JP3290461B2 - Diphenylacetylene polymer - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel diphenylacetylene-based polymer.

[0002]

2. Description of the Related Art Recently, polyacetylenes have attracted attention as functional polymer materials. For example, polyacetylene is considered to be applied to batteries, electronic elements, sensors, and the like by utilizing its electrical characteristics. On the other hand, polymers obtained by polymerizing trimethylsilylpropyne are expected to be used for gas separation membranes. In recent years, a technique for enriching or separating a specific gas such as oxygen or nitrogen from a gas mixture such as air using such a polymer membrane has attracted attention. For example, if oxygen gas and nitrogen gas in the air can be concentrated and separated from the air, the combustion efficiency of a combustion device such as an engine or a boiler can be increased, and energy can be saved. In addition, if clean oxygen-enriched air can be obtained, it can be used for medical equipment such as incubators, artificial lungs, and contact lenses.

As a material for such a gas separation membrane, a polymer obtained by polymerizing various acetylene monomers such as the above-mentioned trimethylsilylpropyne has been developed. For example, a polymer of trimethylgermylpropyne containing germanium of a homologous atom instead of a silicon atom is known (Japanese Patent Application Laid-Open No. 63-171819). Such a trimethylgermylpropyne has the advantage that the polymerization time is significantly shorter than that of trimethylsilylpropyne, thereby enabling the in-situ synthesis of a thin film. However, they are insoluble in organic solvents such as toluene and chloroform, so that they have poor processability and gas permeability as compared with trimethylsilylpropyne.

Accordingly, the present inventors have searched for a polymer that can solve the above-mentioned drawbacks, and as a result, have found that a diphenylacetylene-based polymer having an alkyl group or a silyl group is stable to air and heat and soluble in an organic solvent. It has been reported that it has excellent membrane-forming ability and excellent gas permeability, so that it is promising as a material for a gas separation membrane (JP-A-4-15206, Polymer Preprints, Japan).
n Vol. 39, no. 7 (1990)). But,
The types of polymers that are still considered promising are few, and the development of new polymers is desired.

[0005]

SUMMARY OF THE INVENTION The present inventors have conducted intensive studies to develop a novel polymer useful as a functional polymer material such as a gas separation membrane, and as a result, a diphenylacetylene-based polymer having a germyl group has been developed. It has been found that, like the above-mentioned diphenylacetylene-based polymer having a silyl group, it is stable to air and heat, is soluble in an organic solvent, and has excellent gas permeability. As described above, in the prior art, it was known that when a germyl group was introduced instead of a silyl group, both the solubility and the gas permeability were inferior, but in the case of diphenylacetylene as in the present invention, it was surprising. Even when a germyl group is introduced, the compound has the same solubility and gas permeability as the silyl group, and has completed the present invention based on such findings.

[0006]

According to the present invention, the following formula (I)

Embedded image (R represents a trialkylgermyl group), and a diphenylacetylene-based polymer having a trialkylgermyl group having a weight average molecular weight of 10,000 or more is provided. .

In the present invention, diphenylacetylene having a trialkylgermyl group represented by the following formula (II) is used as a raw material monomer.

Embedded image In the formula, R represents a trialkylgermyl group, and examples of the alkyl group include an alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, and a tertiary butyl group. You.

Specific examples of such diphenylacetylenes having a trialkylgermyl group include 1- (o-trimethylgermylphenyl) -2-phenylacetylene,
1- (m-trimethylgermylphenyl) -2-phenylacetylene, 1- (p-trimethylgermylphenyl) -2-phenylacetylene, 1- (m-dimethylethylgermylphenyl) -2-phenylacetylene, 1
-(M-triethylgermylphenyl) -2-phenylacetylene, 1- (p-triethylgermylphenyl)
2-phenylacetylene, 1- (m-tripropylgermylphenyl) -2-phenylacetylene, 1- (p
-Tripropylgermylphenyl) -2-phenylacetylene, 1- (m-tributylgermylphenyl) -2
-Phenylacetylene, 1- (p-tributylgermylphenyl) -2-phenylacetylene, 1- (p-tert-butyldimethylgermylphenyl) -2-phenylacetylene, and the like.

These diphenylacetylenes may be used alone or in combination of two or more.

[0010] Such diphenylacetylenes can be produced according to a conventional method. For example, it can be obtained by reacting a halo-substituted diphenylacetylene with a lithium reagent or a Grignard reagent, and then gel-milling with a trialkylgermyl halide.

The diphenylacetylene-based polymer of the present invention is obtained by polymerizing the above-mentioned diphenylacetylene using a halide of a transition metal belonging to Group V of the periodic table as a catalyst. Examples of the halides of transition metals of Group V of the periodic table include niobium pentachloride, niobium pentabromide, tantalum pentachloride, tantalum pentabromide and the like. These may be used alone or in combination of two or more.

The amount of the halide of the transition metal of Group V of the periodic table is usually 0.001 to 1 mol, preferably 0.01 to 0.2 mol, per 1 mol of diphenylacetylenes.

In the present invention, a cocatalyst can be used if necessary. As the cocatalyst, for example, triethylaluminum, monochlorodiethylaluminum, dichloroethylaluminum, triethylsilane, triphenylsilane, tetraphenyltin, tetra-n-butyltin,
Triphenylantimony, triphenylbismuth, 9-
Borabicyclo [3.3.1] nonane and the like.

The amount of the cocatalyst to be used is usually 0.01 to 1 with respect to 1 mol of a halide of a transition metal belonging to Group V of the periodic table.
0 mol, preferably in the range of 0.1 to 5 mol.

The polymerization is usually carried out in an atmosphere of an inert gas such as nitrogen using a solvent. Examples of the solvent include aromatic hydrocarbons such as benzene, toluene, and xylene; alicyclic hydrocarbons such as cyclohexane; halogenated hydrocarbons such as carbon tetrachloride, dichloroethane, chlorobenzene, and bromobenzene; anisole, dibutyl ether, and dioxane. Ethers; ketones such as acetone and acetophenone; esters such as ethyl acetate;

The amount of the solvent to be used is appropriately selected so that the concentration of the diphenylacetylene in the solvent is usually 0.01 to 1 mol / l.

The polymerization temperature is appropriately selected within the range of -30 to 100 ° C, preferably 0 to 80 ° C. The polymerization time varies depending on the type of raw material and catalyst, polymerization temperature, etc., but is usually several minutes to
It takes about 100 hours.

The polymer is recovered by a usual method such as pouring the polymer solution into a large amount of a poor solvent, precipitating the polymer, filtering, and drying.

The obtained polymer is a polymer having a repeating unit represented by the above formula (I) and having a weight average molecular weight (converted value of polystyrene determined by gel permeation chromatography) of 10,000 or more. Since such a polymer is stable against air and heat, it can be used as a material requiring heat resistance. Also, since it is soluble in organic solvents, it has excellent moldability. further,
Since it has high permeability to various gases such as oxygen and nitrogen, it can be used as a gas separation membrane.

[0020]

The present invention will be described more specifically with reference to the following examples. Parts and% in Examples and Comparative Examples are based on weight unless otherwise specified.

Reference Example 1 Synthesis of 1- (m-trimethylgermylphenyl) -2-phenylacetylene In a nitrogen atmosphere, 25 ml of tetrahydrofuran was added to a reaction vessel, and 1.6 ml at -30 ° C.
15 ml of a solution of M in normal butyllithium-hexane was added. Next, 20 ml of a tetrahydrofuran solution of 21 mmol of 3-bromodiphenylacetylene was gradually added dropwise and reacted for 1 hour. Thereafter, 5 ml of a tetrahydrofuran solution of 25 mmol of chlorotrimethylgermane was gradually added dropwise, and the temperature was raised to room temperature.
Reacted. After completion of the reaction, a saturated aqueous ammonium chloride solution was added, and the mixture was extracted with ethyl acetate. The organic layer was concentrated under reduced pressure to obtain a solid, which was purified by column chromatography and 2.6 g of white crystals (based on 3-bromodiphenylacetylene). Yield 40.7%). The structure of this thing is ¹ H
-Confirmed by NMR.

¹ H-NMR (CDCl ₃ ) δ: 7.20-
7.80 (m, 9H, ArH) 0.42 (s, 9H, Ge (CH 3) 3)

Example 1 Synthesis of 1- (m-trimethylgermylphenyl) -2-phenylacetylene polymer Tantalum pentachloride 0.48 was placed in a polymerization vessel under an atmosphere of dry nitrogen.
Gram, and add 32.6 ml of toluene and 0.88 ml of tetra-n-butyltin,
And a catalyst solution was prepared. Next, 10 ml of a 0.8 M toluene solution of 1- (m-trimethylgermylphenyl) -2-phenylacetylene was taken in another polymerization vessel under a dry nitrogen atmosphere, and the catalyst solution 10
Milliliter was added and polymerization was allowed to proceed at 80 ° C. 24
After a period of time, the produced polymerization solution was poured into a large amount of methanol to precipitate the produced polymer, which was separated by filtration and dried to obtain a polymer.

The yield of the polymer was 60%, and the weight average molecular weight (Mw) determined by gel permeation chromatography as a polystyrene equivalent value was 1.8 million. The polymer was a yellow powder, and was soluble in organic solvents such as aromatic hydrocarbons such as benzene and toluene, halogenated hydrocarbons such as carbon tetrachloride and chloroform, and ethers such as tetrahydrofuran. Polymer 5
% Weight loss temperature was measured in air using a differential thermogravimetric simultaneous measurement device TG / DTA220 manufactured by Seiko Electronics Industry Co., Ltd.
It was 380 ° C. when measured at a heating rate of 10 ° C./min. The results of NMR measurement of the polymer are shown below.

¹ H-NMR (CDCl ₃ ) δ: 5.55
7.27 (brm, 9H, ArH) -0.48 to 0.52 (brm, 9H, Ge (C
H _{3) 3)}

Example 2 The procedure of Example 1 was repeated, except that 9-borabicyclo [3.3.1] nonane was used instead of tetra-n-butyltin. The yield was 76% and the weight average molecular weight was 11%.
100,000 polymers were obtained.

Example 3 Synthesis of 1- (p-trimethylgermylphenyl) -2-phenylacetylene polymer The synthesis was carried out according to Reference Example 1 in place of 1- (m-trimethylgermylphenyl) -2-phenylacetylene. 1-
By operating according to Example 1 except that (p-trimethylgermylphenyl) -2-phenylacetylene was used, a polymer having a weight average molecular weight of 1.8 million was obtained with a yield of 52%. The polymer was soluble in organic solvents such as aromatic hydrocarbons such as benzene and toluene, halogenated hydrocarbons such as carbon tetrachloride and chloroform, and ethers such as tetrahydrofuran. The 5% weight loss temperature of the polymer was 400 ° C. The results of NMR measurement of the polymer are shown below.

¹ H-NMR (CDCl ₃ ) δ: 5.53 or more
7.20 (brm, 9H, ArH) -0.45 to 0.53 (brm, 9H, Ge (C
H _{3) 3)}

Example 4 The procedure of Example 3 was repeated, except that triethylsilane was used instead of tetra-n-butyltin. As a result, a polymer having a weight average molecular weight of 2.1 million was obtained with a yield of 81%.

Example 5 The procedure of Example 3 was repeated, except that 9-borabicyclo [3.3.1] nonane was used instead of tetra-n-butyltin. The yield was 72% and the weight average molecular weight was 23.
100,000 polymers were obtained.

Reference Example 2 Evaluation of gas permeability of 1- (m-trimethylgermylphenyl) -2-phenylacetylene polymer 1- (m-trimethylgermylphenyl) -2-phenylacetylene obtained in Example 1 One gram of the polymer was dissolved in 175 ml of toluene, cast on a glass plate for casting, and allowed to stand at room temperature for 3 days to produce a 30 μm thick transparent yellow film. This membrane is used as a gas permeability measuring device (K-315- manufactured by Rika Seiki Kogyo Co., Ltd.).
N) at 25 ° C. with oxygen and nitrogen gas permeability coefficients P
O ₂ , PN ₂ (cm ³ (STP) · cm / cm ² · second · cm
Hg) was measured, and the separation coefficient α (PO ₂ / PN ₂ ) was calculated. Also, 1- (m-trimethylsilylphenyl) -2
Similarly, a membrane was prepared for the phenylacetylene polymer, the gas permeability coefficient was measured, and the separation coefficient was calculated. Table 1 shows the results.

[0032]

[Table 1]

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Claims (1)

(57) [Claims] (1) The following formula (I): (R represents a trialkylgermyl group), and a diphenylacetylene-based polymer having a trialkylgermyl group having a weight average molecular weight of 10,000 or more.