JPH09157329A - Preparation of substituted acetylene polymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To efficiently obtain a substd. acetylene polymer having a narrow mol.wt. distribution, high stereotaaticity and high mol.wt. by polymerizing a substd. acetylene compd. in the presence of a specified transition metal complex and an N-, P-, or As-contg. basic compd. SOLUTION: A transition metal complex represented by the formula [M(OR<1> ) L<1> n ]2 (wherein M represents a group VIII transition metal element; R<1> represents an alpiph., alicyclic, arom., or aroaliph. hydrocarbon group; L1 represents an org. compd. having a carbon-carbon multiple bond; and (n) is 1 to 3) is used as the specified. transition metal complex (a). M is pref. rhodium. The amt. of the component (a) used is 1×10<-5> to 10mol/l base on a solvent. E.g. triphenylphosphine is pref. used as the basic compound (b). The amt. of the component (b) used is 0.1 to 10 in terms of molar ratio to the component (a). The acetylene compound (c) is represented by the formula HC≡CR (wherein R represents an aliph, alicyclic, arom., or aroaliph. hydrocarbon group or a heterocyclic group having a hereto element) and is, e.g. phenylacetylene. The polymn. temp. is -78 to 130 deg.C.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for producing a substituted acetylene polymer. More specifically, the present invention polymerizes an acetylene compound with high efficiency,
The present invention relates to a new method capable of producing a high stereoregular high molecular weight substituted acetylene polymer having a narrow molecular weight distribution.

[0002]

2. Description of the Related Art Conventionally, acetylene polymers have been attracting attention as useful for various functional materials such as optical materials and conductive materials. Further, as a polymerization catalyst used for producing a polymer from an acetylene compound, Ti compound / organoaluminum system, iron compound /
Ziegler-Natta catalysts such as organic aluminum catalysts, molybdenum / tungsten catalysts, rhodium complex catalysts, etc. are known.

However, for example, a Ziegler-Natta catalyst gives a high molecular weight polymer to an acetylene compound having a linear alkyl group, but to an acetylene compound having a substituent having a 1-position branch or an aromatic group. However, there is a restriction that they have no polymerization performance or that they give only a polymer having an extremely low molecular weight. In addition, a molybdenum- or tungsten-based catalyst has an ability to polymerize with an acetylene compound having a substituent having a 1-position branch or an aromatic group, and a molybdenum-based catalyst has an extremely narrow molecular weight distribution under specific conditions. However, there is a problem that the stereoregularity is low.

On the other hand, it is known that some rhodium complex catalysts give a polymer having a high stereoregularity and having a polymerization performance for an acetylene compound having an aromatic group (for example, Journal of Polymer Science). : Parr A Polym
er Chemistry, 24, 991, 1986, JP-A-63-275613, JP-A-63-275614).
However, in this case, the polymerization activity was not sufficient, and the obtained polymer had a small molecular weight and was not suitable for use as a polymer material. As the rhodium complex-based catalyst, a chlorine-containing rhodium complex such as [Rh (C ₈ H ₁₂ ) Cl ₂ ] is used as a method for obtaining a polymer having high activity, high stereoregularity, and high molecular weight, and a polymerization solvent As a method, a basic amine compound such as triethylamine is disclosed (“Kagaku”, vol. 46, page 759, 1991). However, this method only gives an acetylene polymer having a wide molecular weight distribution, and remains in the polymer. There have been many industrial problems such as corrosion during processing by chlorine, problems in the manufacturing process due to the use of a large amount of basic compounds as solvents, toxicity due to residual polymer, and odor. Furthermore, as a method for obtaining a polymer having a high stereoregularity and a high molecular weight with a narrow molecular weight distribution, for example, Rh (C = CC ₆ H ₅ ) (C
A method using a rhodium complex having a ethynyl group, such as ₇ H ₈₎ [P (C ₆ H _{5) 3] 2} are also disclosed (Jour
nal of the American Chemical Society, Vol. 116, 1
2131, 1994), this method has a low efficiency as an initiator of the rhodium complex used during polymerization, the polymerization activity is not sufficient, and the synthesis of this rhodium complex is complicated. There was a problem.

According to such conventional methods, it is difficult to polymerize an acetylene compound with high efficiency using a complex that can be easily synthesized to obtain a high molecular weight stereoregular acetylene polymer having a narrow molecular weight distribution. It has been desired to develop a new polymerization catalyst that can overcome these drawbacks and a polymerization method using the same.

[0006]

SUMMARY OF THE INVENTION The present invention has the following formulas for solving the above problems.

[0007]

[Chemical 6]

(Wherein M is a transition metal element belonging to Group VIII of the periodic table, R ¹ is an aliphatic, alicyclic, aromatic or araliphatic hydrocarbon group, and L ¹ is a carbon-carbon multiple bond. In the presence of a basic compound containing a transition metal complex represented by the formula (1), a transition metal complex represented by the formula: n is a positive integer of 1 to 3, and nitrogen, phosphorus or arsenic, or

[0009]

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(In the formula, M is a transition metal element belonging to Group VIII of the periodic table, L ¹ is an organic compound having a carbon-carbon multiple bond, X is a halogen atom, and m and l are positive or negative 1 to 3 respectively. Of the transition metal complex represented by the formula, and m + 1 = 2 or 3)

[0011]

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An alcoholate compound represented by the formula (wherein R ² is an aliphatic, alicyclic, aromatic or araliphatic hydrocarbon group, Y is an alkali metal of Group I of the periodic table) and nitrogen, In the presence of a basic compound containing phosphorus or arsenic, the following formula

[0013]

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(In the formula, R represents an aliphatic, alicyclic, aromatic or araliphatic hydrocarbon group which may have a substituent or a heterocyclic group having a hetero element). Provided is a method for producing a substituted acetylene polymer, which comprises polymerizing an acetylene compound. The present invention also provides a method of causing an amine compound to coexist during the polymerization of the acetylene compound.

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION The transition metal complex as described above is easy to synthesize. In the present invention, the transition metal complex which can be easily synthesized is used as a catalyst component, An acetylene compound having various substituents is polymerized with high efficiency to give a high molecular weight and highly stereoregular substituted acetylene polymer having a narrow molecular weight distribution.

In this case, the metal atom of Group VIII of the periodic table, M, in the complex compound represented by the above general formula is
For example, specifically, iron, ruthenium, osmium, cobalt, rhodium, iridium, nickel, palladium,
Platinum and the like are exemplified, but rhodium is particularly preferable. Further, R ¹ and R ² in the general formulas representing the transition metal complex and the alcoholate compound each represent a hydrocarbon group of a fatty acid, an alicyclic group, an aromatic group or an aromatic fatty acid as a monovalent hydrocarbon group. , And these may optionally have a substituent.

Specifically, for example, methyl, ethyl,
Alkyl groups such as isopropyl and tert-butyl, alkenyl groups such as vinyl, allyl, ethynyl, 1-propyl and 3,3-dimethyl-1-butynyl, cyclopentyl,
Saturated or unsaturated alicyclic groups such as cyclohexyl and cyclohexenyl, aromatic groups such as phenyl, tolyl, xylyl and naphthyl, aromatic fatty acid groups such as benzyl and 2-phenylethynyl, and methoxy having substituents bonded thereto. Hexyl, trifluoromethylcyclohexyl, methylphenyl, 2,4-dimethylphenyl, 2- (2-methoxyphenyl) ethynyl, 2- (2-trifluoromethylphenyl) ethynyl, 2- (4-methoxyphenyl) ethynyl, 2 Substituted hydrocarbon groups such as-(4-trifluoromethylphenyl) ethynyl and the like can be mentioned.

L ¹ represents a ligand composed of an organic compound having a carbon-carbon multiple bond, and specific examples thereof include unsaturated organic compounds such as alkylene, alkynylene, diene, cyclodiene, triene and cyclotriene. Can be mentioned. Of these, cyclodienes such as cyclootadiene and norbornadiene are preferable. Specific examples of the basic compound having nitrogen, phosphorus or arsenic include trimethylamine, triethylamine, pyridine and 4 (N, N).
Amine compounds such as pyridine derivatives such as -dimethyl) aminopyridine; trimethylphosphine, triethylphosphine, triisopropylphosphine, dimethylphenylphosphine, methyldiphenylphosphine, triphenylphosphine, 1,2-bis (diphenylphosphino) ethane, 1, 3-bis (diphenylphosphino) propane, 1,4-bis (diphenylphosphino) butane, 2,3-bis (diphenylphosphino) butane, 2,
2-bis (diphenylphosphino) -1,1'-binaphthyl, 2,2-bis (dicyclohexylphosphino)-
Phosphorus compounds such as 1,1'-binaphthyl; arsenic compounds such as dimethylphenyl arsenic, methyldiphenyl arsenic, triphenyl arsenic and the like are mentioned, and among them, phosphorus compounds such as triphenyl phosphine are particularly preferable.

Further, regarding the acetylene compound in the present invention, as an example of R in the above general formula, an alkyl group, an alkenyl group, a cycloalkyl group, a cycloalkenyl group, an aryl group, an aralkyl group, which may have a substituent, Examples thereof include a heterocyclic group containing a hetero element. More specifically, the acetylene compound used in the present invention is, for example, 1-propyne, 1-butyne, 1-pentyne, 1-hexyne, or 3-methyl-1-butyne or 3-methyl-1 having a substituent. -Pentin, 1-alkyne such as 3-methyl-1-hexyne; tert-butylacetylene, cyclohexylacetylene; phenylacetylene and 2-methylphenylacetylene, 3-methylphenylacetylene, 4-methylphenylacetylene, 2-methoxyphenyl Acetylene, 3-methoxyphenylacetylene, 4-methoxyphenylacetylene,
2-trifluoromethylphenylacetylene, 3-trifluoromethylphenylacetylene, 4-trifluoromethylphenylacetylene, 2-nitrophenylacetylene, 3-nitrophenylacetylene, 4-nitrophenylacetylene, 2-chlorophenylacetylene, 3-
Chlorophenylacetylene, 4-chlorophenylacetylene, 2-cyanophenylacetylene, 3-cyanophenylacetylene, 4-cyanophenylacetylene, 2-
Aminophenylacetylene, 3-aminophenylacetylene, 4-aminophenylacetylene, 2-dimethylaminophenylacetylene, 3-dimethylaminophenylacetylene, 4-dimethylaminophenylacetylene,
2,3-dimethylphenylacetylene, 2,4-dimethylphenylacetylene, 2,5-dimethylphenylacetylene, 2,6-dimethylphenylacetylene, 3,4
-Dimethylphenylacetylene, 3,5-dimethylphenylacetylene, 2,3-dimethoxyphenylacetylene, 2,4-dimethoxyphenylacetylene, 2,5-
Dimethoxyphenylacetylene, 2,6-dimethoxyphenylacetylene, 3,4-dimethoxyphenylacetylene, 3,5-dimethoxyphenylacetylene, 2,
4,6-Trimethylphenylacetylene, 2,4,6-
Substituted phenylacetylene such as trimethoxyphenylacetylene; 1-naphthylacetylene, 2-naphthylacetylene, 1-anthracenylacetylene, 2-anthracenylacetylene, 9-anthracenylacetylene, 1
-Polycyclic aromatic acetylene such as phenanthylacetylene;
2-ethynylpyridine, 3-ethynylpyridine, 4-ethynylpyridine, 4-ethynyl-2-methylpyridine,
Pyridine derivatives such as 4-ethynyl-2,6-dimethylpyridine; compounds such as 4-ethynylquinoline, 2-ethynylpyrrole, 2-ethynylfuran, and 2-ethynylthiophene. Furthermore, phenylacetylene compounds having a substituent containing a mesogenic group as a constituent unit at the ortho, meta, and para positions of the aromatic ring of phenylacetylene can also be mentioned.

In the polymerization reaction of the present invention, a suitable solvent can be used as long as it does not react with the catalyst to deactivate the catalyst or react with the acetylene compound to change the quality thereof. Examples of the solvent include aliphatic hydrocarbons such as pentane, hexane and heptane; aromatic hydrocarbons such as toluene and xylene; halogen-containing hydrocarbon solvents such as methylene chloride; alcohol solvents such as methanol and ethanol; diethyl ether and tetrahydrofuran. , Ether solvent such as 1,4-dioxane; ester solvent such as methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, methyl benzoate and ethyl benzoate.

The amount of the above-mentioned transition metal complex used as a catalyst is usually 1 × 10 ⁻⁵ to the solvent in each case.
The polymerization temperature is −78 ° C. to 1 in the range of 10 mol / l.
Polymerization can be carried out at a temperature of about 30 ° C., preferably −30 ° C. to 100 ° C., and a polymerization time of about 1 minute to 72 hours, preferably 1 minute to 24 hours. The alcoholate compound may be added in a molar ratio of 0.1 to 10, preferably 0.2 to 2, with respect to the transition metal complex.

The above basic compound containing nitrogen, phosphorus or arsenic is also used in a molar ratio of 0.1 to 10, preferably 0.2 to 5, with respect to the transition metal complex. can do. Further, by allowing an amine compound to coexist in the reaction system, it is possible to further narrow the molecular weight distribution of the resulting substituted acetylene polymer.
Specific examples of the amine compound in this case include aliphatic primary amines such as methylamine, ethylamine, n-propylamine, isopropylamine, butylamine and laurylamine; dimethylamine, diethylamine, di-n-propylamine, diisopropyl. Aliphatic secondary amines such as amine and dibutylamine; trimethylamine,
Aliphatic tertiary amines such as triethylamine, tri-n-propylamine, triisopropylamine and tributylamine; aromatic amines such as aniline and N, N-dimethylaniline; piperidine, 2-methylpyridine, 4-methylpyridine, 2 , 4-dimethylpyridine, 2,6-dimethylpyridine, 2,6-tert-butylpyridine,
Examples thereof include nitrogen-containing heterocyclic derivatives such as N-methylpiperidine and 4- (N, N-dimethylamino) pyridine.

These amine compounds are one of transition metal complexes.
It is desirable to add about 100 to 100 times the molar amount, and more preferably about 2 to 20 times the molar amount.

[0024]

EXAMPLES Examples will be shown below to more specifically describe the embodiments of the present invention. The catalyst synthesis and the acetylene compound polymerization operation were all performed in an argon atmosphere. The solvent and reagents used were those stored after purification under an argon atmosphere. Average molecular weight of the polymer,
Molecular weight distribution (Mw / Mn) is determined by gel permeation chromatography (GPC, Waters product Waters 4
86, Shodex KF 802, KF803, KF804 column system). ¹ H-NMR of the polymer was measured using a JEOL EX-207 NMR spectrometer (deuterated chloroform solvent). Reference Example 1 A mixture of 155 mg (0.34 mmol) of [Rh (nbd) Cl] ₂ (nbd; 2,5-norbornadiene) and 10 ml of methylene chloride was added to 56 mg (1 mmo) at room temperature.
A solution of 1) of potassium hydroxide dissolved in 7 ml of methanol was added, and sufficient stirring was continued at room temperature for 4 hours. After removing the solvent from the reaction mixture under reduced pressure, the obtained yellow precipitate was thoroughly washed with methanol. [Rh (OCH ₃ )
(Nbd)] ₂ complex was obtained in a yield of 70 mg. Example 1 Degassing the inside of a Schlenk tube with a three-way cock of 80 ml,
After substituting with argon, 6.8 mg (0.015 mmol) of the metal complex synthesized in Reference Example 1, 9.4 mg (0.036 mmol) of triphenylphosphine, and 3 ml of tetrahydrofuran as a solvent were added, and -25
Stirring was continued for 5 minutes with a magnetic stirrer at 0 ° C. to sufficiently dissolve the complex catalyst. Phenylacetylene 0.165 ml (1.5 mmol), tetralin 0.
A solution of 165 ml dissolved in 1.6 ml of tetrahydrofuran was added to initiate polymerization. After continuing stirring at room temperature for 40 minutes, 0.1 ml of acetic acid was added to terminate the polymerization. The reaction solution was poured into 50 ml of methanol to precipitate a polymer, and then the polymer was collected by filtration. About 5
It was dried under reduced pressure at room temperature for 183 hours to obtain 183 mg of a yellow polymer. Number average molecular weight 13800, Mw / Mn = 1.
33. The ¹ H-NMR spectrum of this polymer showed that the main chain of this polymer possessed high stereoregularity. Example 2 In addition to rhodium complex and triphenylphosphine, N, N
-Dimethylaminopyridine 36.7 mg (0.3 mmo
Example 1 except that l) was added and the reaction time was 10 minutes.
Polymerize phenylacetylene by the same procedure as in 18
0 mg of yellow polymer was obtained. Number average molecular weight 7100,
Mw / Mn = 1.17. Similar to the polymer obtained in Example 1, the ¹ H-NMR spectrum of this polymer showed that the main chain of this polymer possessed high stereoregularity. Example 3 The inside of a Schlenk tube with a three-way cock of 80 ml was deaerated,
After replacement with argon, [Rh (nbd) Cl] ₂ 6.
9 mg (0.015 mmol), triphenylphosphine 15.4 mg (0.06 mmol), and 4-
(N, N-dimethyl) aminopyridine 36.7 mg
(0.3 mmol), and 3 ml of tetrahydrofuran as a solvent were added, and stirring was continued for 5 minutes with a magnetic stirrer at -25 ° C to sufficiently dissolve the complex catalyst. 0.165 ml of phenylacetylene (1.
5 mmol), tetralin 0.165 ml to 1.6 ml
After adding the solution dissolved in tetrahydrofuran of
Polymerization was initiated by adding 6.8 mg of a CH ₃ ONa methanol solution having a concentration of 4.4 mmol / g. After continuing stirring at room temperature for 20 minutes, 0.1 ml of acetic acid was added to terminate the polymerization. The reaction solution was poured into 50 ml of methanol to precipitate a polymer, and then the polymer was collected by filtration. A dry yellow polymer was obtained under reduced pressure at room temperature for about 5 hours. Number average molecular weight 9620, Mw / Mn = 1.10. The ¹ H-NMR spectrum of this polymer showed that the main chain of this polymer had high stereoregularity as in Example 1. Example 4 Degassing the inside of a Schlenk tube with 80 ml three-way cock,
After substituting with argon, 6.8 mg (0.015 mmol) of the metal complex synthesized in Reference Example 1, 9.4 mg (0.036 mmol) of triphenylphosphine, and 4
36.7 mg of-(N, N-dimethyl) aminopyridine
(0.3 mmol), and 3 ml of tetrahydrofuran as a solvent were added, and stirring was continued for 5 minutes with a magnetic stirrer at -25 ° C to sufficiently dissolve the complex catalyst. 0.165 ml of phenylacetylene (1.
5 mmol), tetralin 0.165 ml to 1.6 ml
Polymerization was initiated by adding a solution prepared by dissolving the above in tetrahydrofuran. After stirring at room temperature for 10 minutes, 0.1
The reaction solution (ml) was withdrawn. The monomer conversion rate measured by gas chromatography was 100%. The polymer contained in the reaction solution is 77 in number average molecular weight.
00 and Mw / Mn = 1.15. This reaction solution also contained 0.165 ml (1.5 mm) of phenylacetylene.
ol), was dissolved in 1.6 ml of tetrahydrofuran and converted at room temperature for another 11 minutes for polymerization,
Polymerization was stopped by adding 0.1 ml of acetic acid. Reaction solution 5
After pouring into 0 ml of methanol to precipitate the polymer,
The polymer was recovered by filtration. It was dried under a reduced pressure at room temperature for 5 hours with arrow rain to obtain 358 mg of a yellow polymer. Number average molecular weight 15800, Mw / Mn = 1.28. As with the polymer obtained in Example 1, it was confirmed by ¹ H-NMR spectrum that the main chain of the polymer had high stereoregularity. Example 5 The monomer charged in the second time was 4-methoxyphenylacetylene in place of phenylacetylene, and 12 each after charging the monomer in the first time and the second time.
Polymerization was carried out in the same manner as in Example 4 except that the polymerization was carried out for a polymerization time of minutes. The number average molecular weight of the polymer separated before the second monomer addition was 8900, Mw / Mn was 1.12, the number average molecular weight of the finally obtained block copolymer was 23600, and Mw / Mn = 1.28. Met.
As with the polymer obtained in Example 1, it was confirmed by ¹ H-NMR spectrum that the main chain of the polymer had high stereoregularity. Example 6 The inside of a Schlenk tube equipped with a three-way cock of 80 ml was degassed,
After substituting with argon, 3.6 mg (0.008 mmol) of the metal complex synthesized in Reference Example 1, 5.0 mg (0.019 mmol) of triphenylphosphine, and 4
-(N, N-dimethyl) aminopyridine 19.6 mg
(0.16 mmol) and 7.6 ml of tetrahydrofuran as a solvent were added, and stirring was continued for 5 minutes with a magnetic stir bar at -25 ° C to sufficiently dissolve the complex catalyst. 7. With sufficient stirring at room temperature, ((4'-methoxy (1,1'-biphenyl) -4-yl) oxy) propyl 4-ethynylphenyl ether 143.3 mg (0.4 mmol) and tetralin 0.15 ml were added to 8. A solution dissolved in 0 ml of tetrahydrofuran was added to initiate polymerization. After continuing stirring at room temperature for 78 minutes, 0.1 ml of acetic acid was added to terminate the polymerization. The reaction solution was poured into 50 ml of methanol to precipitate a polymer, and then the polymer was collected by filtration. After drying at room temperature under reduced pressure for about 5 hours, 130.8 mg of a brown polymer was obtained. Number average molecular weight 6600, Mw / M
n = 1.20. The ¹ H-NMR spectrum of this polymer showed that the main chain of this polymer had high stereoregularity. Comparative Example 1 Phenylacetylene was polymerized by the same procedure as in Example 3 except that CH ₃ ONa was not added, but no polymer was obtained.

[0025]

Industrial Applicability According to the method of the present invention, a substituted acetylene polymer having a narrow molecular weight distribution and a high molecular weight and high stereoregularity can be efficiently produced. Therefore, it becomes possible to provide a material having a more uniform composition than the conventional one. Since the obtained polymer has high stereoregularity, it can be applied as an optical material, especially a non-linear optical material.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (71) Applicant 593182026 Takao Ikariya 8-1 Shiruya-cho, Chikusa-ku, Nagoya-shi, Aichi Teahouse No. 907, Coater-Gaka Coater (72) Tatsuya Miyatake 755, Oshinuma, Ichihara-shi, Chiba 3 Chiharadai 3 -32-1-1 (No. 3-701) (72) Inventor Yasuhisa Kishimoto 6-31-17 Shioyacho, Tarumi-ku, Kobe-shi, Hyogo Sanseiso (72) Inventor Takao Ikaya Chikusa-ku, Nagoya, Aichi 8-1 Shiruya-cho Chaya-gasaka Coaters 907 (72) Inventor Ryoji Noyori Nitta 135-417 Umemori-cho Nisshin-shi Aichi

Claims (3)

[Claims] 1. The following formula: (In the formula, M is a transition metal element belonging to Group VIII of the periodic table,
R ¹ is an aliphatic, alicyclic, aromatic or araliphatic hydrocarbon group which may have a substituent, L ¹ is an organic compound having a carbon-carbon multiple bond, n is a positive number of 1 to 3 Indicates an integer)
In the presence of a transition metal complex represented by the following formula and a basic compound containing nitrogen, phosphorus or arsenic, (In the formula, R is an aliphatic which may have a substituent, an alicyclic group,
A method for producing a substituted acetylene polymer, which comprises polymerizing an acetylene compound represented by (an aromatic or araliphatic hydrocarbon group or a heterocyclic group having a hetero element). 2. The following formula: (In the formula, M is a transition metal element belonging to Group VIII of the periodic table,
L ¹ is an organic compound having a carbon-carbon multiple bond, X is a halogen atom, m and l are both positive integers of 1 to 3, and m + l = 2 or 3). The following formula (In the formula, R ² is an aliphatic which may have a substituent, an alicyclic group,
In the presence of an alcoholate compound represented by an aromatic or araliphatic hydrocarbon group, Y is an alkali metal of Group I of the periodic table) and a basic compound containing nitrogen, phosphorus or arsenic, the following formula: Chemical 5] (In the formula, R is an aliphatic which may have a substituent, an alicyclic group,
A method for producing a substituted acetylene polymer, which comprises polymerizing an acetylene compound represented by (an aromatic or araliphatic hydrocarbon group or a heterocyclic group having a hetero element). 3. The method according to claim 1, wherein an amine compound is allowed to coexist when polymerizing the acetylene compound.
A method for producing a substituted acetylene polymer.