JP2974369B2 - Diphenylacetylene polymer having a substituent on the aromatic ring - Google Patents

Description

The present invention relates to a novel diphenylacetylene polymer having a substituent on an aromatic ring, more specifically, unlike conventional polyacetylene, is stable to air, And a polymer having a substituent on a high molecular weight aromatic ring which is soluble in an organic solvent and has excellent film-forming ability and can be applied to, for example, separation membranes, adsorbents, resist materials, semiconductor materials, and memory materials. It is about.

[Related Art] In recent years, research and development of new materials has been actively conducted in various fields, and development of functional polymer materials has been actively attempted in the field of polymer compounds. Polyacetylene is known as one of the functional polymer materials. The polyacetylene has a structure in which hydrogen is attached to a carbon chain formed by alternately bonding hundreds to thousands of carbon atoms with a double bond and a single bond, and as it is, it is a semiconductor close to an insulator. Doping an acceptor like
It is known that when a donor such as sodium or potassium is doped, an n-type semiconductor is obtained, and by further increasing the amount of doping, a semiconductor having high electrical conductivity and excellent conductivity is obtained. Polyacetylene having such electric properties can be applied to, for example, storage batteries, solar cells, display elements, electronic elements, sensors, and the like. However, this polyacetylene easily reacts with oxygen in the air and deteriorates, so that it has a drawback that it is difficult to put into practical use.

The present inventors have conducted repeated studies to develop a practical polyacetylene-based polymer.First, using a catalyst mainly composed of tungsten hexahalide or molybdenum pentahalide, 1-alkylacetylenes and phenyl Successful polymerization of acetylene, and further from 1-phenyl-1-alkynes and 1-trimethylsilyl-1-propyne, using niobium pentachloride or tantalum pentachloride as a catalyst has a molecular weight of several hundred thousand to one million or more. Was found to be obtained.

However, diphenylacetylene is polymerized by using tungsten hexachloride or tantalum pentachloride as a catalyst, but the resulting polymer is insoluble in organic solvents and cannot be melted by heating. Has the disadvantage of being difficult to perform.

[Problems to be Solved by the Invention] Under such circumstances, the present invention provides a novel diphenylacetylene-based material that is stable to air, can be molded, and has high industrial value as a new material. The purpose of the present invention is to provide a high polymer.

[Means for Solving the Problems] The present inventors have conducted intensive studies to develop a novel diphenylacetylene-based high polymer having the above-mentioned preferable properties. By high polymer of diphenylacetylenes introduced by one or more,
The inventors have found that the object can be achieved, and have completed the present invention based on this finding.

That is, the present invention relates to the general formula (In the formula, R is an alkyl group or a silyl group, m is an integer of 1 to 5, and when m is 2 to 5, R may be the same or different.) And a diphenylacetylene polymer having a substituent on an aromatic ring, characterized by having a repeating unit represented by the formula: and a weight average molecular weight of 10,000 or more.

 Hereinafter, the present invention will be described in detail.

In the polymer of the present invention, as a raw material monomer of the main component, a general formula (R and m in the formula have the same meanings as described above). R in this general formula (II) is an alkyl group, preferably C
_1-18 , particularly preferably a _C1-12 alkyl or silyl group, preferably a trialkylsilyl group;
When R is 2 or more and is an integer of from 5 to 5, the Rs may be the same or different from each other.

Examples of the diphenylacetylene represented by the general formula (II) include 1- (p-methylphenyl) -2-phenylacetylene and 1- (p-ethylphenyl) -2-
Phenylacetylene, 1- (pn-butylphenyl)
2-phenylacetylene, 1- (pn-hexylphenyl) -2-phenylacetylene, 1- (pn-octylphenyl) -2-phenylacetylene, 1- (p
-N-butylphenyl) -2-phenylacetylene, 1
-(O-methylphenyl) -2-phenylacetylene,
1- (o-ethylphenyl) -2-phenylacetylene, 1- (m-methylphenyl) -2-phenylacetylene, 1- (2,4,6-trimethylphenyl) -2-phenylacetylene, 1- (2 , 3,4,5-Tetramethylphenyl) -2-phenylacetylene, 1- (2,3,5,6-tetramethylphenyl) -2-phenylacetylene, 1-
(P-trimethylsilylphenyl) -2-phenylacetylene, 1- (m-trimethylsilylphenyl) -2-
Examples thereof include phenylacetylene, 1- (p-triethylsilylphenyl) -2-phenylacetylene, 1- (p-dimethylethylsilylphenyl) -2-phenylacetylene, and the like. These diphenylacetylenes may be used alone or in combination of two or more, and may be copolymerized with other substituted acetylenes.

As the polymerization initiator, for example, transition metal compounds such as molybdenum, tungsten, niobium, and tantalum are used. Among them, a tantalum compound is particularly preferable, and the following two methods can be used. That is, (1) a method using tantalum halide such as tantalum pentachloride, and (2) a method using an initiator having tantalum halide as a main catalyst and a reducing agent as a second component. In the latter method (2), tantalum pentachloride is preferably used as the main component of tantalum halide, and the reducing agent of the second component is usually aluminum, boron, silicon, tin, antimony, bismuth, or the like. An organometallic compound containing lithium or the like is used.

The amount of the polymerization catalyst used in the methods (1) and (2) is usually selected in the range of 0.1 to 5 mol% based on the monomer, and the ratio of the reducing agent to the main catalyst in the method (2) is generally small. It is preferable to use them in a molar ratio of 0.3 to 3.

The polymerization reaction is preferably performed in a solvent.
For example, aromatic hydrocarbons such as toluene, aliphatic hydrocarbons such as cyclohexane, carbon tetrachloride, halogenated hydrocarbons such as ethylene dichloride, anisole, dibutyl ether, ethers such as dioxane, acetone, ketones such as acetophenone, Esters such as ethyl acetate are exemplified. One of these solvents may be used,
Two or more kinds may be used as a mixture.

Further, the polymerization reaction temperature is preferably in the range of -30 to + 100C, particularly preferably in the range of 0 to 80C. The polymerization time depends on the types of the raw material monomers and catalysts, the reaction temperature, the desired degree of polymerization, and the like, and cannot be determined unconditionally.
About 100 hours. Furthermore, the polymerization is advantageously carried out under a dry nitrogen atmosphere.

When copolymerization is performed, there is no particular limitation on the ratio of diphenylacetylenes having a substituent on the aromatic ring represented by the general formula (II) used as a main component and substituted acetylenes used as other components. Instead, both monomers can be used in any ratio.

The thus obtained novel polymer of the present invention is a polymer having a high polymerization degree having a weight average molecular weight of 10,000 or more and having a repeating unit represented by the general formula (I). In addition,
The weight average molecular weight (w) is a value in terms of polystyrene determined by a gel permeation chromatography (GPC) method.

Since the polymer of the present invention has a bulky substituent in the side chain, unlike the conventional polyacetylene, it is stable to air and can be expected as a heat-resistant material. In addition, since it is soluble in organic solvents and has film-forming ability, it can be used as a separation membrane for substances, and because it has a conjugated double bond, it can also be used in semiconductor materials and resist materials. It is possible.

[Examples] Next, the present invention will be described in more detail with reference to Examples.
The present invention is not limited in any way by these examples.

Example 1 20 mmol of tantalum pentachloride and tetra-n were mixed in a well-purified toluene 1 in a dry atmosphere with good stirring.
-20 mmol of butyltin were added and dissolved at 80 ° C. 0.5 mol of 1- (p-trimethylsilylphenyl) -2-phenylacetylene was added to this solution, and polymerization was allowed to proceed at 80 ° C. After 24 hours, the reaction mixture was poured into a large amount of methanol to precipitate a produced polymer, which was separated by filtration and dried. The yield of the polymer was 50% by weight, and its weight average molecular weight was 680,000. FIG. 1 shows the result of NMR measurement of this product.

The obtained polymer was a powder that emitted yellow fluorescence, and was soluble in organic solvents such as aromatic hydrocarbons such as toluene, halogenated hydrocarbons such as carbon tetrachloride, and ethers such as tetrahydrofuran.

Example 2 Polymerization was carried out in the same manner as in Example 1 except that the polymerization time was changed to 72 hours. As a result, a polymer having a weight average molecular weight of 750,000 was obtained with a yield of 60% by weight. Was done.

Example 3 A polymerization was carried out in the same manner as in Example 1 except that 1- (m-trimethylsilylphenyl) -2-phenylacetylene was used as a monomer.
A polymer having a weight average molecular weight of 370,000 was obtained with a yield of% by weight. FIG. 2 shows the result of NMR measurement of this product.

Example 4 The same as Example 1 except that 1- (pn-hexylphenyl) -2-phenylacetylene was used as a monomer and 40 mmol of tetra-n-butyltin was added. As a result, a polymer having a weight average molecular weight of 920,000 was obtained in a yield of 55% by weight.
FIG. 3 shows the result of NMR measurement of this product.

Example 5 Polymerization was carried out in the same manner as in Example 4 except that the reducing agent was changed to 40 mmol of triethylsilane, and a polymer having a weight average molecular weight of 1.2 million and a yield of 60% by weight was obtained. was gotten.

Example 6 A copolymer was prepared in the same manner as in Example 1 except that 0.5 mol of diphenylacetylene was used together with 0.5 mol of 1- (p-trimethylsilylphenyl) -2-phenylacetylene as a monomer. As a result, 1- (p-trimethylsilylphenyl) -2-phenylacetylene and diphenylacetylene were consumed at almost the same rate with the elapse of the polymerization time. After 24 hours, the conversion of both monomers into the polymer was 80 % Has been reached. The GPC curve of the obtained polymer shows a unimodal property, which indicates that a copolymer is formed.

[Effects of the Invention] As is clear from the above results, the diphenylacetylene polymer having a substituent on the aromatic ring of the present invention is a completely novel polymer having a high degree of polymerization having a weight average molecular weight of 10,000 or more. Unlike conventional polyacetylene, it is stable to air and soluble in aromatic hydrocarbons such as halogenated hydrocarbons such as carbon tetrachloride, ethers such as tetrahydrofuran and anisole, and toluene. As a new material, it can be applied to, for example, separation membranes, adsorbents, resist materials, semiconductor materials, storage materials, and the like, and has extremely high industrial value.

[Brief description of the drawings]

FIGS. 1, 2 and 3 are NMR measurement charts of different examples of the polymer of the present invention.

Claims (1)

(57) [Claims] (1) General formula (In the formula, R is an alkyl group or a silyl group, m is an integer of 1 to 5, and when m is 2 to 5, R may be the same or different.) A diphenylacetylene polymer having a substituent on an aromatic ring, having a repeating unit represented by the formula: and a weight average molecular weight of 10,000 or more.