JPS61247714A - Silyl group-containing polymer and its production - Google Patents

Abstract

PURPOSE:To produce in good yields the titled polymer having a high MW and being soluble in organic solvents and excellent in moldability and mechanical strength, by polymerizing a specified 3-silyl-1-alkylene monomer in the presence of a Group VI transition metal compound. CONSTITUTION:A 3-silyl-1-alkylene monomer of formula I (wherein R<1-2> are each a lower alkyl, R<3> is a n-alkyl, sec-alkyl, tert-alkyl or phenyl and R<4> is a n-alkyl) is polymerized at 0-100 deg.C for several tens min-several tens hr in an organic solvent (e.g., benzene) in the presence of 0.2-5mol, per 100mol of the monomer, of a Group VI transition metal compound (e.g., MoCl5) and, optionally, 0.3-3mol, per mol of the transition metal compound, reducing agent (e.g., tetraphenyltin) to obtain a silyl group-containing polymer, MW>=10,000, of formula II (wherein n is the number of repetition of repeating units). USE:Material for gas separation membranes, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a novel silyl group-containing polymer useful as a gas separation membrane material, etc., and a method for producing the same.

[Conventional technology]

Conventionally, for the polymerization of unsubstituted acetylene, acetylene compounds having a triple bond at the molecular end such as Although it is said that mixtures with other compounds are effective, they have been unsatisfactory due to problems such as slow polymerization rate and difficulty in obtaining polymers with a high degree of polymerization.

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. 37312/1989,
No. 20511, Special Publication No. 55-23565, Special Publication No. 1977
-43037, Japanese Patent Publication No. 55-30722, Japanese Patent Publication No. 1973
7-31911, JP-A-57-36106, JP-A-58-32608, JP-A-58-206611, and JP-A-59-93705).

has proposed a method of polymerizing trialkylsilyl acetylene (representing an alkyl group) using a tungsten-based catalyst (Japanese Patent Laid-Open No. 58-206611).

According to this method, a trialkylsilyl acetylene polymer useful as a material for 5-gas permeable membranes and the like can be obtained in high yield.

[Problem that the invention seeks to solve]

However, the polymer obtained by the method described in JP-A-58-206611 is partially insoluble in organic solvents, or even if it is completely soluble, its molecular weight is small, so it cannot be processed into films or the like. The problem is that it is difficult to Therefore, the purpose of the present invention is to solve these problems and to create a new silyl group-containing film that has a high molecular weight, is soluble in organic solvents, has excellent molding processability such as film formability, and can produce a film with high mechanical strength. It is an object of the present invention to provide a polymer, and a further object is to provide a process which allows such a polymer to be polymerized in a relatively short period of time and in a high yield.

[Means for solving problems]

The present invention solves the above-mentioned problems by the general formula (
1) [In the formula, R1 and R2 may be the same or different.

lower alkyl, R3 is n-alkyl group, 5ee
- an alkyl group, a tert-alkyl group or a phenyl group, -H4 is an n-alkyl group, and n is an integer representing the number of repeating units] .

Further, the present invention provides the general formula (II) [wherein R1, R2, R and R4 are represented by the general formula (j
)] (hereinafter referred to as "3-silyl-1-
The present invention provides a method for producing a silyl group-containing polymer represented by the general formula (1), which comprises polymerizing a silyl group-containing polymer (abbreviated as "alkyne") in the presence of a Group (I) transition metal compound.

In general formulas (1) and (■), R1 and R2 may be the same or different, and are lower alkyl groups, such as methyl and ethyl groups. R3 is an n-alkyl group such as methyl, ethyl, propyl, lobutyl, n-amyl, n-hexyl, n-decyl, n-dodecyl; isopropyl,
5ec-alkyl groups such as 5ec-butyl and 5ec-pentyl; t such as tert-butyl and tert-pentyl;
ert-alkyl group; or phenyl group. R4 is an n-alkyl group, preferably methyl, ethyl,
It is an n-alkyl group having 1 to 8 carbon atoms such as n-propyl, n-butyl, n-amyl, n-hexyl, and n-octyl.

In the present invention, a Group (I) transition metal compound is used as a single polymerization catalyst for the polymerization of 3-silyl-1-alkyne.

Group II transition metals include chromium, molybdenum, and tungsten. Specific examples of Group III transition metal compounds used as catalysts include molybdenum pentachloride (M
oC1s), chlorides such as tungsten hexachloride; substances obtained by irradiating a mixture of metal carbonyls such as chromium carbonyl, molybdenum carbonyl, and tungsten carbonyl with organic halides, such as carbon tetrachloride, ethyl trichloroacetate, etc. be able to.

It is appropriate to use these catalysts in an amount of 0.2 to 5 moles per 100 moles of the monomer 3-silyl-1-alkyne.

In addition, in the production method of the present invention, it is preferable to use a reducing agent in combination with the above-mentioned Group Ⅰ transition metal compound, and by using the reducing agent in combination, the action of the catalyst can be promoted, and a polymer with a higher molecular weight can be produced. It is advantageous to obtain Examples of reducing agents that can be used include organometallic compounds such as tetraphenyltin, tetra-n-butyltin, triphenylbismuth, triphenylantimony, and metal hydrides. The amount of this reducing agent used is 0.3 to 3 mol per mol of the Group Ⅰ transition metal compound.
A molar range is preferred.

The polymerization reaction in the production method of the present invention is usually carried out in an organic solvent. As the organic solvent, it is preferable to use hydrocarbons, halogenated hydrocarbons, and the like. In particular, benzene,
Toluene, cyclohexane, and the like are preferred because they can achieve a high yield of the polymer and are easily available.

In the polymerization reaction, the concentration of the monomer 3-silyl-1-alkyne is preferably in the range of 0.1 to 5 mol/Q, the reaction temperature is usually 0 to 100°C, and the reaction time is usually The duration is from several tens of minutes to several tens of hours.

Through the above polymerization reaction, a reaction mixture containing the polymer represented by general formula (1) is obtained, and by diluting the reaction mixture with the organic solvent used in the reaction and then pouring it into a large amount of methanol, The resulting polymer precipitates and can be recovered by filtration.

The polymer of the present invention having the structure of general formula (I) produced in this way has a molecular weight of 10,000 or more.1 Usually 10.0
00 to 3,000,000.

〔Example〕

EXAMPLES Next, the present invention will be specifically explained with reference to Examples, but the scope of the present invention is not limited thereby.

Example 1 (1) Synthesis of 3-trimethylsilyl-1-octyne 1-
It was synthesized by dilithioating the 1st and 3rd positions of octyne, and then reacting the 3rd position with trimethylchlorosilane.

10 mmol of molybdenum monosalt was added to the toluene soluble portion that had been sufficiently purified under a dry nitrogen atmosphere, and dissolved. Next, 0.5 mole of 3-trimethylsilyl-1-octyne was added, and 30
Polymerization was carried out at ℃ for 24 hours. After the reaction was completed, the reaction mixture was poured into a large amount of medanol to precipitate the produced polymer, which was filtered and dried. The yield of methanol-insoluble polymer is 3-
The amount was 77% based on the amount of trimethylsilyl-1-octyne charged.

The weight average molecular weight of the toluene soluble portion of the produced polymer was 180,000. The produced polymer was a yellow powder, which was insoluble in highly polar solvents and soluble in low polar solvents such as toluene, benzene, hexane, and carbon tetrachloride. A durable polymer film could be made by casting the solution onto a smooth flat surface.

The analytical values of the produced polymer are as follows.

○Elemental analysis value (as (CtlHzSl)n): Calculated value 8 12.16%, C72,44%, !;
L IS, 40% actual value 8 12.07%, C7
2,68 stones, Si 15.25%○ Infrared absorption spectrum: Shown in Figure 1.

Absorption based on C=C at 1490 cm-1, 1245 cm
-1,81,5Cm-"+750cm-'15i
Absorption based on (CH3)3 and absorption based on -C11□- were observed in 1460Offl-1.

From the above, it was found that the produced polymer had the following structure.

The resulting poly(3-trimethylsilyl-1-octyne)
When the gas permeability of the film was measured, the oxygen permeability coefficient Po2 = 4.2 x 10-1l (C10-1l (C
・cm/cm2・Sec-cmHg), and the ratio of the permeability coefficients of oxygen and nitrogen was Po, /P = 3.1.

Examples 2 to 14 In Example 1, instead of molybdenum pentachloride,
Polymerization was carried out in the same manner as in Example 1, except that the catalyst shown in the table was used. Table 1 shows the yield and weight average molecular weight of the obtained polymer. However, when a reducing agent was used in combination, the amount used was 10 mmol. Example 15 Same as Example 1 except that 3-trimethylsilyl-1-decyne was used as the monomer instead of 3-trimethylsilyl-1-octyne. Polymerization was carried out in the same manner.

Table 1 shows the yield and weight average molecular weight of the obtained polymer. Moreover, the infrared absorption spectrum of the polymer is shown in FIG.

Example 16 Polymerization was carried out in the same manner as in Example 8, except that 3-trimethylsilyl-1-decyne was used as the monomer instead of 3-trimethylsilyl-1-octyne.

Table 1 shows the yield and weight average molecular weight of the obtained polymer.

Example 17 Polymerization was carried out in the same manner as in Example 1 except that 3-trimethylsilyl-1-hexyne was used as a monomer instead of 3-trimethylsilyl-1-octyne.

Table 1 shows the yield and weight average molecular weight of the obtained polymer. Moreover, the infrared absorption spectrum of the polymer is shown in FIG.

Example 18 Polymerization was carried out in the same manner as in Example 8 except that 3-trimethylsilyl-1-hexyne was used as the monomer instead of 3-trimethylsilyl-1-octyne. Table 1 shows the yield and weight average molecular weight of the obtained polymer.

〔Effect of the invention〕

The novel polymer of the present invention has a high molecular weight of 10,000 or more and is soluble in organic solvents.
Excellent formability such as film forming properties. The polymer has high gas permeability and the mechanical strength of the molded product is high, so it is useful as a gas permeable membrane, especially a gas separation membrane for separating oxygen from air, and various other separation membranes. It is also expected. Furthermore, since it has excellent film forming properties, it is expected to be used as a photoresist, etc.

Moreover, according to the method for producing a polymer of the present invention, such a useful new polymer can be obtained in a high yield in a relatively short polymerization time.

[Brief explanation of drawings]

FIG. 1, FIG. 2, and FIG. 3 respectively show Example 1.
Figure 2 shows the infrared absorption spectra of the polymers of the present invention prepared in Nos. 15 and 17.

Claims (1)

[Claims] 1) General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼... (I) [In the formula, R^1 and R^2 may be the same or different, and is alkyl, R^3 is an n-alkyl group, s
ec-alkyl group, tert-alkyl group, or phenyl group, R^4 is an n-alkyl group, and n is an integer representing the number of repeating units. 2) General formula (II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼... (II) [In the formula, R^1, R^2, R^3 and R^4 are the same as general formula (I) A method for producing a silyl group-containing polymer represented by the general formula (I), which comprises polymerizing a monomer compound represented by the following in the presence of a Group VI transition metal compound.