JPS60208332A - Production of substituted polyacetylene compound modified with organopolysiloxane - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to organopolysiloxane-modified and substituted polyacetylene compounds, and more specifically to organopolysiloxane-modified compounds that have excellent gas permeability, particularly oxygen permeability, and ultraviolet resistance, and that provide molded products with high mechanical strength. This invention relates to substituted polyacetylene compounds.

What is the polymer obtained by polymerizing acetylene?

Since it has a conjugated double bond in its main chain and is highly reactive, it is expected to have various properties, but recently there have been several reports on the polymerization of substituted acetylenes with bulky substituents. The properties of polymers are attracting attention [P
ol! l1erPreprints, 31(8)+
189 (1982), 32 (2) 181 (+983
), same…(8)+171(+983), second time(8)
1175 (1983) etc.], especially polytrimethylsilylpropyiMe3 It has been reported that it is a material with high gas permeability [Poly+ser Preprints, 3
2 (10) 2881 (1883)].

However, it has been reported that certain substituted polyacetylenes show a significant decrease in molecular weight when exposed to ultraviolet rays and other radiation due to conjugated double bonds in the main chain and steric hindrance of bulky substituents.[Po12mer Pre
prints, 32(8)+879(+983)]
The present inventors also studied substituted polyacetylene having a bulky substituent consisting of a repeating unit of the general formula (1) described later, and found that it was soluble in an appropriate solvent and had excellent moldability and strength. , 200~300n+
It was confirmed that it absorbs ultraviolet rays of S, is relatively easily decomposed in the coexistence of oxygen, tends to cause a decrease in molecular weight, and as a result, has the disadvantage that molded products are easily damaged due to insufficient strength.

SUMMARY OF THE INVENTION An object of the present invention is therefore to provide a method for producing a substituted polyacetylene compound which not only has excellent gas permeability but also improved mechanical strength and ultraviolet resistance.

According to the present invention, general formula (1) R1% formula% (1) [wherein R1 represents a hydrogen atom or a lower alkyl group,
R2, R3 and R4 may be the same or different and each represents a hydrogen atom, a monovalent hydrocarbon group having 1 to 8 carbon atoms, or a monovalent organic group containing a silicon atom. A homopolymer or a copolymer or a mixed polymer thereof consisting of one or more repeating units represented by the above formula, and at least two repeating units per molecule in an amount of 0.1 to 50% by weight based on the double polymer. Provided is a method for producing an organopolysiloxane-modified substituted polyacetylene compound, which comprises heating a composition containing an organopolysiloxane having a 5i-H bond at a temperature of 60° C. or higher in the presence or absence of a catalyst. .

The organopolysiloxane-modified substituted polyacetylene produced by the method of the present invention has greater mechanical strength as a molded product than the substituted polyacetylene represented by the general formula (1) above, and can be used under exposure to sunlight, etc. It is possible to provide a molded product that is stable even when exposed to heat and is resistant to strength reduction due to ultraviolet rays or the like. In addition, this olga/hol)siloxane-modified M-converted polyacetylene has high gas permeability,
Moreover, since the ratio of the permeability coefficients of oxygen and nitrogen is large, the oxygen permeability is particularly high. It is also a substance that has a greater affinity for organic solvents such as ethanol than water.

The homopolymer or copolymer comprising one or more types of repeating units represented by the general formula (1) is the object of the present invention.

Formula R" -C=C-9i (R2) (R3) (R'
) 1 of the substituted acetylene compounds (monomers) shown in
It is produced by (co)polymerizing a species or two or more species. That is, polymerization or copolymerization is carried out in an organic solvent such as toluene or cyclohexane at a temperature of 30 to 130°C in the presence of a polymerization catalyst such as WCla, NbCl5, or TaCIL5, and the resulting polymer is precipitated in methanol for purification. and collected.

Although examples of polymerization methods are given below, the present invention is not limited to these. It can also be copolymerized with other acetylene derivatives that do not contain silicon, or a polymer in which some of the unsaturated bonds can be hydrogenated can also be used.

It is desirable that the substituted polyacetylene obtained in this way has a number average molecular weight of approximately 105 or more in terms of polystyrene; if the molecular weight is too small, the mechanical strength when made into a film etc. will be low, making it impractical. .

In the general formula (1), R1 is a hydrogen atom or a lower alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, and R2.1 (3 and 14 may be the same or different, and a hydrogen atom or a monovalent hydrocarbon group having 1 to 8 carbon atoms, such as an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group; an alkenyl group such as a vinyl group or an allyl group; an aryl group such as a phenyl group; is a silicon atom-containing organic group represented by (in the formula, R5 is a methyl group, a chloromethyl group, or a phenyl group, a is a number of 1 or 2; Me means a methyl group).

Next, the organopolysiloxane having at least two 5i-H bonds in one molecule used in the present invention has the average composition formula (2) [where a and b are positive numbers, and 2 ≦a+
b≦3, and R is a monovalent hydrocarbon group having 1 to 8 carbon atoms, preferably a methyl group, ethyl group, propyl group, vinyl group, or phenyl group. ] and has at least two hydrogen atoms directly bonded to a silicon atom in one molecule, linear, branched, or partially cross-bonded, or a combination of two or more of these. Mixtures are included. Specifically, (n2Z, m≧13°H (n≧4), etc. are exemplified.

The above organopolysiloxane having a 5i-H bond is not limited to one type, and two or more types thereof may be used in combination.

The organopolysiloxane-modified substituted polyacetylene compound of the present invention can be prepared by adding the substituted polyacetylene represented by the general formula (1) to a solution of a hydrocarbon such as benzene, toluene or hexane, a halogenated hydrocarbon such as chloroform or tetrachloroethylene, or tetrahydrofuran. formula(
After adding the organopolysiloxane shown in 2) and forming it into a plate shape, film shape, thread shape, hollow fiber shape, etc.,
It can be obtained by heating to denaturation at a temperature of 80 to 130°C or above, preferably 80 to 130°C.

Alternatively, it can be heated and modified in solution form and then molded.

Further, in order to accelerate the modification treatment, heat treatment can be performed in the presence of a catalyst. As the catalyst, a platinum-based catalyst, a rhodium-based catalyst, etc. can be used, and a platinum-based catalyst is preferable, and specific examples include chloroplatinic acid, a complex of chloroplatinic acid and an olefin or vinyl siloxane, etc. I can do it.

The amount of organopolysiloxane added is in the range of 0.1 to 50% by weight, preferably 1 to 30% by weight, based on the substituted polyacetylene. Added amount of organopolysiloxane is 0
．． If the amount is less than 1% by weight, the effect of improving the mechanical strength of the obtained molded product may not be sufficiently exhibited.On the other hand, if the amount added exceeds 50% by weight, the compatibility with the substituted polyacetylene compound is insufficient and the composition may deteriorate. Turbidity occurs and the resulting molded product is brittle and cannot be used for practical purposes.

The organopolysiloxane-modified substituted polyacetylene compound obtained by the production method of the present invention has particularly high oxygen permeability and is suitable as a material for oxygen separation membranes, contact lenses, and the like. Furthermore, since the compound has a greater affinity with organic solvents such as ethanol than with water, it is expected to be used as a liquid separation membrane for separating alcohol from a solution containing alcohol, or as a resist material, for example.

Next, the present invention will be specifically explained with reference to Examples.

Example 1 500 mg of polymerization catalyst TaC 5 was added to 150 m of toluene.
1d, then 15 g of l-methyl-2-trimethylsilylacetylene Me -C=:C-9iC-9i was added and polymerized at 80°C for 6 hours. The resulting polymer was precipitated in excess methanol, filtered and After repeated washing with methanol and drying, 13.5% of the polymer (substituted polyacetylene) corresponding to the formula Me + C=C-)-n Si (Me)3 was
g was obtained.

Methylhydrodiene polysiloxane (Shin-Etsu Chemical, product name KF-98) having a structure of 2% by weight of toluene Me (n = 28) of this substituted polyacetylene was 1
00g and a complex of chloroplatinic acid and vinylsiloxane as a platinum catalyst in an amount of 0.3% by weight based on methylhydrodiene polysiloxane were added and mixed.The resulting composition was cast at a maximum temperature of 50°C. The solvent was evaporated to form a film. Further, IHr heat denaturation treatment was performed at 120°C to produce a homogeneous and transparent film with a thickness of 10 l.

The IR spectrum of the obtained film is shown in FIG. 21
Absorption due to remaining 5i-H bonds is observed at 80 cm-', and absorption due to siloxane bonds is observed at 1040 cm-' and 1100 cm-'.

About this film JIS K7+13-IE17?
When the tensile strength was measured according to the method of
The weight was 79kg1c2. After this film was irradiated with ultraviolet rays for 120 hours at a distance of about 4C11 from the light source using a high-pressure mercury lamp in the presence of air, the tensile strength was 441K.
g/cm2, and it was still a strong film.

Comparative Example 1 Same as Example 1, the maximum temperature was 50℃ by casting.
For the film obtained by evaporating the solvent at 120°
When the tensile strength of C1IHr was measured without heating or denaturation treatment, it was 304 kg/Cm2. After this film was irradiated with ultraviolet rays for 72 hours in the same manner as in Example 1, the tensile strength was 150 kg/C112.

2 From a comparison between Example 1 and Comparative Example 1, it was confirmed that the strength of the molded product increased and the UV resistance improved by heating and deformation treatment.

Examples 2 to 15 Various substituted polyacetylene monomers were polymerized or copolymerized in a toluene solution using catalyst Ta (4s) in the same manner as in Example 1.
An organopolysiloxane having an iH bond and a platinum catalyst were added and a film was formed by casting, followed by heating and modification treatment. The tensile strength of these films was measured in the same manner as in Example 1. For comparison, the tensile strength of the film before heating and modification treatment was also measured.

The results are shown in Table 1. The type of platinum catalyst used and the weight percentage added to the polyorganosiloxane are the same as in Example 1.

In addition, as monomers A to G in the table, monomers having the following structural formula were used.

Seven Tsuma-A: Me Me-C=C-5i -Me ■ 1 Me -C= C-3i-Ph Me Monomer D: ) Ie ■ HC= C-3i->! e Me Monomer E: Me '14e -C== C-3i-Et IIP Me-C+a=C-3i-Pr ■ Me Senzuma-H: Me HCmiC-3i-Ph Me However, Me: -CH3, Et: -CH2(J
13, Pr: CH2CH2CH3, Ph: represents a phenyl group.

Example 16 A homogeneous film with a film thickness of 10 μm was obtained by performing the same procedure as in Example 1, except that no platinum catalyst was used, by casting a 50% polypropylene film, heating it at 120°C for 3 hours, and denaturing it. Had made. The tensile strength of the film was measured before and after heating and modification treatment and after UV irradiation.

The results are shown in Table I.

Example 17 In the same manner as in Example 1, Example 1 was added to 100 g of a double % toluene solution of substituted polyacetylene obtained by polymerizing 1-methyl-2-trimethylsilylacetylene Me-C=C-5i(Me)3. 200 mg of the same organopolysiloxane KF-911 and a small amount of platinum catalyst were added and mixed, and this solution was heated at 110°C for 3) 1r and subjected to modification treatment. This solution was precipitated in excess methanol, filtered and washed repeatedly with methanol, and dried. The obtained organopolysiloxane-modified substituted polyacetylene was dissolved in toluene and cast to a film thickness of 10 g.
I made a film of m. IR specs of this film)・
The measurement result was 104104O', 1100c'1
Absorption due to siloxane bonds was observed at 2180c+s-'', and absorption due to 5i-H bonds was observed at 2180c+s-''.

The tensile strength of this film was 451 kg/cm2.

[Brief explanation of the drawing]

FIG. 1 shows the IR spectrum of the film obtained in Example 1. Patent Applicant Shin-Etsu Chemical Co., Ltd. Agent Patent Attorney Shushi Iwamitani Written Amendment (May 1, 1980 Commissioner of the Patent Office Kazutoshi Wakasugi 1, Indication of Case Patent Application No. 0135480 of 1982)
No. 2, Name of the invention Process for producing an organopolysiloxane-modified substituted polyacetylene compound 3, Person making the amendment 1 Relationship with the matter Patent applicant Name Representative Yutabe Koita 4, Agent address 6 Akasaka, Minato-ku, Tokyo Chome 10-45 No. 74 Detailed explanation of the invention of the specification subject to the amendment +! 1, Column 8, Detailed Description of the Invention in the Statement of Contents of Amendment, is amended as follows. (1) Description of “before amendment” in the parts shown in the table below in the specification (2)
The following statement in the first line of page 8 is "(R)a HbSi04-ab -= (2)1-". (3) Correct the following formula [% formula %() on page 12, line 1O, as follows: (Me)35i-(-0-5i-)y O-Si (M
e) 3Me 1 .

Claims (1)

[Claims] (1) General formula: R1 3 [wherein R1 represents a hydrogen atom or a lower alkyl group,
R2,) i3 and R4 may be the same or different and represent a hydrogen atom, a monovalent hydrohydrogen group having 1 to 8 carbon atoms, or a monovalent organic group containing a silicon atom; a homopolymer or copolymer or a mixed polymer thereof consisting of two or more types, and an organopolysiloxane having at least two 5i-H bonds in one molecule in an amount of 0.1 to 50% by weight based on the above polymer. A method for producing an organopolysiloxane-modified substituted polyacetylene compound, which comprises heating a composition containing the following at a temperature of 60° C. or lower in the presence or absence of a catalyst. (2) The manufacturing method according to claim 1, wherein the catalyst is a platinum-based catalyst. (3) The manufacturing method according to claim 1 or ff12, wherein the composition A manufacturing method in which the molded material is heated.