JPH0325452B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to an organopolysiloxane-substituted polyacetylene composition, and more specifically, an organopolysiloxane-substituted polyacetylene composition having gas permeability, particularly oxygen permeability with high stability over time. , relates to organopolysiloxane-substituted polyacetylene compositions that give molded articles with high mechanical strength. [Prior Art] Recently, there have been several reports on the polymerization of substituted acetylenes having bulky substituents, and the properties of the resulting polymers have attracted attention. [Polymer
Preprints, 31 (6) 1189 (1982), 32 (2) 181 (1983)
,
32 (6) 1171 (1983), 32 (6) 1175 (1983), etc.]. In particular, it has been reported that polytrimethylsilylpropyne: [Formula] (wherein Me is a methyl group) is a material with extremely high gas permeability. [Polymer Preprints,
32(10), 2981 (1983), Japanese Patent Publication No. 59-154106]. The inventors also used the following general formula: When we investigated a substituted polyacetylene compound having a high substituent group consisting of repeating units represented by confirmed. Recently, interpenetrating polymer networks (IPN) have been developed as a method for modifying the physical properties of polymeric materials and introducing new functions.
Networks) is attracting attention [J.
Polymer Sci.: Macromolecular Reviews, 12 ,
141-181 (1977); Polymer alloys (edited by the Society of Polymer Science) 338-348; Plastics, 27 , 50-53
(1976); Polymer, 33 , 632 (1984); Chemical Industry, 26 ,
1025-1028 (1984), especially for silicone.
Various proposals have been made regarding the application of IPN [JP-A-50-151958, US Pat. No. 4,250,074, JP-A-58-189257]. Japanese Patent Application Laid-Open No. 50-151958 is
The combination of acrylic acid-based hydrophilic polymer and siloxane
The present invention relates to IPN and provides a solid molded body suitable as a contact lens material. US Pat. No. 4,250,074 relates to IPN of epoxy resin and siloxane, and is intended to improve the acid resistance and solvent resistance of epoxy resin. Furthermore, JP-A-58-189257 relates to an IPN of thermoplastic plastic and siloxane, which is said to impart the surface properties and dielectric properties of silicone while retaining the mechanical properties of the thermoplastic resin matrix. It is something. As described above, no attempts have been made to modify gas permeable materials with IPN. [Problems to be solved by the invention] As mentioned above, substituted polyacetylenes having bulky substituents are materials with high gas permeability, but their stability over time is low and gas permeability gradually decreases. Because of this tendency, there is a problem that stable performance cannot be obtained over a long period of time when formed into a gas separation membrane or the like. SUMMARY OF THE INVENTION Therefore, an object of the present invention is to provide a polymer composition that maintains the excellent gas permeability of substituted polyacetylenes and has improved stability over time. [Means for Solving the Problems] The present invention solves the problems of the conventional substituted polyacetylenes as described above ^. an atom or a lower alkyl group such as a methyl group, ethyl group, propyl group, butyl group, and R ² , R ³ , and R ⁴ may be the same or different, and a hydrogen atom or a carbon atom having 1 to 8 carbon atoms. valent hydrocarbon groups, e.g. alkyl groups such as methyl, ethyl, propyl, butyl; aryl groups such as phenyl, or e.g. A silicon atom-containing monovalent organic group represented by (in the formula
R ⁵ is a methyl group, a chloromethyl group or a phenyl group, a is a number of 1 or 2; Me means a methyl group). ] A substituted polyacetylene compound having one or more types of structural units represented by (B) 0.1 to the substituted polyacetylene compound;
The present invention provides an organopolysiloxane-substituted polyacetylene composition (hereinafter abbreviated as "polymer composition") comprising ~100% by weight of organopolysiloxane and having an interpenetrating network structure. The polymer composition of the present invention has the general formula ()
A substituted polyacetylene compound having one or more types of structural units represented by the above is combined with at least two types of organosiloxanes having mutual crosslinking properties.
After mixing the prepolymer to form an organopolysiloxane of 0.1 to 100% by weight based on the substituted polyacetylene compound, the organosiloxane
It can be manufactured by crosslinking a prepolymer. Typically substituted polyacetylene compounds
The prepolymer may be used in an amount of 0.1 to 100 parts by weight per 100 parts by weight. The substituted polyacetylene compound which is component (A) of the polymer composition has the general formula () [In the formula, R ¹ , R ² , R ³ and R ⁴ are general formulas ()
] Substituted acetylene compound (monomer) represented by
It is produced by homopolymerizing or copolymerizing one or more of the following. i.e. in organic solvents such as toluene, cyclohexane, etc.
It is produced by polymerization or copolymerization at a temperature of 30 to 130°C in the presence of a polymerization catalyst such as WClb, NbCl ₅ or TaCl ₅ , and the resulting polymer is purified and recovered by precipitation in methanol. The polymerization method of the substituted polyacetylene compound is not limited to the above example, and during polymerization, it is also possible to copolymerize with other silicon-free acetylene derivatives other than the substituted polyacetylene compound of the above general formula (). Alternatively, a polymer in which some of the unsaturated bonds are hydrogenated can also be used. Therefore, the substituted polyacetylene compound may contain structural units other than the structural units of the general formula (), but in terms of gas permeability of the composition, the structural units of the general formula () are at least 50 mol%.
or more, preferably 80 mol% or more,
Most preferably it is 100 mol%. In this way, the substituted polyacetylene compound as component (A) may be a homopolymer consisting of structural units represented by the same general formula (), or may be a homopolymer consisting of structural units represented by two or more general formulas (), and in some cases It may even be a copolymer containing other structural units. Furthermore, a mixed polymer of such polymers may be used. It is desirable that this substituted polyacetylene compound has a molecular weight of about 10 ⁵ or more in terms of polystyrene; if the molecular weight is too small, the mechanical strength of the polymer composition when made into a film etc. will be low, making it impractical. Not. Among the substituted polyacetylene compounds explained above, the following formula (): formula(): It consists of a structural unit represented by 30 to 95 moles of the structural unit of formula (), and 70 to 5 moles of the structural unit of formula ().
The polymer containing mol% is particularly preferred because it has good compatibility with the organosiloxane prepolymer for producing component (B) and the resulting polymer composition has excellent gas permeability. As mentioned above, the organopolysiloxane which is the component (B) of the polymer composition of the present invention is composed of at least two kinds of organosiloxanes having mutual crosslinking properties.
By crosslinking the prepolymer mixed with the substituted polyacetylene compound (A), IPN
It is obtained in a state where it is formed. The inter-crosslinkable organosiloxane prepolymers used in the above production method include (a) those that are crosslinked by an addition type reaction, (b) those that are crosslinked by a condensation type reaction, and (c) those that are crosslinked by a free radical type reaction. There are things that do. These intercrosslinkable organosiloxane prepolymers are mixed with a solution of the substituted polyacetylene compound (A) in a suitable solvent, such as a hydrocarbon such as toluene, benzene, or cyclohexane, and if necessary, a suitable catalyst is added. In addition, a polymer composition in which an IPN of a substituted polyacetylene compound and an organopolysiloxane is formed by molding into an appropriate shape and then crosslinking, or by crosslinking and then molding into an appropriate shape. is obtained. Specifically, the above type (a) prepolymer is composed of an organopolysiloxane having at least two vinyl groups in one molecule and an organopolysiloxane having at least two Si-H bonds in one molecule. Combinations of organopolysiloxanes having at least two vinyl groups in one molecule and organopolysiloxanes having at least two mercapto groups in one molecule can be used, and the former may be platinum-based, rhodium-based, etc. The latter can be crosslinked by light irradiation by using as a catalyst, preferably chloroplatinic acid, a complex of chloroplatinic acid and an olefin or a vinylsiloxane, and by heat treatment. Generally, the number of moles of -SiH bond or the number of moles of meltcapto group is preferably in the range of 1:5 to 5:1 with respect to the number of moles of vinyl group, and photocrosslinking between mercapto group and SiCH= _CH2 is generally preferred. When carried out, it is preferable to add a photosensitizer. Type (b) prepolymers include organopolysiloxanes having at least two SiOH groups in one molecule and Si-X groups in one molecule [where X is -H group, -OH group, - ₃ OCH groups, ₅ −OC ₂ H groups,
[Formula] [Formula] [Formula] [Formula] [Formula] (R ₁ and R ₂ represent hydrogen or a lower alkyl group) etc. , dehydrated type, dealcoholized type, acetated type, dehydroxyamine type, deoxime type, deamined type, and deacetonized type, and it is preferable to use a known catalyst for promoting each reaction. As the type (c) prepolymer, an organopolysiloxane having a vinyl group and a methyl group in one molecule can be used, and an organic peroxide or the like is added thereto and crosslinked by heating. In the resulting polymer composition, the organopolysiloxane component (B) accounts for 0.1 to 100% by weight of the substituted polyacetylene compound component (A), and when producing the polymer, 100% by weight of component (A) is used. per department
From 0.1 to 100 parts by weight of organopolysiloxane prepolymer is used. If the organopolysiloxane component (B) is less than 0.1% by weight relative to component (A) in the polymer composition, it is difficult to stabilize the gas permeability of the resulting polymer composition over time. When it exceeds 100% by weight, the polymer composition becomes rubbery and its mechanical strength decreases. The composition of the present invention can be manufactured as a molded article having a certain shape, and can also be molded into a desired shape after manufacturing. Moreover, it can be made into a molded body alone, and it can also be molded as a composite material by molding it on a porous base material or the like depending on the purpose. There are no restrictions on the formability or shape of the molded product. For example, when used as a separation membrane, it is necessary to have a dense layer with substantially no pores. The composition alone can be used as a homogeneous membrane or a heterogeneous membrane with a dense layer, and can also be molded onto a porous flat membrane substrate, a porous hollow tube substrate, a porous hollow system substrate, etc. It can be used as a composite membrane. [Example] The present invention will be specifically described below with reference to Examples. In all other cases, parts are by weight. Example 1 1 part of tantalum pentachloride was dissolved in 160 parts of toluene,
1-trimethylsilyl-1-propyne 18 parts and 1-(1',1',3',3'-tetramethyl-
1',3'-disila-butyl)-1-propyne 2 parts were added and polymerized at 80°C for 3 hours, the reaction mixture was poured into excess methanol, the resulting polymer was precipitated and purified, and a copolymer with a weight average molecular weight of 1.6 x 10 ⁶ in terms of polystyrene was obtained. I got it.
In 100 parts of a 2% by weight toluene solution of this copolymer,
Dimethylpolysiloxane with vinyl groups at both ends, containing 0.21 mole of vinyl groups per 100g 0.80 parts dimethylpolysiloxane with SiH groups on both ends 0.17 parts, polyfunctional methylhydrodiene polysiloxane containing 1.54 moles of SiH groups in 100g 0.07 part was added and mixed. At this time, the weight fraction of the siloxane component to the substituted polyacetylene was 52.0.
% by weight, and the molar ratio of SiH groups/vinyl groups is 1.24
It is. As a platinum-based catalyst, a complex of chloroplatinic acid and vinylsiloxane (Pt concentration 2%) was added and mixed in an amount of 0.3% by weight based on the organohydrodiene polysiloxane component, and the resulting mixed solution was cast. Heat treatment was performed at 120°C for 1 hour to crosslink the silicone component, creating a homogeneous and transparent film with a thickness of 10 μm. No absorption due to Si-H bonds was observed in the IR spectrum of the obtained film.
Almost no Si-H bonds remained. Also
At 1030cm ^-1 to 1100cm ^-1 there is absorption due to siloxane bonds, at 1260cm ^-1 and around 800cm ^-1 there is Si-CH ₃ absorption.
Absorption due to binding was observed. When evaluating the gas permeability of this film, the oxygen permeability coefficient was found to be
Po ₂ = 3.5×10 ^-8 [cm ³ (STP)・cm/cm ²・sec・cm
Hg], ratio of oxygen and nitrogen permeability coefficients P _O2 /P _N2 = 2.7
It was hot. Meanwhile, this film was heated at 100℃ and humidity 100℃.
After heating and _humidifying for _{500 hours} under conditions of
It showed stable performance. The tensile strength of the film was 320 Kg/cm ² even after the above-mentioned heating and humidification treatment, and it was sufficiently resistant to thinning. Comparative Example 1 In Example 1, when the siloxane component was mixed with the substituted polyacetylene and no post-crosslinking was performed, the siloxane component was partially liberated on the film surface and a homogeneous film was not obtained, and the gas permeability deteriorated over time. There was no improvement in stability. Comparative Example 2 A film having a thickness of 10 μm was prepared by casting a toluene solution of the substituted polyacetylene copolymer obtained in Example 1. When we evaluated the gas permeability of this film, we found that the initial
P _O2 = 3×10 ^-7 [cm ³ (STP)・cm/cm ²・sec・cmHg]
However, the P _O2 /P _N2 = 1.6 was small, and after treatment for 500 hours at 100°C and 100% RH, the P _O2 = 1.0×10 ^-8 [cm ³ (STP) cm/
^cm2・sec・cmHg] and was not stable over time. Example 2 Using a substituted polyacetylene copolymer produced in the same manner as in Example 1, a polyfunctional organoleptic containing 0.70 mol of vinyl groups per 100 g was added to 100 parts of a 2% by weight toluene solution of this copolymer. vinyl siloxane 0.20 parts, polyfunctional methyl mercaptoethyl polysiloxane containing 0.5 mol of SiH groups in 100 g 0.30 parts of benzophenone in an amount of 0.3% by weight of the methylmercaptoethylpolysiloxane;
After mixing, the resulting mixed solution was cast and supported on a polysulfone porous membrane, and then irradiated with low-energy ultraviolet rays for 20 minutes to crosslink the silicone component and produce a composite film. When we measured the gas permeation performance of this film, we found that the oxygen permeation rate Q _O2 = 1.6×10 ^-4 [cm ³ (STP)/cm ²・sec・cm
Hg] under the conditions of 100℃ and 100%RH of wet film.
There was no change even after treatment for 500 hours. Example 3 500 mg of tantalum pentachloride was dissolved in 150 parts of toluene, and then 1-trimethylsilyl-1-propyne was dissolved. 15g of was added and polymerized at 80°C for 6 hours. The reaction mixture was precipitated in excess methanol and purified, giving the formula Polystyrene equivalent weight average molecular weight 7.0
13.5 g of x10 ⁵ polymer was obtained. Add vinyl groups to 100g of this polymer in 100 parts of a 2% by weight toluene solution.
0.30 part of dimethylpolysiloxane with vinyl groups on both ends containing 0.15 mol and dimethylpolysiloxane with SiH groups on both ends Add 0.25 parts of chloroplatinic acid and vinyl siloxane complex (Pt concentration 2) as a platinum catalyst and mix.
%) was added in an amount of 0.3% by weight based on the organohydrodiene polysiloxane component, and the resulting mixed solvent was cast, dried at 100° C. for 1 hour, and heat treated to crosslink the silicone component. A homogeneous and transparent film with a thickness of 7 μm was obtained, and when the gas permeation performance of this film was measured, the oxygen permeability coefficient P _O2 = 6.0 × 10 ^-8 [cm ³ (STP) cm/cm ² s cm
Hg], P _O2 /P _N2 = 2.3, and the tensile strength was 380 Kg/cm ² . Example 4 Using substituted polyacetylene produced in the same manner as in Example 3, a 2% by weight toluene solution of this polymer was prepared.
100 copies contain oxime-free silicone RTV (product name
After diluting 0.8 parts of KE-45 (manufactured by Shin-Etsu Chemical) in toluene and mixing, it was cast, dried and heat-treated at 100°C for 3 hours to crosslink the silicone component. A homogeneous and transparent film with a thickness of 10 μm was obtained, and had good gas permeability and film strength. Examples 5 to 7 Polymer compositions consisting of components (A) and (B) shown in Table 1 were produced under the conditions shown. The composition is summarized in Table 1. In both cases, it was possible to form a thin film with a thickness of 5 μm or less, which had good gas permeability and tensile strength, and was stable over time. [Table] [Table] [Effects of the Invention] The organopolysiloxane-substituted polyacetylene composition of the present invention has stable performance that does not change over time while maintaining the excellent gas permeability of substituted polyacetylene. . In addition, it is possible to provide a molded article that has high mechanical strength, is stable even when used under exposure to sunlight, and is resistant to decrease in strength due to ultraviolet rays or the like. The composition of the present invention has particularly high oxygen permeability,
It is suitable as a material for oxygen separation membranes, contact lenses, etc. Furthermore, since the composition has a greater affinity with organic solvents such as ethanol than with water, it is expected to be used as a liquid separation membrane to separate alcohol from a solution containing alcohol, or as a resist material. .

Claims (1)

[Claims] 1 (A) General formula () [In the formula, R ¹ represents a hydrogen atom or a lower alkyl group, and R ² , R ³ and R ⁴ may be the same or different and represent a hydrogen atom, a monovalent hydrocarbon group having 1 to 8 carbon atoms, or a silicon atom. Indicates the monovalent organic group contained. ]
A substituted polyacetylene compound having one or more structural units represented by (B) an organopolysiloxane in an amount of 0.1 to 100% by weight based on the substituted polyacetylene compound, and having an interpenetrating network structure. Organopolysiloxane-substituted polyacetylene composition. 2 1 of the structural unit represented by the above general formula ()
After mixing an organosiloxane prepolymer having intercrosslinking properties with a substituted polyacetylene compound having one or more species so as to form an organopolysiloxane in an amount of 0.1 to 100% by weight based on the substituted polyacetylene compound, the organosiloxane Consisting of crosslinking a prepolymer,
A method for producing an organopolysiloxane-substituted polyacetylene composition having an interpenetrating network structure.