5AlCl2, (C2H,)2AIH.

(1so-C4H9)2AIH1(C2H5)2AIO
C2H5, (1so-C4H;)' ) 3Al, (C
2H5)3A12C13, (CH3)4Ge, (CH3
)4 Sn, (n-C4Hg)4Sn, (C2H5)3
SiH1(nCa H13) s A l, (n-C3
H17) 3Al, LiH, NaH, B2H6, NaBH
, , AlH3, LiAl)L, , S i H4, and the like.

It is also possible to use a mixture of two or more compounds that produce these compounds through reaction.

(B) Components include Zn, B, AI, Si and Sn.
Organometallic compounds are preferred, and compounds having at least one methyl group bonded to these metals are particularly preferably used.

The quantitative relationship between the human component and component (B) is the metal atomic ratio (8:
(B) is 1:1 to 1:20, preferably 1:2 to 1:1
Used in the range 0.

The catalyst prepared from the above two components (A) and (B) usually has high activity for the polymerization of the present invention, but if desired, the catalyst prepared from the following two components (C) (activated agent)
It is also possible to obtain a catalyst with higher activity or with a different reactivity ratio in copolymerization by adding .

Various compounds can be used as component (C), and particularly preferably used compounds include the following.

(1) Elemental boron, BF3 voice C13, B (0-n-C
4H0) 3, (C2H50)2BF, B2O3, H2
Inorganic metal compounds of boron such as BO3, Si(OC2
Non-organometallic compounds of silicon such as H5)4, (2) alcohols, hydroperoxides and peroxides, (3) water, (4) oxygen, (5) carbonyl compounds such as aldehydes and ketones, (6) cyclic ethers such as ethylene oxide, epichlorohydrin, and oxetane; (7) amides such as N-N-diethylformamide and N-N-dimethylacetamide; amines such as aniline, morpholine, and piperidine; and azo compounds such as azobenzene.

The amount of component (C) varies depending on its type and the types of components (5) and (B), but is usually in the range of 0.5 to 20, preferably 1 to IO per mole of metal atom of component (A). used.

In the present invention, there is no restriction on the order of mixing the catalyst components, but a method is usually used in which the other component is added to a mixture of monomers and one component.

There is also no particular restriction on the method of adding component (C).

A method of adding component (B) [or human] to a reaction mixture of component (A) (or (B)) and component (C) is preferred.

The amount of the catalyst used is in the range of 200 to 0.1, preferably 20 to 0.2 mmol of component (A) per mol of the monomer or monomer mixture.

The reactions of the invention can be carried out in the presence or absence of a solvent.

Suitable solvents include hexane, heptane, benzene,
Hydrocarbons such as toluene, halogenated hydrocarbons such as chloroform, 1,2-dichloroethane, chlorobenzene, ethers such as diethyl ether, dibutyl ether, diphenyl ether, tetrahydrofuran, esters such as ethyl acetate, methyl propionate, or mixtures thereof. However, any catalyst can be used as long as it does not inactivate the catalyst component for the polymerization according to the present invention.

The temperature suitable for carrying out the method of the present invention is -30° to -10°.
Although the temperature is 200°C, a temperature of 00 to +150°C is usually preferred.

The molecular weight of the (co)polymer obtained in the polymerization of the present invention can be adjusted by adjusting reaction conditions such as catalyst type, concentration, polymerization temperature, solvent type, and monomer concentration. More preferably, the reaction is controlled by adding an appropriate amount of a compound having at least one carbon-carbon double bond or triple bond in the molecule, such as α-olefins or α・ω-diolefins, to the reaction system. Ru.

By this method, the molecular weight of the polymer can be adjusted without essentially changing the yield, microstructure, and other properties of the polymer.

The concentration of the monomer can be any concentration, but 0.
It is preferably 1% by weight or more.

The method of the present invention can be carried out in either a homogeneous or heterogeneous system, and can be carried out either batchwise or continuously.

Since the catalyst used in carrying out the process of the present invention is relatively unstable to atmospheric oxygen and moisture, the reaction is usually carried out in an inert atmosphere such as nitrogen, helium, or argon, and is not suitable for use. It is desirable to degas and dehydrate the monomer and solvent in advance.

The polymer obtained by the method of the present invention includes ethanol,
It can be recovered from the polymer solution by conventional methods including the addition of a non-solvent such as a lower alcohol such as methanol.

The polymer may contain known antioxidants, such as 2,6-sheeter
tert-butyl-4-methylphenol, 2,2'-dioxy-3,3'-di-tert-butyl-5,5'-cy)
By adding tyldiphenylmethane, phenyl-β-naphthylamine, etc., it can be stabilized against the action of oxygen.

The properties of the (co)polymer obtained by the polymerization of the present invention vary depending on the type of (co)monomer used and the reaction conditions, ranging from rubber-like to hard resin-like.
Suitable as molding materials, paints, coatings, and hydrophilic materials.

Also, due to the diverse reactivity of the acid anhydride groups present in the molecule, it can be used as a starting material for a large number of novel polymers.

Next, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to these Examples unless the gist thereof is exceeded.

Example 1 Internal volume: 50TLl, cleaned, dried and replaced with nitrogen in advance
0.92 P of 5-norbornene-2,3-dicarboxylic anhydride (I) (petroleum ether) in a glass ampoule of
recrystallized from benzene and dried under reduced pressure).
Add 15ml* of chlorobenzene to this and dissolve.

In this system, a WCl6 chlorobenzene solution (concentration 0.0'
After adding 2 ml of 5 mol/g) and stirring for 5 minutes (CH3), 2 ml of a chlorobenzene solution of 5AIC11,5 (0.1 mol/l) was added.

After sealing the ampoule at 0°C, it was crushed in a constant temperature bath at 65°C and reacted for 4 hours.

After the reaction is complete, the contents of the ampoule are diluted with about 200ml of methanol containing a small amount of 2.6 ditertiary butyl p-cresol.
The precipitated polymer was washed several times with methanol and then dried under reduced pressure at 60° C. for 20 hours.

A powdery polymer was obtained with a yield o, i y'' (yield 10%).

The IR spectrum (KBr method) of this product is 1775cr
Characteristic absorption of acid anhydride group in fL', C in 965 F-1-
It exhibited characteristic absorption of -C bonds, suggesting that it was a polymer with the following structure.

Example 2 Chlorobenzene 157711 was placed in an ampoule prepared in the same manner as in Example 1, followed by compound (■) 0, 46.
After adding f and stirring to dissolve, cyclooctene 2. ．． -21rll was added.

A toluene solution of dimethylformamide (0,1
After adding 0.3 ml of WCl6 chlorobenzene solution (0.05 mol/l) and mixing well,
Add 2 ml of (CH/l) and stir for 5 minutes, then add (CH
3) Chlorobenzene solution of 1.5 AIC1t i 5 (
0.1 mol/A) 2 ml was added.

The ampoule was cooled to 0°C, sealed, and immersed in a water bath kept at 65°C to react for 4 hours.

After the reaction was completed, the polymer was recovered in the same manner as in Example 1.

The yield of polymer was 1.93P (yield 88%).

The polymer was dissolved in chlorobenzene, and its IR spectrum showed characteristic absorption of acid anhydride groups, suggesting the formation of a copolymer.

Example 3 The experiment of Example 2 was repeated using 0.05 ml of cytotraethoxysilane instead of the toluene solution of dimethylformamide.

As a result, a polymer yield of 1.79 ft and a yield of 82% were obtained.

Example 4 In the experiment of Example 2, a toluene solution of dimethylformamide was not used, and a chlorobenzene solution of (CH3)4Sn (0, 5,
The reaction was carried out under the same conditions except that 0.4 rnl (mol/l) was used.

J As a result, the yield of polymer was 1.8'l, yield 85%.
I got it.

Example 5 Using 2.5 ml of cyclopentene instead of cyclooctene and using (CH3) 1.5 AIC11 instead of using the chlorobenzene solution of (CH3) 4 S n
, 5 chlorobenzene solution (0.1 mol/73)
The experiment of Example 4 was repeated using 2 ml.

As a result, the yield of polymer was 0.21? , a yield of 9% was obtained.

゛Example 6 Chlorobenzene solution of WC16 (0,'05 mol/
Example 2 using 4 ml of A) and 2 ml of a chlorobenzene solution of A4(C2H5)3 (0.4 mol/, g).
A mixture of compound (I) and cyclooctene was reacted under the same conditions as described above.

As a result, a polymer was obtained with a yield of 0.09 f (yield 3%).

Example 7 Instead of using a chlorobenzene solution of A 1 (C2H5) 3 in the experiment of Example 6, a hexane solution of n-butyllithium (0,5'mol/ 13 )1.
The reaction was carried out under the same conditions except that 6 ml was used.

As a result, a polymer yield of 0.11 P and a yield of 5% were obtained.

Example 8 In the experiment of Example 2, 5-
Methyl(III) norbornene-2-carboxylate'
The reaction was carried out under the same conditions except that 2.4 ml was used and the toluene solution of dimethylformamide was not added.

As a result, the yield was 1.85? A polymer was obtained (yield 60%).

The IR spectrum of this product shows absorption due to ester groups ('
1730cIn'), absorption due to acid anhydride group was shown at 1775crrL'.

Example 9 In the same manner as in Example 1, 0.5 f of compound (I) was weighed into a 5 oml glass ampoule, and N-N-dimethyl-5-norbornene-2-carboxylic acid amide (5) was added to it.
1.6 ml, WCl 6 toluene solution (concentration 0,
05 mol/l) 1 ml, 1・2- of the solvent
After stirring, 10 ml of ethane was added and the mixture was stirred until a homogeneous solution was obtained.

Next, a toluene solution of Al(C2H5)3 (
After adding and mixing 0.15 ml (concentration: 1.0 mol/l), the ampoule was sealed and reacted for 14 hours with shaking in a constant temperature bath at 50°C.

After the reaction, a small amount of methanol was added to the reaction mixture to stop the reaction, and then poured into a large amount of petroleum ether containing a small amount of 2,6-ditertiarybutyl para-cresol (anti-aging agent) to precipitate the polymer. , the polymer was washed with petroleum ether and then dried under reduced pressure.6 Yield: 1.4'? (Yield 5
5%) and colored resinous polymer was obtained.

The obtained polymer is soluble in methanol, which is a non-solvent for the homopolymer of compound (I), and its IR spectrum shows an absorption (1625 cm') assigned to C=0 of the amide group.
) and 1780cr assigned to C=O of acid anhydride.
It had an absorption of fL'.

From these facts, it is clear that a copolymer of compound (I) and compound (2) was obtained.

Example 10 The reaction was carried out under the same conditions as in Example 8 except that 5-norbornene-2-nitrino'(V) 2 rnl was used instead of compound (m).

As a result, a resinous polymer was obtained with a yield of 1.31P (yield 42%).

The IR spectrum of this product shows absorption due to acid anhydride groups (1
780Cr/L') and absorption due to nitrile group was shown at 2210CrfL'.

Example 11 Compound (I) 0.929 and N-n-propyl-5-norbornene-2,3-dicarboxylic acid imide (VlO, 51
Weigh f and add 1,2-dichloroethane as a solvent to it.
Added 5wLl.

Next, this mixture was added with 21rLl of a chlorobenzene solution of WCl6 (concentration 0.05mol7) and (CH3), Sn
After adding and mixing 0.4 ml of chlorobenzene solution (same as that used in Example 4), the angle was sealed.
Constant temperature of 65℃.

The mixture was allowed to react for 16 hours while being shaken in a tank.

After the reaction, the polymer was recovered in the same manner as in Example (2).

The yield of the powdered polymer was 0.37y (yield 26%), and the IR spectrum of this product was due to absorption by acid anhydride groups (17
80cIrL') and 1690crfL-1 showed absorption due to the cyclic imide group.

Example 12 In the experiment of Example 8, 2.5 ml of 5-chloro-2-norbornene (■) was used instead of compound (m), and compound (■) was followed by 0.05 ml of tetraethoxysilane.
The reaction was carried out under the same conditions except that m1 was added.

As a result, the yield of polymer was 2.61? (yield: 88%), and the IR spectrum of the polymer shows that the absorption due to the acid anhydride group is 1
780Z771'.

Example 13 In the experiment of Example 8, Mo was used instead of the WC16 solution.
(QC2H5) 2 Using 2 ml of a chlorobenzene solution (concentration 0.1 mol/l) of 1 g of C,
CH3) J-5 AICI 1.5 Solution The reaction was carried out under the same conditions except that the amount used was 0.6 ml.

As a result, the yield of polymer was 1.029 (yield 33%).

Example 14 In the experiment of Example 6, an ether solution of CH3MgBr (concentration 0.2 m
The reaction was carried out under the same conditions except that 4 m, l was used.

As a result, the yield of polymer was 0.13f! , a yield of 6% was obtained.

Example 15 (C2H5)2zn-chlorobenzene solution (concentration 0.2 mol/73) instead of Al(C2H3)3 solution
As a result of repeating the experiment of Example 6 using 2 rul, the polymer yield was 0.19? , yield was 9%.

Example 16 (“2H5)3SIH instead of Al(C2H5)s solution
Chlorobenzene solution (concentration 0.2 mol/73
) The experiment of Example 6 was repeated using 4 ml, and as a result, the yield of the polymer was o, osy, and the yield was 4%.

Claims (1)

[Claims] 1 A small number of selected compounds from norbornene derivatives having a cyclic acid anhydride group (or cholerato), norbornene derivatives having nistyl, nitrile, amide, imide and/or halogen as a substituent, and cycloalkenes A mixture with at least one selected from the group consisting of (A) at least one compound selected from the group consisting of W and Mo; Norbornene dicarboxylic acid anhydrides, which are brought into contact with a catalyst essentially containing at least one selected from organometallic compounds and hydrides of group metals, in the presence or absence of an inert solvent. (Co)polymer manufacturing method.