JPH0143766B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a novel polymer and a method for producing the same, and the first object of the present invention is to provide a novel polymer containing 2-alkynes as a monomer. A second object of the invention is to provide a method for producing such polymers at a high reaction rate. According to the present invention, the first object is expressed by the general formula () CH ₃ -C≡C-R () (in this formula, R represents an alkyl group having no substituents other than a methyl group). General formula () using 2-alkyne as a monomer The second object is achieved by a chain polymer having a weight average molecular weight of 10,000 or more, and the second object is achieved by converting the 2-alkyne represented by the formula () into molybdenum pentachloride or hexachloride. This is achieved by polymerization in the presence of a catalyst comprising a combination of tungsten chloride and an organometallic reducing agent containing boron, aluminum, silicon, tin, lead, arsenic or antimony. Conventionally, Ziegler-type catalysts (e.g., titanium tetra-n
-butoxide or mixtures of iron acetylacetonate and organoaluminium compounds) were very effective catalysts, giving high yields of high molecular weight polymers. However, internal acetylenes such as 2-alkynes are not substantially polymerized by Ziegler catalysts due to steric hindrance, and high molecular weight polymers have not been obtained. The present inventors previously proposed a method for producing polymers from acetylene derivatives using a catalyst mainly composed of tungsten hexachloride (Japanese Patent Publication No. 55-23565
(Special Publication No. 17042, Special Publication No. 17042, Special Publication No. 43037, Special Publication No. 54-43037, Special Publication No. 30722, Special Publication No. 1983, Special Patent Application No. 1982-106456). The present inventors have further conducted extensive research on polymerization methods for obtaining high polymers from internal acetylene, and have found that 2- It was discovered that the polymerization of alkynes proceeds easily, and the resulting polymer is soluble and has a very large molecular weight (molecular weight of 10,000 or more, especially 100,000 to 1,000,000).Based on this knowledge, the present invention was developed. It was completed. The present invention will be explained in detail below. In the 2-alkynes represented by the general formula CH ₃ -C≡C-R of the present invention, R is an alkyl group having no substituents other than a methyl group. The polymerization catalyst used in the present invention has molybdenum pentachloride (MoCl ₅ ) or tungsten hexachloride (WCl ₆ ) as the main catalyst, and is combined with various reducing agents as a second component. As this reducing agent, an organic metal reducing agent containing boron, aluminum, silicon, tin, lead, arsenic or antimony is used. Among these, organic tin compounds such as tetraphenyltin and tetra-n-butyltin are particularly preferred in terms of ease of handling, availability, and effectiveness. The ratio of the 2-alkynes, which are monomers, to the main catalyst is preferably in the range of 100 for the former to 5 to 0.2 for the latter, and the ratio of the reducing agent to the main catalyst is in the molar ratio.
A range of 0.3 to 3 is preferred. The catalyst is used in the form of a solution, and the main catalyst and reducing agent are dissolved in a solvent (the same as the polymerization reaction solvent described later), and the mixture is heated for 30 to 60 minutes.
It is best to use it after leaving it at ℃ for 10 to 60 minutes. As the solvent for the polymerization reaction, it is preferable to use hydrocarbons, halogenated hydrocarbons, and the like. In particular, hydrocarbons such as benzene, toluene, and cyclohexane are preferred because they are readily available and can achieve high yields in polymerization. The monomer concentration in the polymerization reaction is preferably in the range of 0.1 to 5 mol/mol. The temperature of the polymerization reaction is usually selected from 0 to 60°C, and the reaction time is selected from the range of several tens of minutes to several tens of hours. After the reaction is completed, the reaction system is diluted with the solvent used in the reaction and then poured into a large amount of methanol, which precipitates the produced polymer, which is then dried separately. According to the present invention, novel chain polymers can be obtained in high yield from 2-alkynes. The resulting polymer has a molecular weight of 10,000 or more, particularly 100,000 to 1,000,000, which is extremely high for an acetylene polymer, and is also characterized by being completely soluble in hydrocarbons such as toluene and cyclohexane.
The polymer thus obtained can be used as a semiconductor, gas adsorbent,
It can be applied to separation membranes, photoresists, etc. Next, the present invention will be explained in more detail with reference to Examples. Example 1 Toluene 1 sufficiently purified under dry nitrogen atmosphere
30 mmol of molybdenum pentachloride and 30 mmol of tetraphenyltin were added thereto, and the mixture was aged at 30°C for about 15 minutes. 1.0 mol of 2-hexyne was added to the obtained catalyst solution, and polymerization was carried out at 30°C for 24 hours. After the reaction was completed, the mixture was dissolved in toluene (5) and poured into a large amount of methanol to precipitate the resulting polymer, which was then dried separately. The amount of methanol-insoluble polymer produced was 82% of the amount of 2-hexyne charged. The weight average molecular weight of the produced polymer was 1,100,000 according to a light scattering method, and the intrinsic viscosity measured at 30° C. in toluene was 4.55 dl/g. The produced polymer is a white solid, completely soluble in benzene, toluene, cyclohexane, n-hexane, and tetrahydrofuran, partially soluble in carbon tetrachloride, chloroform, diethyl ether, ethylene dichloride, acetone, ethyl acetate, It was insoluble in nitrobenzene and acetonitrile. The analytical values of the produced polymer are as follows. Elemental analysis value [as (C ₆ H ₁₀ ) _o ]; Calculated value, C, 87.73%; H, 12.27% Actual value, C, 87.49%; H, 12.27% Infrared absorption spectrum; 3000-2850 (s), 1650-1580 (w), 1470 (s),
1370 (m), 1260 (w), 1110-1000 (m), 800 (w)
),
720 (m) cm ^-1 . Ultraviolet absorption spectrum; (cyclohexane) λmax 290nm, εmax 1700n
m, absorption limit 350 nm. Carbon-13 nuclear magnetic resonance spectrum (deuterated chloroform) δ138.0 (C ₃ ), 132.3 (C ₂ ), 36.0 (C ₄ ), 20.5 (C ₁
),
19.8 ( _C5 ), 15.0 ( _C6 ) ppm. From the above analysis results, it is concluded that the produced polymer has the expected structure shown below. (n is 13,000 on weight average) The softening point of the produced polymer was 227 to 231°C, and according to differential thermal analysis, only heat generation was observed near the softening point. Even when this polymer was left in the air at room temperature for several months, the molecular weight hardly decreased. Example 2 Polymerization of 2-hexyne was carried out in the same manner as in Example 1 except that tungsten hexachloride was used instead of molybdenum pentachloride as the main catalyst. The amount of methanol-insoluble polymer produced is based on the amount of monomer charged.
It was 57%. The weight average molecular weight of the produced polymer is 20
Intrinsic viscosity at 30℃ in toluene is 0.54
It was dl/g. Comparative Example 1 A reaction was carried out in the same manner as in Example 1 except that molybdenum pentachloride or tungsten hexachloride as the main catalyst was used alone without using a reducing agent. The yield of coalescence was 0%. Example 3 Using molybdenum pentachloride as the main catalyst and the compounds shown in the table below as the reducing agent, Example 1
Polymerization of 2-hexyne was carried out in the same manner as described above. Yield and intrinsic viscosity of the produced polymer (in toluene, 30
°C) are shown in the table below.

[Table] Example 4 The reaction was carried out in the same manner as in Example 1 except that ethylene dichloride was used instead of toluene as the solvent, and the amount of polymer produced was proportional to the amount of monomer charged. 29%, the intrinsic viscosity of the polymer is 3.11 dl/
g (molecular weight approximately 350,000). Example 5 Polymerization was carried out at 60°C in the same manner as in Example 1. The amount of polymer produced was 68% of the amount of monomer charged, and the intrinsic viscosity of the polymer was 2.20 dl/g (molecular weight 230,000). Example 6 Polymerization was carried out in the same manner as in Example 1 except that 0.50 mol of 2-heptyne was used as the monomer, and 2
- A chain polymer of heptine was obtained. The yield of the produced polymer was 51%, and the intrinsic viscosity (in toluene, 30℃) was 3.50.
dl/g (molecular weight approximately 500,000). The solubility of the produced polymer in various solvents is that of poly(2-hexyne).
It was the same as in the case of . The infrared absorption spectrum and ultraviolet absorption spectrum of this product were as follows. Infrared absorption spectrum; 3000-2850 (s), 1650-1850 (w), 1470 (s),
1370 (m), 1280 (w), 1200 (w), 1100 (m), 10
00
(w), 720 (w), UV absorption spectrum (in cyclohexane); shoulder at 290 nm (ε810) absorption limit 350 nm Example 7 Same as Example 1 except that 0.50 mol of 2-octyne was used as the monomer. to perform polymerization, 2
- A chain polymer of octyne was obtained. The yield of the produced polymer was 63%, and the intrinsic viscosity (in toluene, 30℃) was 3.16.
dl/g (molecular weight approximately 380,000). The solubility of the produced polymer in various solvents is that of poly(2-hexyne).
It was the same as in the case of . The analytical values of the produced polymer were as follows. Elemental analysis value [as (C ₈ H ₁₄ ) _o ]; Calculated value, C, 87.19; H, 12.81; Actual value, C, 86.67; H, 12.91; Infrared absorption spectrum; 3000-2850 (s), 1650- 1580(w), 1470(s),
1370 (m), 1260 (w), 1100 (m), 1010 (m), 80
0
(w), 720(m), Example 8 Polymerization was carried out in the same manner as in Example 1 except that 0.50 mol of 2-nonine was used as a monomer, and 2-
A chain polymer of nonine was obtained. The yield of the produced polymer is
60%, intrinsic viscosity (in toluene, 30℃) is 2.20dl/
g (molecular weight approximately 210,000). The solubility of the resulting polymer in various solvents was similar to that of poly(2-hexyne). Further, the infrared absorption spectrum and ultraviolet absorption spectrum of this product were as follows. Infrared absorption spectrum; 3000-2850 (s), 1660-1580 (w), 1470-1450
(s), 1370-1360 (m), 1110 (m), 1070 (w),
1010 (m), 720 (m) Ultraviolet absorption spectrum; Shoulder at 280 nm (ε950) Absorption limit 345 nm Example 9 Polymerization was carried out in the same manner as in Example 1, except that 0.50 mol of 2-decyne was used as the monomer. , 2-
A chain polymer of decine was obtained. The yield of the produced polymer is
50%, and the intrinsic viscosity was 2.31 dl/g (molecular weight approximately 250,000). The solubility of the resulting polymer in various solvents was similar to that of poly(2-hexyne). The analytical values of the produced polymer were as follows. Elemental analysis value [as (C ₁₀ H ₁₈ ) _o ]; Calculated value, C, 86.88; H, 13.12 Actual value, C, 86.51; H, 12.98 Infrared absorption spectrum; 3000-2850 (s), 1650-1580 ( w), 1470(s),
1370 (m), 1260 (w), 1100 (m), 1030-1010
(m), 800 (w), 720 (m) Ultraviolet absorption spectrum; Shoulder at 290 nm (ε500) Absorption limit 335 nm Example 10 Tetra-n-butyltin was used as the reducing agent instead of tetraphenyltin, as shown in the table below. Polymerization was carried out in the same manner as in Example 1 except that 0.50 mol of 2-alkyne was used, and the results shown in the table below were obtained.

[Table] The polymers obtained in Examples 1, 3, 6, 7, 8, 9 and 10 were dissolved in toluene and casted to obtain transparent and durable films. The flexibility of the polymer film increased in the order of 2-hexyne, 2-heptyne, 2-octyne, 2-nonine, and 2-decyne. What has been explained above and shown in the examples is related to typical examples to help the understanding of the present invention, and the present invention is not limited to these examples, and other changes may be made within the gist of the invention. An example can be taken.

Claims (1)

[Claims] 1 2-alkyne represented by the general formula () CH ₃ -C≡C-R () (in this formula, R represents an alkyl group having no substituent other than a methyl group) General formula for mass () A chain polymer with a weight average molecular weight of 10,000 or more. 2 A 2-alkyne represented by the general formula () CH ₃ -C≡C-R () (in this formula, R represents an alkyl group having no substituent except a methyl group) is converted into molybdenum pentachloride or hexachloride. Tungsten and boron, aluminum, silicon, tin, lead,
A method for polymerizing 2-alkynes, which comprises polymerizing in the presence of a catalyst in combination with an organometallic reducing agent containing arsenic or antimony.