JPH0586128A - Production of diphenylacetylene polymer - Google Patents

Abstract

PURPOSE:To obtain a diphenylacetylene polymer of a lowered molecular weight in good yields. CONSTITUTION:The title process comprises polymerizing a diphenylacetylene monomer in the presence of a catalyst comprising a halide of a group V transition metal of the periodic table and an organometallic compound and a diacetylene compound.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a method for producing a diphenylacetylene polymer.

[0002]

2. Description of the Related Art Conventionally, diphenylacetylene-based polymers obtained by polymerizing diphenylacetylene-based monomers such as (p-trimethylsilyl) diphenylacetylene are excellent in thermal stability and have good gas permeability and separation characteristics. Known to have.

As a method for producing such a diphenylacetylene-based polymer, for example, a method in which a diphenylacetylene-based monomer is polymerized in the presence of tantalum pentachloride and an organic tin compound is known (Polymer Preprior).
nt, JapanVol, 39, P2056-205
8, No. 7 (1990), The 60th Autumn Meeting of the Chemical Society of Japan, p499, (1990)).

However, the polymer solution obtained by such a method becomes highly viscous, which makes it difficult to stir, transfer, dissolve and dilute the solution during polymerization, and further make it difficult to redissolve the obtained polymer in an organic solvent. There was a problem in terms of operation and handling. Therefore, in order to obtain a polymer that is easier to handle, a method for reducing the molecular weight of the polymer has been studied. For example, a method of lowering the molecular weight of the polymer by increasing the ratio of the catalyst concentration to the monomer concentration can be considered, but this method may cause a large amount of catalyst residue to be included in the polymer, which may adversely affect various properties. I'm worried.

[0005]

DISCLOSURE OF THE INVENTION As a result of intensive research aimed at solving the above problems, the present inventors have found that a halide of a Group V transition metal of the periodic table and an organometallic compound having a reducing property with respect to the halide. It was found that it is possible to lower the molecular weight of the polymer without increasing the amount of the transition metal halide by polymerizing the diphenylacetylene-based monomer in the presence of a catalyst and a diacetylene compound. The present invention has been completed based on this finding.

[0006]

Thus, according to the present invention, in the presence of a diacetylene compound and a catalyst comprising a halide of a transition metal of Group V of the periodic table and an organometallic compound having a reducing property to the halide. There is provided a method for producing a diphenylacetylene-based polymer, which comprises polymerizing a diphenylacetylene-based monomer.

The diphenylacetylene-based monomer used in the present invention is diphenylacetylene or diphenylacetylene having a substituent. The substituent is not particularly limited as long as it does not inhibit polymerization, and examples thereof include an alkyl group, a cycloalkyl group, a haloalkyl group, an aryl group and a substituted silyl group. Such a substituent is bonded to two benzene rings forming diphenylacetylene, but the number and position thereof are not particularly limited.

Examples of the alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, neopentyl group. Group, n-hexyl group, isohexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group and the like.

Examples of the cycloalkyl group include a cyclopentyl group, a cyclohexyl group, a cycloheptyl group and a cyclooctyl group.

Examples of the haloalkyl group include chloromethyl group, brommethyl group, iodomethyl group, 1-chloro-1-ethyl group, 2-chloro-1-ethyl group, 1-bromo-1-ethyl group and 2-bromo-group. A 1-ethyl group and the like can be mentioned.

As the aryl group, for example, a phenyl group,
Examples thereof include a tolyl group, a xylyl group, a cumenyl group and a mesityl group.

Examples of the substituted silyl group include trimethylsilyl group, dimethylethylsilyl group, dimethylphenylsilyl group, diethylmethylsilyl group, diphenylmethylsilyl group, triethylsilyl group and triphenylsilyl group.

Among these substituents, an alkyl group, a substituted silyl group and the like are favored.

In the present invention, the halide of the group V transition metal of the periodic table is a halide such as niobium or tantalum, and examples thereof include tantalum pentafluoride, tantalum pentachloride, tantalum pentabromide, niobium pentafluoride and pentanitride. Examples thereof include niobium chloride and niobium pentabromide. Tantalum halides are preferred because of their reactivity. Also, these compounds may be used as a mixture of two or more kinds.

The organometallic compound having a reducing property with respect to a halide of a transition metal of Group V of the periodic table includes compounds containing a metal such as aluminum, silicon, tin, antimony, bismuth, boron and lithium. For example, trimethylaluminum, triethylaluminum, monochlorodiethylaluminum, dichloroethylaluminum, triethylsilane, dimethylethylsilane, triphenylsilane, tetramethyltin, tetra-n-butyltin, tetraphenyltin, triphenylantimony, triphenylbismuth, 9-Porabicyclo [3,3,1] nonane, n-butyllithium and the like can be mentioned.

Among these organometallic compounds, compounds containing aluminum, silicon and tin are preferred.

In the present invention, a diacetylene compound is used as a molecular weight regulator. The diacetylene compound is 1,3-butadiyne which may have a substituent, and examples of the substituent include an alkyl group, a cycloalkyl group,
A haloalkyl group, an aryl group, a substituted silyl group and the like.

Examples of the alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, neopentyl group. Group, n-hexyl group, isohexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group and the like.

Examples of the cycloalkyl group include a cyclopentyl group, a cyclohexyl group, a cycloheptyl group and a cyclooctyl group.

Examples of the haloalkyl group include a chloromethyl group, a brommethyl group, an iodomethyl group, a 1-chloro-1-ethyl group, a 2-chloro-1-ethyl group, a 1-bromo-1-ethyl group and a 2-bromo-group. A 1-ethyl group and the like can be mentioned.

As the aryl group, for example, a phenyl group,
Examples thereof include a tolyl group, a xylyl group, a cumenyl group and a mesityl group.

Examples of the substituted silyl group include trimethylsilyl group, dimethylethylsilyl group, dimethylphenylsilyl group, diethylmethylsilyl group, diphenylmethylsilyl group, triethylsilyl group and triphenylsilyl group.

The substituent is preferably an aryl group, and more preferably a disubstituted group.

In the polymerization, the amount of the halide of a transition metal of Group V of the periodic table is usually 0.001 to 1 mol, preferably 0.01 to 0.2 mol, based on 1 mol of the diphenylacetylene-based monomer. The range is.

The amount of the organometallic compound having a reducing property with respect to the halide of the transition metal of Group V of the periodic table is
With respect to 1 mol of a Group V transition metal halide of the periodic table,
Usually, it is in the range of 0.01 to 10 mol, preferably 0.1 to 5 mol.

On the other hand, the amount of the diacetylene compound used is in the range of 0.01 to 10 mol, preferably 0.1 to 5 mol, based on 1 mol of the halide of the Group V transition metal of the periodic table.

Polymerization of the diphenylacetylene type monomer is usually carried out using a solvent under a nitrogen atmosphere. Examples of the solvent include aromatic hydrocarbons such as benzene, toluene and xylene, carbon tetrachloride, chloroform and 1,2-
Halogenated hydrocarbons such as dichloroethane, chlorobenzene and bromobenzene, alicyclic hydrocarbons such as cyclohexane and cyclohexene, and mixtures of two or more thereof.

The amount of the solvent used is such that the concentration of the diphenylacetylene-based monomer in the solvent is usually 0.01 to 1 mol / mol.
It is appropriately selected within the range of liter.

In the method of the present invention, the order of addition of each component and the preparation method of the catalyst dissolution temperature are not particularly limited, but usually, a solvent is a halide of a Group V transition metal of the periodic table and a reducing property for the halide. A catalyst composed of an organometallic compound having a diamine, a diacetylene compound, agitated at a predetermined polymerization temperature, and then a substituted diphenylacetylene-based monomer, or a solvent of Group V transition in the periodic table. A solution obtained by adding a diacetylene compound and a diphenylacetylene-based monomer to a solution to which a catalyst composed of a metal halide and an organometallic compound having a reducing property with respect to the halide is added, and stirred at a predetermined polymerization temperature. There are ways to do it.

The polymerization temperature can be arbitrarily changed from room temperature to the boiling point of the solvent, but is preferably 50 to 100 ° C.

The polymerization time depends on the polymerization temperature, but is 50-
At 100 ° C., it is usually several hours to several tens of hours.

The diphenylacetylene polymer obtained by polymerization as described above is recovered by a usual method such as adding a polymer solution to a large amount of a poor solvent to precipitate the polymer, filtering and drying. You can

The diphenylacetylene polymer is a light yellow to orange fiber or powder and has a weight average molecular weight of about 10,000 to 2,000,000.

The diphenylacetylene polymer can be applied to semiconductors, photoconductive materials, gas adsorbents, gas separation media, liquid separation media, chromic materials, resists, biocompatible materials and the like.

[0035]

As described above, according to the present invention, the molecular weight of the polymer can be lowered without increasing the amount of the catalyst used, so that the amount of the catalyst residue remaining in the produced polymer can be suppressed to a low level. Thus, a polymer of higher purity can be obtained without a troublesome purification operation. By lowering the molecular weight of the polymer, it is possible to reduce the viscosity of the polymer solution. In addition, since the polymerization solution has fluidity, operations such as stirring and transfer of the polymerization solution can be easily performed. Therefore, it is easy to redissolve the obtained polymer in an organic solvent in a short time. Is possible.

[0036]

EXAMPLES The present invention will be described in more detail with reference to the following examples. The parts and% in the examples and comparative examples are based on weight unless otherwise specified. Example 1 0.17 tantalum pentachloride in a polymerization vessel under a dry nitrogen atmosphere.
10 g, toluene 14.5 ml, tetra-n-
Butyltin (0.31 ml) was added, and the mixture was stirred at room temperature for 20 minutes to prepare a catalyst solution. Next, in a dry nitrogen atmosphere, another polymerization container (p-trimethylsilyl) was added.
Take 5 ml of 0.8 M toluene solution of diphenylacetylene and 1,4-diphenylbutadiyne so that the molar ratio to tantalum pentachloride is the value shown in Table 1, transfer to a constant temperature bath at 80 ° C. and leave for 10 minutes. did. 5 ml of the above catalyst solution was added to this to initiate polymerization. The reaction solution gradually became viscous with the passage of time, and the reaction was carried out at 80 ° C. for 20 hours. After the reaction
The polymerization vessel was tilted and the fluidity of the resulting polymerization solution was observed. Next, the produced polymerization solution was precipitated in a large amount of methanol and then filtered and dried to obtain a polymer. The yield of the polymer was calculated from the yield of the polymer with respect to the charged amount of the monomer. The polymer weight average molecular weight (Mw) was determined as a polystyrene conversion value by gel permeation chromatography (manufactured by Tosoh Corporation; HLC-8020) measurement. In addition, the molecular weight distribution represented by the ratio of the weight average molecular weight and the number average molecular weight (MW
D) was measured. The results are shown in Table 1. From Table 1, 1,4-
It can be seen that when diphenylbutadiyne is added, the resulting polymerization solution has fluidity and the molecular weight of the obtained polymer decreases.

[0037]

[Table 1]

Example 2 The procedure of Example 1 was repeated except that (p-tertbutyl) diphenylacetylene was used in place of (p-trimethylsilyl) diphenylacetylene, and the fluidity of the resulting polymerization solution was observed. Next, the produced polymerization solution is precipitated in a large amount of methanol, then filtered and dried to obtain a polymer,
Yield and weight average molecular weight (Mw) and molecular weight distribution (MW
D) was measured. The results are shown in Table 2. It can be seen from Table 2 that even if the kind of the diphenylacetylene-based monomer is changed, when 1,4-diphenylbutadiyne is added, the resulting polymerization solution has fluidity and the molecular weight of the obtained polymer is lowered.

[0039]

[Table 2]

Example 3 The same operation as in Example 1 was carried out except that the organometallic compounds shown in Table 3 were used in place of tetra-n-butyltin, and the fluidity of the resulting polymerization solution was observed. Next, the produced polymerization solution was precipitated in a large amount of methanol, and then filtered and dried to obtain a polymer, and the yield, weight average molecular weight (Mw) and molecular weight distribution (MWD) were measured. The results are shown in Table 3. From Table 3, 1,4-even if the type of organometallic compound is changed
It can be seen that when diphenylbutadiyne is added, the resulting polymerization solution has fluidity and the molecular weight of the obtained polymer decreases.

[Table 3]

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Yasuhiro Mitsuda 1-2-1 Yokou, Kawasaki-ku, Kawasaki-shi, Kanagawa Japan Zeon Corporation Research and Development Center

Claims (1)

[Claims] 1. Polymerization of a diphenylacetylene-based monomer in the presence of a catalyst comprising a halide of a transition metal of Group V of the periodic table and an organometallic compound having a reducing property with respect to the halide and a diacetylene compound. A method for producing a characteristic diphenylacetylene-based polymer.