JPS6043367B2 - Method for producing (co)polymer of norbornene derivative - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for polymerizing or copolymerizing norbornene derivatives having polar substituents.

More specifically, high-performance and easy-to-handle polymers or copolymers from norbornene derivatives having ester, ether, nitrile, amide, imide, acid anhydride, halogen or silyl groups as polar substituents. The purpose is to provide a new catalyst. Conventionally, regarding the ring-opening polymerization method of cycloolefin hydrocarbons such as cyclopentene and cyclooctene! Detailed research has been conducted on this topic, and many catalysts have been discovered.

Polymers produced by such polymerization have come to attract industrial attention as new rubber or resin materials. On the other hand, ring-opening polymers of cyclic unsaturated compounds containing polar substituents such as carbonyl groups and cyano groups are expected to have even more diverse properties. Much knowledge has been gained. A typical example of such a method is a method in which a compound of a noble metal such as Ru, Ir, or α is used as a catalyst and polymerization is carried out in an emulsion in alcohol or water (French Patent Nos. 1,556,215 and 1,594,934).

However, the precious metal compounds used in this method are expensive, and it is not possible to produce polymers of compounds containing nitrile groups (E.W. Michel O.
tti et al., J OumalOfPOlymerscien
cel Vol. 3, pp. 895-905). A more practical method is to use a so-called Ziegler type catalyst consisting of a compound of W, MO or Ta and an organometallic compound of an element of group 1A, ■A, ■B or ■A of the periodic table, or to use peroxide, water, etc. , alcohols, epoxides, acetals, orthocarboxylic acid esters, or organic halides. No. 1005 (4), 1920
No. 9-67999, No. 49-779). Such Ziegler-type catalysts are widely known not only for the ring-opening polymerization of norbornenes with polar substituents, but also for the polymerization of olefins and diolefins, but their distinctive feature is that they often contain N as an essential component. Contains organometallic compounds. Such organometallic compounds are generally flammable in the air and react explosively with water, so handling them is dangerous and requires extreme caution. In order to overcome these difficulties in the polymerization of olefins and diolefins, great efforts have been made to develop catalysts that do not contain organometallic compounds. There are very few examples of catalysts suitable for implementation on an industrial scale. The present inventors have developed a catalyst system with high activity, ease of handling, and easier removal of catalyst components than polymers for polymerization or copolymerization of norbornene derivatives having polar substituents on an industrial scale. We are conducting intensive research to develop this, but in the process of this research,
When combining a certain W or MO compound, a Ti tetrahalide, a compound having an electron-accepting π-electron system, N-halogen-substituted cyclic acid imides, sulfides, sulfoxides, or phosphines, an organic metal It has been discovered that even without the use of a compound, a catalyst with extremely high activity can be obtained for the polymerization of the norbornene derivative having a polar group, and the present invention has been achieved based on this knowledge.
That is, the present invention provides esters, ethers, nitriles, amides, imides,
At least one polar group selected from acid anhydride, halogen, and silyl, or at least one norbornene derivative substituted with such a polar group (hereinafter referred to as polar group-substituted norbornene derivative), or these and a polar group. and at least one species selected from the group consisting of cycloalkenes that do not have carbon-carbon double bonds and polymers that contain carbon-carbon double bonds (
a) at least one kind selected from coordination compounds of W or MO having an oxidation number of 2, 1 or 0, (b) at least one tetrahalide of T1, and (c) J electron-accepting π A polar group-substituted norbornene derivative is produced by contacting a catalyst comprising a combination of at least one component selected from a compound having a bond, N-halogen-substituted cyclic acid imides, sulfides, sulfoxides, and phosphines. There is a method for producing the 7 (co)polymer.

The method of the present invention has superior activity compared to the two-component catalyst formed by combining the above components (a) and (b), and since it does not use an organometallic compound, it is superior to conventionally known methods. It has the advantage that it is much less dangerous to handle. Next, the constituent elements of the present invention will be explained in detail.

The catalyst used in the present invention has (a) an oxygen number of 2,1
(b) at least one tetrahalide of Ti; and (c) a compound having an electron-accepting π bond; N-halogen-substituted It is prepared from at least one type of three components selected from the group consisting of cyclic acid imides, sulfides, sulfoxides, and phosphines. Here, the coordination number of W or MO is the formal number of charges remaining on W or MO when all electrons involved in bonding with each ligand of a coordination compound are considered to belong to the ligand. shall mean. Coordination compounds of W or MO suitable as component (a) include carbonyl complexes, substituted carbonyl complexes, π-arene complexes, olefin complexes, cyclopentadienyl complexes, and isonitrile complexes, but preferably those of the general formula (CO) NML or D(CO).

(1) Carbonyl complexes and substituted carbonyl complexes represented by the following formula, and particularly preferred are carbonylcarpene complexes represented by the general formula [wherein M is W or MO, and L is an alkene of QRS..Cl to 20]. or alkadiene, C6-20 aromatic hydrocarbon, cyclopentadienyl group, allyl group, 5-HROCN or pyridine, L'' is halogen, -CORa or Ra, D
is hydrogen, Lj, Na or RmaN. ．． n is an integer of 1 to 6, m is an integer of 0 to 4, and n+m is 4, 5 or 6. (In addition, Q is N, P, AS or Sb, and R
a, RO is a C1-20 hydrocarbon group, Rd is C1-10
R1' is a C1-20 hydrocarbon group or 0R°, and Re is a C1-20 hydrocarbon group)]. It is also possible to use mixtures of two or more compounds which produce these compounds by reaction. Specific examples of such compounds include W(CO)6,
M0(CO)6, (C6H6)W(CO)3, (meditylene)W(CO)3, (toluene)MO(CO)3, [
(CO)5WC1] [(CH3)4N], [(CO)5
WBr] [(CH3)4N], (CO)5WC(0CH
3) CH3,,(CO)5M0C(0CH3C2H5,
(CO)5WC (0C2H5)C6H5, (CO)5M
0C(0CH3)C6H5, (CO)5WC(0C5H
5) C4H9, (CO)5M0C(0CH3)(C4H
9),(CO)5WC(0CH3)C2H5,(CO)
5WC(C6H5)2, [(CH3)4N] [(CO)
5WC0C6H5], [(Cll3)4N] [(CO)
5M0C0C6H5], [(C2l(5)4N][C
O)5WC0CH3], [(C2H5)4N] [(CO
．． MOCOCH3], [(C,H9)4N][(CO
)5WC0C6H5], [(CH3)4N] [(CO)
5M0C0C4H9], (CO)4[P (C6H5)
3]WC(0CH3)C6ll,,(CO)4[AS(
C6H5)3]WC(0C2H5)CH3,(CO)5
WCP(C4H9)3], (CH3CN)3W(CO)
3, (CH3CN)2W(CO)4, (CH3CN)3
M0(CO)3,(pyridine)W(CO)5,(CO)
5M0 [P (C6H5)3], (C6H6)2M0,
(C5H5)2W, (norbornene)W(CO)5, (
CH2=CHCOCH3)3W, (CO)5M09? Target aim θ, (C5Fl5)2M0(CH3CN), CH3
MO(CO)3C5H5,7(C5l(5)W(CO)
3C1 etc. Also, C5H5(CO)3W-W(C
O)3C5H5,C5H5(CO)3M0-MO(CO
)3C5H5,C5H5(CO)3W-MO(CO)3
It is also possible to use dinuclear complexes such as C5H5.
In the above structural formula, C5H5 represents a π-cyclopentadienonyl group, and C6l (6 represents benzene. Compounds suitable as component (b) are Ti tetrahalides, namely TiF4, TiCl4, TjBr4 and TiI4. , TiCl4 are preferred. Compounds having an electron-accepting π bond suitable for use as component (C) include olefins or polyolefins having a conjugated electron-withdrawing substituent, and TiCl4 having a conjugated electron-withdrawing substituent. Among aromatic compounds and quinones, quinones and related compounds are preferred.

Specific examples of such compounds include p-benzoquinone, 4-0-torquinone, diuroquinone, chloro-p-benzoquinone, dichloro-p-benzoquinone, 2,3-dicyano p-benzoquinone, diphequinone, 1,4-naphthoquinone, 2- Chlorol 1.4-naphthoquinone, 5,
6,7,8-tetrachloro-1,4-naphthoquinone, chloranil, 9,10-anthraquinone, 1,4-anthraquinone, 1-chloroanthraquinone, 1-nitroanthraquinone, 1,8-dichloroanthraquinone, 1,
5-dinitroanthraquinone, 2,7-dichloroanthraquinone, Fuchsone, anthraquinone-1,2-dicarboxylic anhydride, dianthrone, p-quinone diphenylimine, p-quinone tetramethyl diimmonium salt, tetracyanoquinodimethane, anhydrous Maleic acid, citraconic anhydride, chloromaleic anhydride, phenanthraquinone, phthalic anhydride, naphthalene-2,3-dicarboxylic anhydride, maleimide, N-nitrophenylmaleimide, tetracyanoethylene, vinylidene cyanide, methylene malonic acid Diphenyl, nitrobenzene, m-dinitrobenzene, trinitrobenzene, picryl chloride and the like can be mentioned. Further, as the N-halogen-substituted cyclic acid imides used as component (c), N-chlor and N-bromine of cyclic imides of dibasic acids are suitable, and specific examples of such compounds include , N-chlorosuccinimide, N-bromosuccinimide, N-chlorophthalic acid imide, N-chlormaleimide, and the like.

Furthermore, the sulfides, sulfoxides and phosphines used as component (c) each have the general formula RaS.
Rb, RCSORd, P. Those represented by ljf are suitable [wherein Ra, Rb, RC, and Rd are C1-1.

is a hydrocarbon group or a halogenated hydrocarbon group, and Re
, Rf, and Rg are hydrogen or C1-10 hydrocarbon groups. ]. Specific examples of such compounds include dimethyl sulfide, methyl ethyl sulfide, ethyl isopropylsulfide, di-tert-butyl sulfide, dichloromethyl sulfide, chloromethyl ethyl sulfide, diphenyl sulfide, dimethyl sulfoxide, methyl ethyl sulfoxide, ethyl isopropylsulfoxide. , di-tert-butyl sulfoxide, dichloromethyl sulfoxide, chloromethyl sulfoxide, diphenyl sulfoxide, tetrahydrothiophene, ethylphosphine, propylphosphine, phenylphosphine,
Diethylphosphine, dipropylphosphine, ethylphenylphosphine, diphenylphosphine, triethylphosphine, ethyldiphenylphosphine, diethylphenylphosphine, triphenylphosphine, tricyclohexylphosphine, diphenylbenzylphosphine, tri(p-tolyl)phosphine, tri(0-tolyl) )
phosphine), trinaphthylphosphine, etc.

In carrying out the present invention, there are no particular restrictions on the method for preparing the catalyst, but (a) and (b) are prepared in advance in an inert solvent.
A preferred method is to mix the three components () and (c) and then add the monomer.

At this time, the activity of the catalyst may be improved by aging or heat treatment at an appropriate temperature before adding the monomer, or by irradiating it with light of 200 to 700 nn1 in the presence or absence of the monomer. can. The amount of the catalyst (a) component used in the method of the present invention is 0.01 to 20 mmol per mol of monomer, preferably 0.0
It is 5-2.

The amount of component (b) used is 1 to 5 CE or 2 to 20 moles per mole of component (a). The amount of component (C) to be used varies depending on the type of component (C), but is usually 0.1 to 0.0 moles per mole of component (a).
．． It is 2-5. Examples of the polar group-substituted norbornene derivatives used in the present invention include general formula 11)1
or 11)1)l.

[In the formula, A and B are hydrogen or a C1-10 hydrocarbon group, X and Y are hydrogen, a C1-10 hydrocarbon group, halogen, a C1-10 hydrocarbon group substituted with halogen, -
(CH2)NCOORl, - (CH2). ．． 0C0R
1,1 (CH2)NORl,1 (CH2)NCN,1 (CH2)NCONR2R3,1 (CI-12)NC
OOZ, -(CH2)NOCOZ, -(CH2)NOZ
, -(CH2). ．． composed of T or x and Y
]0 or Rrv4, and at least one of X and Y is hydrogen or a group other than a hydrocarbon group.

(R1 is a C1-20 hydrocarbon group, R2, R3,
R4 is hydrogen or a C1-20 hydrocarbon group, Z is a halogen-substituted hydrocarbon group, T is SiRRD3-p(R
5 is a C1-10 hydrocarbon group, D is a halogen, 0C0
R5 or 0R5, p is an integer of 0 to 3), n is O to 10
indicates an integer. )] Specific examples include methyl 5-norbornene-2-carboxylate, 5-norbornene-2-
Ethyl carbozoate, phenyl 5-norbornene-2-carboxylate, methyl 2-methyl-5-norbornene-2-carboxylate, butyl 3-phenyl-5-norbornene-2-carboxylate, dimethyl 5-norbornene-2,3-dicarboxylate, 5- cyclohexyl norbornene-2-carboxylate, allyl 5-norbornene-2-carboxylate, 5-norbornene-2-yl acetate, 5-norbornene-2-nitrile, 3-methyl-5-norbornene-2-nitrile, 2,3-dimethyl-5-norbornene-2 , 3-dinitrile, 5-norbornene-2-carboxylic acid amide, N-methyl-5-norbornene-2-carboxylic acid amide, N,N-diethyl-5-norbornene-2-carboxylic acid amide, N,N,N″,N″-tetramethyl- 5-norbornene-2,3-dicarboxylic acid diamide, 5-chloro-2-norbornene, 5-methyl-5-
Chlor-2-norbornene, chloroethyl 5-norbornene-2-carboxylate, diprompropyl 5-norbornene-2-carboxylate, dichloropropyl 5-norbornene-2-carboxylate, 5-norbornene-2-monochlorophenyl, 5-norbornene-2-carboxylate Monobromphenyl 2-carboxylate, tribromphenyl 5-norbornene-2-carboxylate, 2,3-dichloro-5-norbornene, 2-bromo-5-norbornene, 2-bromomethyl-5-norbornene, tribromobenzyl 5-norbornene-2-carboxylate , 5-norbornene-2,3-
Dicarboxylic anhydride (hymic anhydride), 2,3-dimethyl-5-norbornene-2,3-dicarboxylic anhydride, 5-norbornene-2,3-dicarboxylic acid imide,
N-phenyl-2-methyl-5-norbornene-2,3
-dicarboxylic acid imide, 2-trichlorosilyl-5-norbornene, 2-(dimethylmethoxysilyl)-5-norbornene, 2-(dimethylacetylsilyl)-5-norbornene, 2-trimethylsilyl-5-norbornene, and the like.

In addition, as a compound represented by the general formula 1( )( )1, 2-cyano 1,2,3,4,4a,5,8
, 8a-octahydro 1,4,5,8-dimethanonaphthalene, 2-carbomethoxy 1,2,3,4,4a,
5,8,8a-octahydro 1,4; 5,8-dimethanonaphthalene, 2-chloro 1,2,3,4,4a,5
, 8, &l-octahydro 1,4; 5,8-dimethanonaphthalene and the like. Furthermore, these copolymers can also be obtained using a mixture of these polar group-substituted norbornene derivatives and a cycloalkene having no polar substituent and/or a polymer containing a carbon-carbon double bond.

Suitable cycloalkenes without polar substituents are, for example, compounds represented by the following general formula.

Here, Z represents a hydrocarbon having no double bond or triple bond in a conjugated state, and examples of -Z- include the following general formulas.

-Z-ni (CR?+.,.+C Spotted situation CR6=CR7 SakiC
Rg) a-c are integers that satisfy the following conditions.

a≧1 (excluding a=4), b≧1, c≧1, b+c
≧3 Those having a polycyclo ring are also effective, but in the case of a compound having a bicyclo ring, -Z- is represented by the following formula, for example.

i 1 1-S. child? So -Y- is one (CRr)e- or KCR↓3
)FCRl4=CRl5-+. CR↓6+Gd−g is an integer, d≧0, e≧0, d+e≧1, f≧0, g≧0, where R5 to Rl6 are hydrogen or an alkyl group, an aryl group, an alkenyl group, an aralkyl group, etc. Represents hydrocarbon base.

Also, in the formula R5, R8, RlO, Rl2, 13, R16
are not necessarily the same group. More specific examples of the above compounds include cyclobutene, cyclopentene, cycloheptene, cyclooctene, cyclononene, cyclodecene, cycloundecene, cyclododecene, cyclooctadecene, 1,5-cyclooctadiene, 1,5,9-cyclododeca Examples include triene, norbornene, norbonadiene, 3-methylcyclopentene, 4-methylcyclopentene, 5-methylnorbornene, 5-vinyl-2-norbornene, tetrahydroindene, and dicyclopentadiene.

Polymers containing carbon-carbon double bonds include polybutadiene, styrene-butadiene copolymer, acrylonitrile-butadiene copolymer, polychloroprene, polyisoprene, natural rubber, ethylene-propylene-diene terpolymer, polyalkenamer, butyl rubber. etc. can be cited as representative examples.

The properties of these polymers may be liquid, rubber, or resin. The ratio of the cycloalkene having no polar substituent and/or the polymer containing a carbon-carbon double bond to the polar group-substituted norbornene derivative is not particularly limited, but is usually 0 to 95% by weight.

The method of the invention can be carried out in the presence or absence of a solvent. Suitable solvents include hydrocarbons such as hexane, heptane, benzene, toluene and cyclohexane, halogenated hydrocarbons such as chlorobenzene, dichloromethane, 1,2-dichloroethane, chloroform, tetrachloroethylene and trichlorethylene, diethyl ether, dibutyl ether, Ethers such as diphenyl ether, tetrahydrofuran, or mixtures thereof may be mentioned, but any ether that does not inactivate the catalyst or its components for the reaction of the present invention can be used. The temperature suitable for carrying out the method of the invention is −
30. ~+200'C, but temperatures of 10 to ~150°C are preferred. The molecular weight of the (co)polymer obtained by the method of the present invention can be adjusted by changing reaction conditions such as catalyst type, concentration, polymerization temperature, solvent type and amount, and monomer concentration. More preferably, compounds having at least one carbon-carbon double bond or triple bond in the molecule, such as α-olefins, α,ω-diolefins or acetylenes, or allyl chloride, acetic acid It is controlled by adding an appropriate amount of a polar allyl compound such as allyl or trimethylallyloxysilane to the reaction system. By this method, it is possible to adjust the molecular weight of the polymer without essentially changing its properties such as yield and microstructure. The concentration of the monomer can be any concentration, but 0. It is preferable that it is 1% by weight or more.

The method of the present invention can be carried out either batchwise or continuously. When carrying out the method of the present invention, the reaction is preferably carried out in an inert atmosphere such as nitrogen, argon, helium, carbon dioxide, etc., and the monomers and solvent are dehydrated and/or dehydrated before use. It is preferable to keep this in mind. Further, in order to remove impurities, the material may be treated with Ti tetrahalide prior to use. The polymer obtained by the method of the present invention can be recovered by a known method such as addition of a non-solvent such as a lower alcohol such as ethanol or methanol, steam clamming, or direct solvent removal using a vent ruder. I can do it.

The polymer may contain known antioxidants, such as 2,6-di-Ter.
It can be stabilized by adding t-butyl-4-methylphenol, 2,2''-dioxy-3,3''-di-Tert-butyl-5,5''-dimethyldiphenylmethane, phenyl-β-naphthylamine, etc.Next, The present invention will be explained in more detail with reference to Examples, but the present invention is not limited to these Examples as long as the gist thereof is not exceeded.

Example 1 A thoroughly washed and dried glass ampoule with a volume of 100 m1 was replaced with nitrogen, and then heated under a nitrogen stream (CO) with 5WC (0C).
2H5) C6H5 [W(CO)6 and PhLl and Et
Synthesized from 3OBF4 by a known method]
．． 05rn01/En-heptane solution 0.2ml (a)
．． 01mm01), 0.1m01/'n- of TiCl4
Heptane solution 0.5TLL (0.05n1m01), and 10rr1m0I (7) p-bennozoquinone 10
0.05 mt of the mixture suspended in 0 ml of n-heptane
was added and mixed well.

After standing at room temperature for 1 minute, 15.2 g of methyl 5-norbornene-2-carboxylate was added, the ampoule was sealed, and the ampoule was sealed.
The mixture was allowed to react for several hours while being shaken in a constant temperature bath at 0°C. After the reaction was completed, the solidified reaction product was dissolved in chloroform and poured into methanol containing a small amount of 2,6-di-tert-butyl-4-methylphenol (antiaging agent), and the precipitated polymer was washed door to door with methanol. The mixture was dried under reduced pressure at 40°C overnight to obtain 8.8 g (% yield) of a white resinous material. The intrinsic viscosity of this product measured in toluene at 30°C was 2.3 dt/g.

Furthermore, as a result of comparing its infrared absorption spectrum and NMR spectrum with that of a polymer of methyl 5-norbornene-2-carboxylate prepared by a conventionally known method, it was found that the ring-opened polymer (1
). Differential differential calorimeter (DSC)
The glass transition temperature (Tg) of the polymer measured was 61°C.

The polymer was completely dissolved in toluene, and no gel formation was observed. Example 2 The amount of methyl 5-norbornene-2-carboxylate used was 7
．． 6g, and instead of p-benzoquinone, 10n
The same experiment as in Example 1 was repeated, except that 0.05 ml of a mixture of 1 ml of anthraquinone suspended in 100 ml (7) n-heptane was used.

7.6 g (yield: 100%) of a slightly yellow resinous polymer was obtained.

Example 3 The amount of anthraquinone-n-heptane mixture used was 0.1
577! The experiment of Example 2 was repeated by changing to 1.

The yield of polymer was 7.4 g (97% yield). Example 4 (CO)5WC(0C2H5)C6H5 solution was replaced with 0.05n101/e di. Chlormethane solution 0.2ml
The experiment of Example 2 was repeated using

The yield of the polymer was 2.8y (yield 37%). Example 5 In a glass ampoule with a volume of 50 m1 prepared in the same manner as in Example 1, [(CH3)4N][(CO)5WC0C
6H5] 0.05m01/e dichloromethane solution 1m
11 Anthraquinone 10mm01<15n-heptane 1
0.15 mL of a mixture of 00 ml and 1 m of TiCI4
0.25 ml of 01/Fn-heptane solution was added and mixed.

After standing at room temperature for 5 minutes, 5-norbornene-2-nitrile 6y was added, the ampoule was sealed, and the mixture was allowed to react for one hour while being shaken in a constant temperature bath at 70°C. After the reaction, the contents of the ampoule were diluted with a small amount of 2,6-di-tert-butyl-4.
- It was placed in methanol containing methylphenol and left at room temperature overnight. Next, the polymer was thoroughly washed with methanol, and then dried under reduced pressure at 50°C overnight to obtain 2,8y (yield: 4
8%) of a slightly yellow resinous product was obtained.The intrinsic viscosity of this product measured at 30°C in chloroform was 0.93 d1/
It was hot at g.

Further, when its infrared absorption spectrum and NMR spectrum were compared with those of a 5-norbornene-2-nitrile polymer prepared by a conventionally known method, it was found to be a ring-opened polymer (■). The glass transition temperature (Tg) of the polymer measured with a differential calorimeter (DSC) was 140°C.

The polymer was completely dissolved in chloroform and acetone, and no gel formation was observed. Example 6 The amount of anthraquinone-n-heptane mixture used was 0.2
The experiment of Example 5 was repeated except that the weight was changed to 5 mt.

The results are shown in Table-1. Example 7 The amount of anthraquinone-n-heptane mixture used was 0.7
The experiment of Example 5 was repeated except that the volume was changed to 5 ml.

The results are shown in Table-1. Example 8 The amount of anthraquinone-n-heptane mixture used was 1 ml.
The experiment of Example 5 was repeated with the following changes.

The results are shown in Table-1. Example 9 In a glass ampoule with a volume of 50 m1 prepared in the same manner as in Example 1, 6 g of 5-norbornene-2-nitrile and 12 mt of dehydrated and degassed 1,2 dichloroethane were placed, and further 0.1 m01/'n- of TiCl4 was added. Heptane solution 0.
5ml was added and mixed well.

Separately, after drying a test tube with a volume of 20 m1 and replacing it with nitrogen,
0.05n101/' dichloromethane solution of [(CH3)4N][(CO)5WC0C6F15] 5ml 11 Anthraquinone-n-heptane mixture described in Example 51.
25mt. ．． 1.25 ml of a 1 m01/'n-heptane solution of TiC14 was added, mixed well, and allowed to stand at room temperature for 2 minutes.

After adding 1 ml of this mixture into the above-mentioned ampoule, the ampoule was sealed and the mixture was stirred in a constant temperature bath at 70° C. and reacted for hours. After the reaction, the polymer was recovered in the same manner as in Example 5, and a resinous polymer was obtained in a yield of 2.8y (yield 46%). Example 10 Instead of anthraquinone-n-heptane mixture, 10
rT1m01 p-benzoquinone and n-heptane 100
The experiment of Example 5 was repeated using 0.25 ml of the ml mixture.

The polymer yield was 2.6y (yield 43%). Example 1
1 instead of the anthraquinone-n-heptane mixture, 10
n1m01 maleic anhydride and n-heptane 100ml
The experiment of Example 5 was repeated using 0.25 ml of the mixture.

The polymer yield was 1.7 Da (yield 29%). Example 1
2 The amount of the maleic anhydride-n-heptane mixture used was 0.
The experiment in Example 11 was repeated with the volume changed to 75 mL, and the yield was 1.
4 g (yield 23%) of the polymer was obtained.

Example 13 10m instead of anthraquinone-n-heptane mixture
m01 tetracyanoethylene and n-heptane 100m
The experiment of Example 5 was repeated using 0.25 mt of the mixture of L.

The yield of the polymer was 1.2y (yield 20%). Example 14 0.1 mO1/'n-heptane solution of nitrobenzene 0.75 instead of anthraquinone-n-heptane mixture
The experiment of Example 5 was repeated using m1.

The polymer yield was 1.1y (yield 18%). Example 1
The experiment of Example 5 was repeated using a mixture of chloranil 10r]1m01 (5n-heptane 100ml) instead of the 5-anthraquinone-n-heptane mixture.

The polymer yield was 2.3y (yield %). Example 16 0.1 mO I/e toluene solution 0.25 m of nitrosobenzene instead of anthraquinone-n-heptane mixture
The experiment of Example 5 was repeated using No. 1.

A polymer was obtained in a yield of 1.3y (yield 22%). Comparative example 1
The experiment of Example 5 was repeated without using the anthraquinone-n-heptane mixture.

The yield of the polymer was 0.73 (12%), and the intrinsic viscosity measured at 30° C. in chloroform was 0.49 d1/da. Example 17 The experiment of Example 9 was repeated using 6 g of 2-methyl-5-norbornene-2-nitrile instead of 5-norbornene-2-nitrile.

A light yellow resinous polymer was obtained in a yield of 2.1y (yield 35%). The glass transition temperature (Tg) of this product measured by DSC was 153°C. Example 18 In a 100 ml glass ampoule prepared in the same manner as in Example 1, (CO)5WC(0C2H5)C was added under a nitrogen stream.
6H5 0.0511101/En-heptane solution 1m
1 (0.051 mm01), 0.15 m11 of the anthraquinone-n-heptane mixture described in Example 5 and Ti
CI4 book 1m01/En-heptane solution 0.25ml
was added, mixed, and left to stand at room temperature.

Next, methyl 5-norbornene-2-carboxylate 7.6V
and 3.4 f of cyclopentene were added, the ampoule was sealed, and the mixture was stirred in a constant temperature bath at 70° C. to react for one period. After the reaction, the polymer was recovered in the same manner as in Example 5.
The polymer yield was 10.9 g (yield 99%). The obtained polymer was confirmed to contain both monomers from its infrared absorption spectrum and NMR spectrum, and thin layer chromatography analysis was performed using silica gel as a carrier and benzene as a developing agent. As a result, the formation of a copolymer was confirmed. Example 19 In place of the mixture of methyl 5-norbornene-2-carboxylate and cyclopentene, 5-
Tribromphenyl norbornene-2-carboxylate 8
Example 18 using 55 mt of 00 g/' toluene solution
The experiment was repeated.

A white powdery polymer was obtained in a yield of 32y (yield 73%).

Example 20 A thoroughly washed and dried glass ampoule with a volume of 50 ml was replaced with nitrogen, and then [(CH3)4N][(
CO)5WC0C6H5] in 0.05Tn01/e dichloromethane solution 1ml (0.051T1m01), Ti
1 m01 of Cl4/0.25 m1 of En-heptane solution (
0.5 mt (0.05 TT1 m01) of a solution of triphenylphosphine dissolved in 100 mt n-heptane was added and mixed well.

After the mixture was allowed to stand at room temperature, 5.95 f of 5-norbornene-2-nitrile was added, the ampoule was sealed, and the mixture was allowed to react for 19 hours with stirring in a constant temperature bath at 70°C. After the reaction was completed, the contents of the ampoule were placed in methanol containing a small amount of 2,6-di-tert-butyl-4-methylphenol and left at room temperature overnight. The polymer was then thoroughly washed with methanol and then dried under reduced pressure at 50°C overnight to obtain a slightly yellow resinous product of 5V (yield: 84%). The intrinsic viscosity of this substance measured at 30°C in chloroform is 0.71d1
/g.

Further, as a result of comparing its infrared absorption spectrum and NMR spectrum with that of a 5-norbornene-2-nitrile polymer prepared by a conventionally known method, it was found to be a ring-opened polymer (■). The glass transition temperature (Tg) of the polymer measured with a differential calorimeter (DSC) was 141°C.

The polymer was completely dissolved in toluene, and no gel formation was observed. The yields are shown in Table 12 along with Examples 21 to 23.
are summarized in the following. Triphenylphosphine solution (a)
．． 1 m01/Fn-heptane) to 0.25 m1 (0
．． The experiment of Example 20 was repeated except that the diameter was changed to 0.025 mm.

The results are shown in Table-2. Example n Triphenylphosphine solution (a). 1m01/1n-
heptane) amount to 0.75ml (a). 075n1m0
The experiment of Example 20 was repeated except that 1) was changed.

The results are shown in Table-2. Example 23 Triphenylphosphine solution (4). 1m01/En-
The experiment of Example 20 was repeated except that the amount of heptane) was changed to 1.0 Tn1 (0.1 mm0 I).

The results are shown in Table-2. Example 24 Instead of the triphenylphosphine solution, 0.25 ml (a) of a mixture of 10 mm 01 dimethyl sulfoxide suspended in 100 ml (7) n-heptane was used. 025mm
The experiment of Example 20 was repeated using 01).

The results are shown in Table-3. Example 25 The amount of dimethyl sulfoxide n-heptane mixture was reduced to 0.
5m1 (a). The experiment of Example 24 was repeated except that the temperature was changed to 0.5 mm.

The results are shown in Table-3. Example 26 The amount of dimethyl sulfoxide n-heptane mixture was reduced to 0.
Example 2 by changing to 75Tn1 (0.075rr1m0)
Experiment 4 was repeated.

The results are shown in Table-3. Example 27 The amount of dimethyl sulfoxide n-heptane mixture was 1.
The experiment of Example 24 was repeated by changing the size to 5 m1 (0.15 m1 m01).

The results are shown in Table-3. Example 28 Instead of triphenylphosphine solution, Tert
-butyl sulfide 10rnm01 100ml (7)
Solution (a) dissolved in n-heptane solution. 1m01/E
n-heptane) 0.3 ml (a). The experiment of Example 20 was repeated using 03mm0I).

The results are shown in Table-4. Example 29 The amount of di-tert-butyl sulfide was 0.5 ml (4). 05mm01)
The experiment of Example 28 was repeated with the following changes.

The results are shown in Table-4. Example 30 The amount of di-tert-butyl sulfide was 1.577LL
(stomach). 15n1m01) and repeated the experiment of Example 28.

The results are shown in Table-4. Example 31 Instead of the triphenylphosphine solution, a solution (4) in which triethylphosphine 10rT1m01 was dissolved in 100ml (7) n-heptane. 1m01/En-heptane) 0.25m1 (a). The experiment of Example 20 was repeated using 025n1m01).

The yield of the polymer was 2.1y (yield 36%). Example 32 0.0% of (CO)5WC(0C2H5)C6H5 instead of [(CH3)4N][(CO)5WC0C6H5] solution.
The experiment of Example n was repeated using 1 mL of 05rr101/'n-heptane solution.

The yield of the polymer was 1y (yield 17%). Example 33
In a 50 mL glass ampoule prepared in the same manner as in Example 20, 0 of (CO)5WC(0C2H5)C6H,
．． 05m] 0I/1n-heptane solution 0.2T! Lt(
0.01mm0, TiCl, 0.1m01/En-
0.5Tnt (0.05nlml) of heptane solution and 0.1ml(4).01mmml of triphenylphosphine solution in n-heptane were added and mixed.

After allowing the powder to stand at room temperature, 7.6y of methyl 5-norbornene-2-carboxylate was added, the ampoule was sealed, and the ampoule was sealed.
The mixture was allowed to react for one hour while being shaken in a constant temperature bath at 0°C. After the reaction, the solidified reaction product was dissolved in chloroform, and a small amount of 2
, 6-di-tert-butyl-4-methylphenol in methanol and left at room temperature overnight. Next, the polymer was thoroughly washed with methanol and then dried under reduced pressure at 40° C. overnight to obtain a white resin-like material of 7.6y (yield: 100%). The intrinsic viscosity of this product measured in toluene at 30°C was 4.6 dL/g.

In addition, as a result of comparing its infrared absorption spectrum and NMR spectrum with that of a polymer of methyl 5-norbornene-2-carboxylate prepared by a conventionally known method, it was found that the ring-opened polymer (■
). Differential differential calorimeter (DSC)
The glass transition temperature (Tg) of the polymer measured was 61°C.

The polymer was completely dissolved in toluene and no gel formation was observed. Example 34 The amount of triphenylphosphine was adjusted to 0.2 ml (0.02 r
The same experiment as in Example 33 was repeated by changing to .nm01).

The yield of the polymer was 6.2y (yield 82%). Example 35 Di-tert-butyl sulfide n-heptane solution (a) instead of triphenylphosphine. 1m01/En
-Heptane) 0.1 ml (0.01 mm 01) was used to repeat the same experiment as the example feather.

The yield of polymer was 6.8 J (yield 90%). Example 36 The same experiment as Example 20 was repeated using 6 g of 2-methyl-5-norbornene-2-nitrile instead of 5-norbornene-2-nitrile.

A pale yellow resinous heavy substance was obtained with a yield of 4.6V (yield 77%). Glass transition temperature (Tg) measured by DSC
The temperature was 153°C. Example 37 The same experiment as Example 26 was repeated using 5-chloromethyl-2-norbornene 14.2' instead of 5-norbornene-2-nitrile.

A white resinous material was obtained in a yield of 14.2y (yield 100%). The glass transition temperature (Tg) measured by DSC is 7
It was 1℃. Example 38 (CO)5WC(0C2H5) in a 100 ml glass ampoule prepared in the same manner as in Example 20 under a nitrogen stream.
0.05n101/En-heptane solution of C6H5 1m
1 (a). 05rr1m0, di-tert-butyl sulfide n-heptane solution described in Example 28 0.3m
0.25 ml of a 1 m01/'n-heptane solution of 11 and TlCl4 was added and mixed, and the mixture was allowed to stand at room temperature.

Next, 76y of methyl 5-norbornene-2-carboxylate and 3.4y of cyclopentene were added, the ampoule was sealed, and the mixture was allowed to react for 17 hours with stirring in a constant temperature bath at 70'C.

After the reaction, the polymer was recovered in the same manner as in Example 33. The polymer yield was 10.9y (yield 99%). The obtained polymer was confirmed to contain both units from its infrared absorption spectrum and NMR spectrum, and thin layer chromatography analysis using silica gel as a carrier and benzene as a developing agent revealed that the copolymer was The formation of coalescence was confirmed. Example 39 Instead of triphenylphosphine, a mixture of 0.25 ml (0.025 rr1 m
The experiment of Example 20 was repeated using 01).

The yield of the polymer was 4.7y (yield 78%). Example 40 Example 39 by changing the amount of N-chlorosuccinimide n-heptane mixture to 0.5 ml (0.05rnm01)
The experiment was repeated.

The yield of the polymer was 4.5y (yield 75%). Example 41 The experiment of Example 39 was repeated except that the amount of N-resuccinimide n-heptane mixture used was changed to 0.75 mt (0.075 n1 m01).

The yield of the polymer was 3.7y (yield 62%). Example 42 In a glass ampoule with a volume of 50 m1 prepared in the same manner as in Example 20, 5-norbornene-2-nitrile modified, 1
, 5 ml of 2-dichloroethane and 6.4 y of styrene-butadiene copolymer (trade name JSRl5O2, manufactured by Nippon Gosei Rubber Co., Ltd., bound styrene 23%, purified by reprecipitation with chloroform-methanol and dried under reduced pressure at 40°C overnight) to 100 ml. Solution 10 in 1,2 dichloroethane
m1 and further 0.1 m01/En- of TiCl4
0.5 ml of heptane solution was added and mixed well.

Especially the volume is 2077! The test tube of t was dried and replaced with nitrogen [(CH3)4N] [(CO)5WC0C6H5]
0.05rT101/e dichloromethane solution 5ml
1.25 ml of a 1 m01/En-heptane solution of 1.5 Tnt1TiC14 of the N-chlorosuccinimide n-heptane mixture of Example 39 was added and mixed to cause a two-powder reaction.

After adding Lml of this mixture into the above ampoule, the ampoule was sealed and a one-hour reaction was carried out at 70° C. in the same manner as in Example 20. After the reaction, the polymer was recovered in the same manner as in Example 20 to obtain a resinous polymer in a yield of 2.7y (yield 41%). The infrared absorption spectrum, NMR spectrum and thin layer chromatography of this product confirmed that it contained both norbornene nitrile and styrene-butadiene copolymer chains. The glass transition temperature (Tg) measured with a differential calorimeter (DSC) is 13
It was rC. Example 43 Using 2.5 ml of the triphenylphosphine solution described in Example 20 instead of the N-chlorosuccinimide n-heptane mixture
Experiment 2 was repeated.

The yield of the polymer was 2.1y (yield 32%).Example 44 The amounts of (CO)5WC(0C2H5)C6H5 solution, triphenylphosphine solution, and TiCl4 solution were 0.4ml, 110.2ml, and 0.0ml, respectively. .1 ml, and instead of methyl 5-norbornene-2-carboxylate,
0.64y/Mll of tribromphenyl 5-norbornene-2-carboxylate, 2 dichloroethane solution 28ml
The experiment of Example 33 was repeated using

Claims (1)

[Claims] 1. In the presence or absence of an inert solvent, ester,
Norbornene derivatives substituted with at least one polar group selected from ether, nitrile, amide, imide, acid anhydride, halogen, and silyl, or a substituent having such a polar group (hereinafter referred to as polar group-substituted norbornene derivative) or at least one selected from the group consisting of cycloalkenes having no polar group and polymers containing carbon-carbon double bonds,
(a) at least one type selected from coordination compounds of W or Mo having an oxidation number of 2, 1, or 0, (b) at least one type of Ti halide, and (c) electron-accepting π Compounds having a bond, N-halogen-substituted cyclic acid imides,
1. A method for producing a (co)polymer of norbornene derivatives, which comprises contacting a (co)polymer of norbornene derivatives with a catalyst comprising a combination of at least one type of three components selected from sulfides, sulfoxides, and phosphines. 2 Polar group-substituted norbornene derivatives have the general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, A and B are hydrogen or C_1_～_
1_0 hydrocarbon group, halogen, C_1_ to_1_0 hydrocarbon group substituted with halogen, -(CH_2)_n
COOR^1, (CH_2)_nOCOR^1, -(C
H_2)_nOR^1, -(CH_2)_nCN, -(
CH_2)_nCONR^2R^3, -(CH_2)_
nCOOZ, -(CH_2)_nOCOZ, (CH_2
)_nOZ, -(CH_2)_nT or ▲There is a mathematical formula, chemical formula, table, etc.▼ consisting of X and Y, or ▲There is a mathematical formula, chemical formula, table, etc.▼, and at least one of X and Y is hydrogen. Or it is a group other than a hydrocarbon group. (R^1 is a hydrocarbon group of C_1_ to_2_0, R
^2, R^3, R^4 are hydrogen or C_1_~_2_0
a hydrocarbon group, Z is a halogen-substituted hydrocarbon group,
T has ▲mathematical formulas, chemical formulas, tables, etc.▼(R^5 is C_
1_~_1_0 hydrocarbon group, D is halogen, OCO
R^5 or OR^5, p is an integer from 0 to 3), n is 0 to
Indicates an integer of 10. )] is at least one compound selected from the following. 3 The polar group-substituted norbornene derivative is methyl 5-norbornene-2-carboxylate, ethyl 5-norbornene-2-carboxylate, butyl 5-norbornene-2-carboxylate, phenyl 5-norbornene-2-carboxylate, 2- Methyl-5-norbornene-2-carboxylate, ethyl 3-methyl-5-norbornene-2-carboxylate, methyl 3-phenyl-5-norbornene-2-carboxylate, cyclohexyl 5-norbornene-2-carboxylate, 5-norbornen-2-yl acetate,
Chlorethyl 5-norbornene-2-carboxylate, 5-
dibrolpropyl norbornene-2-carboxylate, 5-
Dichloropropyl norbornene-2-carboxylate, 5-
monochlorophenyl norbornene-2-carboxylate, 5
-monobromphenyl norbornene-2-carboxylate,
Tribromphenyl 5-norbornene-2-carboxylate, tribromobenzyl 5-norbornene-2-carboxylate, 5-norbornene-2-nitrile, 2-methyl-5
-Norbornene-2-nitrile, 3-methyl-5-norbornene-2-nitrile, 3-phenyl-5-norbornene-2-nitrile, N,N-dimethyl-5-norbornene-2-carboxylic acid amide, N,N -diethyl-5-
norbornene-2-carboxylic acid amide, N,N-diphenyl-5-norbornene-2-carboxylic acid amide, N,
N-pentethylene-5-norbornene-2-carboxylic acid amide, and N-phenyl-5-norbornene-2,
The manufacturing method according to claim 2, wherein at least one selected from 3-dicarboxylic acid imides is used. 4 Cycloalkenes without polar substituents include cyclobutene, cyclopentene, cycloheptene, cyclooctene, cyclodecene, cyclododecene, cyclohexadecene, 1,5-cyclooctadiene, 1,5,9-cyclodecatriene, norbornene, norbornadiene, cyclo Pentadiene, 3-methylcyclopentene, 5-methylnorbornene, 5-phenylnorbornene, tetrahydroindene, ethylidenenorbornene, 5-vinyl-
2. The manufacturing method according to claim 1, which is at least one selected from 2-norbornene, dicyclopentadiene, and dihydrodicyclopentadiene. 5 The polymer containing carbon-carbon double bonds is polybutadiene, polyisoprene, styrene-butadiene copolymer, acrylonitrile-butadiene copolymer, natural rubber, polychloroprene, styrene-butadiene block copolymer, ethylene-propylene 2. The manufacturing method according to claim 1, wherein the manufacturing method is at least one selected from -terpolymer, polypentenamer, polyoctenamer, and butyl rubber. 6 The coordination compound of W or Mo has the general formula (CO)_5MCR^aR^b or D(CO)_5M
COR^a [In the formula, M is W, D is ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ or Li, and R^a is C_1_～_
2_0 is a hydrocarbon group, R^d is a C_1_ to_1_0 hydrocarbon group, R^b is a C_1_ to_2_0 hydrocarbon group or OR^e, and R^e is a C_1_ to_2_0 hydrocarbon group. ] The manufacturing method according to claim 1, wherein the carbonyl-carbene complex is at least one selected from the following. 7. The manufacturing method according to claim 1, wherein the Ti tetrahalide is TiCl_4. 8. The manufacturing method according to claim 1, wherein the compound having an electron-accepting π-bond is at least one selected from benzoquinone, naphthoquinone, anthraquinone, substituted products thereof, and tetracyanoquinodimethane. 9. The manufacturing method according to claim 1, wherein the N-halogen-substituted cyclic acid imide is at least one selected from N-chlorosuccinimide and N-chlorophthalic acid imide. 10 Sulfides, sulfoxides and phosphines include dimethyl sulfide, methyl ethyl sulfide, ethyl isopropylsulfide, di-tert-butyl sulfide, diphenyl sulfide, dimethyl sulfoxide, methyl ethyl sulfoxide, ethyl isopropylsulfoxide, di-tert-butyl sulfoxide, diphenyl Sulfoxide, tetrahydrothiophene, ethylphosphine, propylphosphine, phenylphosphine, diethylphosphine, di-propylphosphine, ethylphenylphosphine, diethylphenylphosphine,
At least one selected from diphenylphosphine, triethylphosphine, ethyldiphenylphosphine, triphenylphosphine, tricyclohexylphosphine, diphenylbenzylphosphine, tri(p-tolyl)phosphine, tri(o-tolyl)phosphine, and trinaphthylphosphine. A manufacturing method according to claim 1.