JPH02263808A - Production of vinylsilane-based polymer - Google Patents

Abstract

PURPOSE:To obtain the title polymer useful as an oxygen enriching film, bio- compatible medical material, bioseparator material, electronic material, heat- resistant rubber and heat-resistant resin by polyserizing a vinylsilane-based monomer in an inert organic solvent using a specific catalyst. CONSTITUTION:A vinylsilane-based monomer (preferably dimethylphenylvinylsilane) shown by the formula (R<1> is 1-20C alkyl or 6-20C aryl; R<2> to R<6> are H, methyl or ethyl) is polymerized in an inert organic solvent using a catalyst comprising an organic alkali metal (preferably n-butyllithium) and a nitrogen atom-containing electron donor (preferably N,N,N',N'- tetramethylethylenediamine) to give the aimed polymer.

Description

[Detailed Description of the Invention] [Field of Industrial Application] The present invention is applicable to various functions including oxygen-enriching membranes, biocompatible medical materials, electronic materials, bioseparator materials, heat-resistant rubber, and heat-resistant resins. The present invention relates to a method for producing a vinylsilane polymer that is useful as a plastic material.

[Conventional technology]

In recent years, requirements for industrial materials include mechanical suitability, heat resistance,
Materials that not only have weather resistance properties, but also have functions such as gas separation functions such as oxygen enrichment membranes, biocompatibility when used as artificial organs, and optical nonlinearity that converts the wavelength of light. There is a growing interest in

Vinylsilane polymers have been studied for a long time as materials that meet these demands, and the following examples are known.

Namely, N, S-Nametkine et al. [J, P
o1yn+, Sci, sPart C, No, 4.
1053 (1963)), by polymerizing dimethylphenylvinylsilane in heptane using ethyllithium as an initiator, only polydimethylphenylvinylsilane represented by -(CH, -CH), 1 CH, -3i -CHl was produced. is reported to be generated.

Also, Japanese Patent Publication No. 48-15472 and Japanese Unexamined Patent Publication No. 51
Publication No. 38381 discloses that block copolymers and random copolymers can be obtained by polymerizing a triorganovinylsilane compound, a conjugated diene compound, and a styrene derivative. However, in all of these triorganovinylsilane compounds, only a polymer having a structure in which a triorganosilyl group is added to a side chain is obtained by addition polymerization with a vinyl group.

In addition, G. K. Rickle (J. Macr.
os+o1. Sci,+Chew+,Ed,,""h
1287 (1986)) investigated the polymerization of trimethylvinylsilane using an ether such as 1,2-dimethoxyethane or tetrahydrofuran and an organolithium catalyst, but the polymerization conversion rate of the monomer was low and the molecular weight was too low. There are problems such as low Moreover, the formation of a polymer in which the trimethylsilyl group has a structure in which it is added to a side chain and a silicon atom is included in the main chain has not been reported.

Furthermore, R, Asaa+i et al. (Poly+wer J,
Jj), 699 (198B)] is N, N, N'
, suggests a structure in which trimethylvinylsilane is polymerized using N'-tetramethylethylenediamine and n-butyllithium as an initiator, and a trimethylsilyl group is added to the side chain, as well as a structure in which a silicon atom enters the main chain.

However, the trimethylsilyl group has a problem in that its heat resistance is rather low.

On the other hand, as a polymer having a structure in which silicon atoms are included in the main chain, N. S. Nametkine et al. [J, Po
lym.

Sci, Part C, No. 4.1043 (
[1963] reported the synthesis of a polymer obtained by ring-opening polymerization of ]1,1-dialkyl-1-silacyclobutane.

However, the synthesis of these monomers is complicated and there are manufacturing problems such as high polymerization temperatures.

Moreover, the resulting polymers can only have a structure in which silicon atoms are present only in the main chain.

As described above, the current state of the art is that there is still no method for producing a satisfactory vinyl silane polymer.

[Problem to be solved by the invention]

The present invention was made against the background of the above-mentioned conventional technical problems, and it produces a vinylsilane polymer that has high heat resistance and can change its molecular properties from resin-like to rubber-like even with a single monomer. The purpose is to provide a method.

[Means to solve the problem]

The present invention is characterized in that a vinylsilane monomer represented by the following general formula (I) is polymerized using a catalyst consisting of an organic alkali metal and an electron donor containing a nitrogen atom in an inert organic solvent. The present invention provides a method for producing a vinyl silane polymer.

(In the formula, R1 is an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms; Rz and Rh are the same or different and represent a hydrogen atom, a methyl group, or an ethyl group) Examples of polymerization solvents include inert organic solvents, such as aromatic hydrocarbon solvents such as benzene, toluene, and xylene; n-pentane, n-hexane, and n-hexane.
- aliphatic hydrocarbon solvents such as butane, cyclohexane;
Alicyclic hydrocarbon solvents such as methylcyclopentane, cyclohexane, and mixtures thereof can be used.

Next, examples of the organic alkali metal that is one of the components constituting the catalyst include organic lithium compounds. Specific examples of this organic lithium compound include ethyllithium, propyllithium, n-butyllithium, 5e
c-butyllithium, t-butyllithium, hexyllithium, 1,4-dilithiobutane, a reaction product of butyllithium and divinylbenzene, alkylene dilithium, phenyllithium, stilbenedilithium, isopropenylbenzenedilithium, lithium naphthalene, etc. Preferred is n-butyllithium.

Examples of the nitrogen-containing electron donor constituting the other catalyst component include trialkylamines such as triethylamine, methyldiethylamine, tri-n-propylamine, and methyldiropropylamine; N-methylpyrrolidine, N-methylpiperidine; cyclic tertiary amines such as N,N,N'N'-tetramethylethylenediamine,
Examples include tertiary diamines such as 1,2-dibiperidinoethane, and preferably N, N, N', N'-
Tetramethylethylenediamine.

In addition, in the case of an organic alkali metal, the amount of the catalyst used in the present invention is 0.01 to 0.0 per mole of monomer.
0001 times mole, preferably 0.05 to 0.0001 times mole.

The amount of the electron donor containing a nitrogen atom used is 0.1 to 15 times the mole of the organic alkali compound, preferably 0.2 to 10 times the mole, and less than 0.1 times the mole of the silyl The group enters the side chain, resulting in poor heat resistance of the resulting polymer.On the other hand, if the amount exceeds 15 times the mole, the polymerization rate slows down and the molecular weight decreases.

To prepare the catalyst, for example, an organic alkali compound dissolved in an inert organic solvent and a nitrogen atom-containing electron donor can be reacted, but by adding the electron donor during the polymerization reaction, The structure in which silicon atoms enter the side chain and the structure in which the silicon atom enters the main chain can be changed continuously or in blocks.

Next, the monomer used in the present invention is the general formula (I
) is a vinylsilane monomer represented by Here, in the general formula (I), R1 is preferably a methyl group or an ethyl group in order to increase the polymerization rate, and preferably a phenyl group or a tolyl group in order to improve heat resistance.

In the general formula (I), R1 to R6 are preferably hydrogen atoms in order to increase the polymerization rate, and in order to increase the heat resistance, an alkyl group such as a methyl group or an ethyl group, or an aryl group such as a phenyl group. Groups are preferred.

Specific examples of vinylsilane monomers include dimethylphenylvinylsilane, methylbutylphenylvinylsilane, methylbutylphenylvinylsilane, methyldiphenylvinylsilane, methylbutyl-(p-methylphenyl)vinylsilane, methyldi(p-methylphenyl)vinylsilane, and methyl- Examples include (p-methylphenyl)vinylsilane, and dimethylphenylvinylsilane is preferred.

These vinylsilane monomers can be used alone or in combination of two or more.

In addition to the vinylsilane monomer, the present invention also includes trimethylvinylsilane, triethylvinylsilane,
70 mol% or less, preferably 10 to 60 mol% of trialkylvinylsilane such as dibutylmethylvinylsilane
By copolymerizing to a certain degree, the heat resistance and glass transition temperature of the resulting polymer can be adjusted.

In the polymerization method applied to the present invention, the inert organic solvent used in the present invention,
Polymerization is carried out by charging a catalyst and a vinylsilane monomer (and trialkylvinylsilane if necessary), or by adding them intermittently or continuously.

The polymerization temperature is usually -120°C to 150°C, preferably -80 to 120°C.The polymerization time is usually 5 minutes to 80°C.
0 hours, preferably 10 minutes to 50 hours.

Regarding the polymerization temperature, the reaction may be carried out at a constant temperature within the above-mentioned temperature range, or may be carried out at elevated temperature or under adiabatic conditions, and the polymerization reaction may be carried out batchwise or continuously.

Note that the monomer concentration in the solvent is usually 5 to 100% by weight.
, preferably 10 to 50% by weight.

In addition, in order to prevent deactivation of the catalyst and polymer of the present invention in order to produce the polymer, consideration must be given to minimizing the incorporation of compounds with a deactivation effect such as oxygen, water, or carbon dioxide gas into the polymerization system. is necessary.

The vinyl silane polymer obtained by the present invention is IH-
Through NMR analysis, it is estimated that they have structure (A) and structure (B) represented by the following formula (If).

Old/ Structure (A) [In the formula, Mi R1, R6 m and n are structure (A) Said - Formula (II) Structure (B) is the same as the general formula (I) above, and structure CB), ] , n is less than 10 mol% If the temperature is too high, the heat resistance will be poor.

After the polymerization reaction is complete, steam is blown into the polymer solution to remove the solvent, or a poor solvent such as methanol is added to solidify the vinylsilane polymer, and then the polymer is obtained by drying with a hot roll or under reduced pressure. be able to.

Alternatively, the polymer can be obtained by directly removing the solvent from the polymer solution under reduced pressure.

Although the molecular weight of the vinylsilane polymer obtained in the present invention can be varied over a wide range, the number average molecular weight in terms of polystyrene is usually 5,000.
A range of 0 to 600,000 is preferred.

Thus, the vinylsilane polymer obtained according to the present invention can be used for gas separation membranes such as oxygen enrichment membranes, biocompatible medical materials such as artificial organs, catheters, optical materials for light conversion, and resists for electronic circuit manufacturing. It can also be used as a material, heat-resistant rubber, and heat-resistant resin in general industrial products.

〔Example〕

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to the following Examples as long as the gist thereof is not exceeded.

In the examples, parts and percentages are based on weight unless otherwise specified.

Moreover, various measurements in the examples were based on the following methods.

Thermogravimetric analysis (TGA) is performed using a thermogravimetric analyzer (manufactured by Rigakusha).
THI! RMOFLEX TG8110 type) and data processing device (Thermal Analysis 5tat)
ion TAS 100 type) was used. Measurement is 5-1
A sample of 0.0 cm was accurately weighed, and the temperature was raised at a rate of 20° C. per minute under a nitrogen gas flow.

The number average molecular weight is determined by gel permini-silane chromatograph 4-(GPC) (%1 manufactured by Aters, cpc).

244 type) in terms of polystyrene.

'H-NMR (proton nuclear magnetic resonance apparatus) is VARI
ANT XL-200 Fourier transform nuclear magnetic resonance apparatus (
Measurement was carried out at 20° C. using tetramethylsilane or methylene chloride as a standard sample in each solvent of carbon tetrachloride or deuterium chloroform.

The structure of the polymer obtained in the present invention is determined by I) 0, 2 to 2. It was determined from the peak area of silylmethylene near 0.5 ppm and silylmethine near 0.9 ppm in the OppmSl range from the ratio of silicon atoms entering the side chain and the ratio of silicon atoms entering the main chain. The greater the isomerization rate, the greater the proportion of silicon atoms entering the main chain.

Example 1 Dimethylphenylvinyl silica 7 (DMP) was placed in a glass flask containing a rotor and having an internal volume of 100 rml, each sealed in a glass tube with a breaker seal under vacuum.
VS)3. Og (18,5 mmol), n-butyllithium (n-BuLi) 0.024 g (0,37 mmol), N,N,N',N'tetramethylethylenediamine (TMEDA) 0.045 g (0,39 mmol), then add 30 mmol of cyclohexane under vacuum.
11 was introduced, and the flask was sealed.

The flask was then placed in a 25°C water bath and the n-BuL
The breaker seal was broken in the order of T, TMEDA, and DMPVS to start the polymerization reaction.

After 48 hours, a large amount of methanol was added to obtain a polymer.

Table 1 shows the polymerization results and polymer analysis results.

In addition, FIG. 1 shows the IH-NM of the polymer obtained in this example.
The R analysis chart and the thermogravimetric analysis results of the polymer obtained in this example are shown in FIG. 2.

Comparative Example 1 Using the same apparatus as in Example 1, dimethylphenylvinylsilane was polymerized in the same manner as in Example 1 without using N,N,N'N'-tetramethylethylenediamine.

Table 1 shows the polymerization results and polymer analysis results.

In addition, Fig. 2 shows the thermogravimetric analysis results of the polymer obtained in this comparative example, and Fig. 3 shows the IH-N of the polymer obtained in this comparative example.
An MR analysis chart is shown.

From the comparison between Example 1 and Comparative Example 1, when the isomerization rate is high,
It can be seen that the thermal decomposition temperature is high.

Comparative Example 2 Trimethylvinylsilane was polymerized in the same manner as in Example 1, except that trimethylvinylsilane (TMVS) was used instead of dimethylphenylvinylsilane in Example 1.

Table 1 shows the polymerization results and polymer analysis results.

Further, FIG. 2 shows the results of thermogravimetric analysis of the polymer obtained in this comparative example.

Comparative Example 3 Trimethylvinylsilane was used instead of dimethylphenylvinylsilane in Example 1, and N,N.

Trimethylvinylsilane was polymerized in the same manner as in Example 1, except that N',N'-tetramethylethylenediamine was not used.

Table 1 shows the polymerization results and polymer analysis results.

Further, FIG. 2 shows the results of thermogravimetric analysis of the polymer obtained in this comparative example.

A comparison between Example 1 and Comparative Examples 2 and 3 shows that the polymer of dimethylphenylvinylsilane has a higher decomposition temperature than the polymer of trimethylvinylsilane.

Examples 2 to 4 Using the same apparatus as in Example 1, dimethylphenylvinylsilane was polymerized under the conditions shown in Table 1. Table 1 shows the polymerization results and polymer analysis results.

Further, FIG. 4 shows the results of thermogravimetric analysis of the polymers obtained in Examples 2 to 4.

Comparative Example 4 Dimethylphenylvinylsilane was polymerized in the same manner as in Example 1, except that 1,2-dimethoxyethane was used instead of N,N,N',N'-tetramethylethylenediamine in Example 1.

The polymer yield was 67%.

Further, the isomerization rate determined from 'H-NMR was 5%.

Example 5 The same apparatus as in Example 1 was used, except that 1.5 g (9.3 mmol) of dimethylphenylvinylsilane and 0.93 g (9.3 mmol) of trimethylvinylsilane were used as monomers. Copolymerization of dimethylphenylvinylsilane and trimethylvinylsilane was carried out in the same manner as in Example 1.

The polymer yield was 98%, and the number average molecular weight of the obtained copolymer was 56,000 and the weight average molecular weight was 94,000.
, Mw/Mn=1.68.

Further, the isomerization rate determined from 'H-NMR was 85%, and the thermal decomposition temperature was 412°C.

(The following is a blank space) Table 1 Table 1 (Continued) [Effects of the Invention] The present invention uses a catalyst comprising an organic alkali metal and an electron donor containing a nitrogen atom, and uses a catalyst represented by the general formula (I) above. By polymerizing vinylsilane monomers, it is possible to produce vinylsilane polymers in which silicon atoms are introduced into the main chain and side chains of the polymer at any desired ratio.

The resulting polymer has excellent heat resistance and is useful as various functional materials including oxygen-enriching membranes, biocompatible medical materials, bioseparator materials, electronic materials, heat-resistant rubbers, and heat-resistant resins.

NMR analysis chart, Figure 2 shows Example 1 and Comparative Example 1
Fig. 3 is a thermogravimetric analysis chart of the polymer obtained in Comparative Example 1 and Fig. 4 is a thermogravimetric analysis chart of the polymer obtained in Comparative Example 1 and Examples 2 to 4. 2 is a thermogravimetric analysis chart of the obtained polymer.

Patent applicant: Japan Synthetic Rubber Co., Ltd. Agent: Patent Attorney Takashi Shirai l No. figure No. figure

Claims (2)

[Claims] (1) Using a catalyst consisting of an organic alkali metal and an electron donor containing a nitrogen atom in an inert organic solvent, the following general formula (
A method for producing a vinylsilane polymer, which comprises polymerizing a vinylsilane monomer represented by I). ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(I) (In the formula, R^1 is an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, and R^2 to R^6 are The same or different, indicating a hydrogen atom, methyl group or ethyl group.) (2) The method for producing a vinylsilane polymer according to claim 1, wherein a vinylsilane monomer represented by general formula (I) and trialkylvinylsilane are used as the monomers.