JPH0367098B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for producing block copolymers, and its purpose is to

[Formula] A polyvinyl polymer, especially a polyvinyl ester polymer, having a group (X represents a halogen atom, R ¹ and R ² represent a hydrocarbon group) (hereinafter sometimes abbreviated as -SiX group), In particular, polyvinyl acetate polymer is used at the end.

[Formula] Polysiloxane having a group {Y is OM, OH, OR, X ¹
(M is an alkali metal, R is an alkyl group having 1 to 6 carbon atoms, X ¹ is a halogen atom), R ³ ,
R ⁴ represents a hydrocarbon group. }, (hereinafter sometimes abbreviated as YSi- group) to obtain a polyvinyl polymer, especially a polyvinyl ester polymer, especially a block copolymer of a polyvinyl acetate polymer and a polysiloxane. It is in. Polyvinyl polymers include inexpensive vinyl monomers, such as vinyl ester monomers such as vinyl acetate, vinyl propionate, and vinyl versatate, vinyl chloride, styrene, α-methylstyrene, methyl methacrylate, ethyl acrylate, It is obtained by monopolymerizing or copolymerizing butyl acrylate, butadiene, ethylene, etc. from radical polymers, and has good moldability as an organic material and good mechanical performance, so it is used in films, sheets, molded products, adhesives, etc. It is widely used in paints, etc. On the other hand, polysiloxanes such as polydimethylsiloxane, polyphenylmethylsiloxane, etc. are used as silicone resins such as silicone oil, silicone rubber, and silicone varnish, and are used in various applications by taking advantage of their properties such as heat resistance and water repellency based on their inorganic silicate bonds. used for purposes. We expected that by combining an inorganic material with the above-mentioned organic material, we would be able to create a new material that has the characteristics of both materials, and first we considered a method of blending both materials, but the compatibility of the two materials was poor.
Good materials could not be obtained. The present inventors further investigated the bonding method of both materials, and found that by reacting a specific polyvinyl polymer having a -SiX group at the end of the polymer with a specific polysiloxane having a YSi- group at the end, polyvinyl The present invention was achieved by discovering that a block copolymer containing both an organic component and an inorganic component in which a polysiloxane and a polysiloxane are combined can be obtained. The feature of the present invention is that a polyvinyl copolymer having a specific terminal group called -SiX group and a polysiloxane having a specific terminal group called YSi- group are used, and the terminal ends are reacted with each other. The block copolymer thus obtained has excellent hydrolysis resistance because the bonds between the polysiloxane and the polyvinyl polymer are carbon-silicon (C-Si) bonds.
Unlike the C-O-Si bond found in many siloxane derivatives, it does not easily hydrolyze or break the bond. Furthermore, this block copolymer has excellent adhesion properties as an adhesive between organic materials and inorganic materials such as metals, glass, and cement, and also has excellent adhesion properties between polyvinyl polymers and polysiloxane. The block component has a microphase-separated structure and has excellent mechanical performance when molded, so it has the advantage of being useful as a functional material such as a separation membrane. The present invention will be specifically explained below. The specific polyvinyl polymer having -SiX group at the end used in the present invention has the general formula R ¹ R ² Si(X)H
{R ¹ and R ² represent a hydrocarbon group, such as an aliphatic group (such as an alkyl group) or an aromatic hydrocarbon group having 1 to 10 carbon atoms. Preferred hydrocarbon groups include methyl and phenyl groups. Also
The hydrocarbons of R ¹ and R ² may be the same or different. X represents a halogen atom,
Examples include chlorine atom and bromine atom, with chlorine atom being preferred. } It can be easily obtained by radical polymerization of one or more olefinic unsaturated monomers in the coexistence of a dialkylhydrohalosilane. Through this polymerization, R ¹ R ² Si(X)H acts as a chain transfer agent,
At the end of polyvinyl polymer

A polymer having the formula [formula] attached thereto is obtained. That is, if an olefinic unsaturated monomer is represented by C=C,

A polymer having the structure of [Formula] is obtained. As the olefinic unsaturated monomer, any monomer or copolymerizable radical polymerizable monomer can be used. For example, vinyl esters such as vinyl acetate, vinyl propionate, vinyl formate, and vinyl versatate; acrylic acids such as methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, 2-hydroxyethyl methacrylate, and hexyl methacrylate. Acrylic monomers such as esters and methacrylic acid esters, acrylonitrile and methacrylonitrile, (meth)acrylamide monomers such as acrylamide, methacrylamide, and dimethylaminopropylmethacrylamide, vinyl chloride, vinyl bromide, and fluoride. Vinyl, halogenated vinyl monomers such as vinylidene chloride, styrene monomers such as styrene and α-methylstyrene, olefins and diolefins such as ethylene, butadiene, isoprene, and chloroprene, and almost no single radical polymerizability. but,
Examples of radical copolymerizable monomers include vinyl ethers such as methyl vinyl ether, butyl vinyl ether, and lauryl vinyl ether, and olefins such as isobutylene and octene. Vinyl esters, especially vinyl acetate, which have a large chain transfer constant to dialkylhydrohalosilanes, can efficiently obtain polymers with -SiX groups at the end. It is desirable to polymerize the monomers. Polymerization of the olefinic unsaturated monomer is carried out by a conventional radical polymerization method. That is, bulk polymerization, solution polymerization, and slurry polymerization are performed using radical polymerization initiators such as azobisisobutyronitrile, benzoyl peroxide, lauroyl peroxide, and diisopropoxy peroxydicarbonate, and radiation such as γ rays and electron beams. Polymerization is carried out by a known method such as a batch method, a semi-continuous method, or a continuous method. Since dialkylhydrohalosilane, which is a chain transfer agent, is consumed during polymerization, it is preferable to replenish it so that the concentration (relative to the monomer) in the polymerization system is constant. Polysiloxane with YSi- group at the end is
A polysiloxane with YSi- groups at one or both ends, the siloxane bond in the main chain is dimethyl,
Single or co-condensate of dialkylsiloxane such as diethyl or diphenylsiloxane,
Particularly preferred are polydimethylsiloxane and polydiphenylsiloxane. terminal

[Formula] The group Y is OM, OH, OR, X ¹ (M is an alkali metal such as Li, Na, K, etc., R is an alkyl group having 1 to 6 carbon atoms,
X ¹ represents a halogen atom such as a chlorine atom or a bromine atom. ), among which OM is preferred, and -ONa is the best. R ³ and R ⁴ represent a hydrocarbon group, such as an aliphatic (such as an alkyl group) or an aromatic hydrocarbon group having 1 to 10 carbon atoms. Preferred hydrocarbon groups include methyl, ethyl, propyl, and phenyl groups;
Among these, methyl and phenyl groups are preferred. Especially ^R3
and R ⁴ is a methyl group

[Formula] The group is preferred because of its high reactivity with the terminal end of the -SiX group. Further, the hydrocarbon groups of R ³ and R ⁴ may be the same or different. Directly if Y is OM

[Formula] By reacting with a polyvinyl compound having terminals, both terminals can be efficiently reacted and bonded, which is particularly preferable. In the case of OH, alkaline compounds such as sodium hydroxide, potassium hydroxide, sodium methoxide, ammonia, trimethylamine, diethylamine, and butylamine are eliminated by reaction to promote the reaction. Elimination, promotion, and neutralization of hydrogen halides. It is desirable to use it as an agent. When Y is OR or X, it is desirable to use water and the above-mentioned alkali compound together. The polyvinyl polymer having a specific -SiX group at the end of the present invention and the polysiloxane having a specific YSi group can be reacted by bringing the two into contact. In order to proceed with the reaction more smoothly, it is preferable to mix and contact both polymers more uniformly, and for this purpose, it is desirable to mix a solution in which both polymers are dissolved in an appropriate solvent. Solvents include benzene, toluene, tetrahydrofuran,
Those that can dissolve polyvinyl polymers and polysiloxanes, such as diethyl ether and chloroform, are preferred. The reaction temperature is appropriately selected at a temperature at which the reaction proceeds, but is preferably in the range of 10 to 80°C in view of the balance between suppression of side reactions and reaction rate. The ratio of the polyvinyl polymer and polysiloxane is appropriately selected depending on the performance of the target block copolymer, but the -
It is preferable that the molar ratio of the YSi group at the end of the polysiloxane to the SiX group is 1 or more because the reaction rate is high. When a polysiloxane having YSi- groups at both ends is used and the reaction is carried out under conditions where the molar ratio of YSi- groups/-SiX groups is 1 or more, leaving the unreacted YSi- group ends as is is not suitable for heat molding. For example, as shown in the formula (') below, R ⁵ R ⁶ R ⁷ SiX
{Here, R ⁵ , R ⁶ and R ⁷ represent a hydrocarbon group,
Examples include aliphatic (such as an alkyl group) or aromatic hydrocarbon group having 1 to 10 carbon atoms. Preferred hydrocarbon groups include methyl and phenyl groups. Further, R ⁵ , R ⁶ and R ⁷ may be the same or different. } is preferably stabilized by reacting a monofunctional silane low molecular weight compound with the remaining YSi- group. This reaction scheme is

[Formula] A polyvinyl acetate polymer having a group and both ends

An example of the production of a block copolymer by reaction of polydimethylsiloxane having the formula [Formula] is as follows. The degree of polymerization of the polyvinyl polymer and polysiloxane is appropriately selected depending on the composition and performance of the target block copolymer.
~10000 preferably 100-2000, polysiloxane 5
-5000, preferably 10-1000, from the viewpoint of the balance between the reactivity of the terminal group and the performance of the copolymer. The block copolymer obtained by the method of the present invention can be easily molded by heat melting or solution casting, and can be used in the form of films, sheets, fibers, and general molded products, and can also be used as adhesives, paints, etc. It can also be used as a processing agent such as a coating agent. For these various uses, block copolymers have the following properties: their heat resistance is higher than that of organic materials, their adhesive strength is high and effective as an adhesive between inorganic and organic materials, their water repellency is high, and they are resistant to oxygen. It is expected that the properties such as high permeability and high selectivity will be utilized and applied. Furthermore, the block copolymer of the present invention can be used not only alone, but also in combination with a polyvinyl polymer or polysiloxane, and the compatibility of both polymers can be improved by mixing the block copolymer. It is effective for Also, organic polymers other than polyvinyl polymers, glass fibers, mica,
It is also possible to use it in combination with inorganic fillers such as silica, clay, and calcium carbonate. The present invention will be specifically described below with reference to Examples, but is not limited to the Examples. Further, unless otherwise specified, parts indicate parts by weight, and degree of polymerization and molecular weight indicate average degree of polymerization and average molecular weight. Example 1 46.5 parts of vinyl acetate, 2.4 parts of dimethylchlorohydrosilane {(CH ₃ ) ₂ Si(Cl)H}, 0.27 parts of azobisisobutyronitrile and 50 parts by volume of benzene were placed in a polymerization tube, and the tube was purged with nitrogen. The container was sealed and polymerized by heating at 60° C. for 6 hours while stirring. After the polymerization was completed, benzene, unreacted vinyl acetate, and (CH ₃ ) ₂ Si(Cl)H were removed by vacuum distillation of the liquid in the polymerization tube, yielding 10 parts of a polymer. As a result of GPC analysis, the degree of polymerization was 128. This polymer is dehydrated and dried with benzene.
Dissolve in 100 parts by volume and add polydimethylsiloxane terminal sodium silanolate {degree of polymerization 18}
Add 48 parts of NaO-((CH ₃ ) ₂ Si-O)nNa} and 150 parts by volume of dry benzene, stir and react at room temperature for 1 hour.
Then trimethylchlorosilane {(CH ₃ ) ₃ SiCl}
10 parts by volume were added, and the mixture was further stirred for 1 hour. After removing the generated NaCl by filtering the reaction mixture,
After heating the liquid to distill off benzene, the remaining polymer was extracted and washed with n-hexane to remove the polydimethylsiloxane homopolymer, and then dried to obtain 12 parts of residual polymer. As a result of proton nuclear magnetic resonance (NMR) spectrum analysis of the polymer in deuterated chloroform at 60 MHz, in addition to the signal based on polyvinyl acetate, a signal from the methyl proton of polydimethylsiloxane was observed at 0.17 ppm, and from the signal intensity It was found that it contained 14 mol% of dimethylsiloxane units.
Furthermore, gel permeation chromatography (GPC) analysis of the produced polymer revealed a peak on the lower count side, that is, on the higher degree of polymerization side, than that of the polydimethylsiloxane used, and a peak at the position corresponding to polydimethylsiloxane. It wasn't recognized. That is, it was found that the peak on the high degree of polymerization side was based on a block copolymer of polyvinyl acetate and polydimethylsiloxane.
The NMR and GPC analysis results revealed that the produced polymer was a polyvinyl acetate-polydimethylsiloxane block polymer, containing 14 mol% of polydimethylsiloxane, and having a molecular weight of 12,000. A 20% solution of the obtained block copolymer dissolved in toluene was applied to a glass surface at a coating amount of 20 g/m ² , pressure-bonded with kraft paper, and left at room temperature for 2 days. The adhesive strength at 20°C and 70°C was measured by peeling at a width of 2 cm at 90° at a head speed of 100 mm/min and measuring the peel stress. As a result, 20℃ and
The adhesive strength at 70°C was 1000 g/cm and 900 g/cm, respectively, and it was found that the heat-resistant adhesive strength was particularly high. On the other hand, as a control, we measured the adhesive strength between glass and kraft paper using polyvinyl acetate with a molecular weight of 11,000, and found that the adhesive strength at 20°C was 110 g/cm, and 70
There was almost no adhesive strength at ℃. Example 2 93 parts of vinyl acetate, 3 parts of diphenylhydrochlorosilane, 0.4 parts of benzoyl peroxide, and 50 parts of tetrahydrofuran were placed in a polymerization tank, the atmosphere was replaced with nitrogen, and the mixture was heated and polymerized at 60°C for 5 hours while stirring in a nitrogen atmosphere. did. After a predetermined time, the contents of the polymerization tank were vacuum distilled to remove tetrahydrofuran, unreacted vinyl acetate, and diphenylhydrochlorosilane, yielding 18 parts of a polymer.
As a result of GPC analysis, the degree of polymerization was 490. 10 parts of this polymer was dissolved in 100 parts of dehydrated and dry tetrahydrofuran, and polydiphenylsiloxane terminal potassium silanolate (

[Formula] Degree of polymerization 12) Add 10 parts of a dry tetrahydrofuran solution containing 0.28 parts.
The mixture was added dropwise while stirring at 40°C, and after the dropwise addition was completed, the mixture was further stirred at 40°C for 2 hours. After filtering the reaction mixture to separate the formed crystals, the liquid was heated to distill off the tetrahydrofuran, leaving 10.5% of the remaining solid polymer.
I got a department. When this polymer was analyzed by GPC in the same manner as in Example 1, a large peak was observed on the higher molecular weight side than the reaction raw materials polyvinyl acetate polymer and polydiphenylsiloxane, and the molecular weight was 86,000. Further, as a result of NMR analysis, it was found that it contained 2 mol% of diphenylsiloxane units, and it was confirmed that a block copolymer of polyphenylsiloxane and polyvinyl acetate was obtained. Example 3 50 parts of vinyl acetate, 1.5 parts of diethylchlorohydrosilane {(C ₂ H ₅ ) ₂ Si(Cl)H}, 2,2'-azobis-
0.2 parts of 2,4-dimethylpareronitrile was placed in a polymerization tank, the atmosphere was replaced with nitrogen, and the mixture was heated and polymerized at 55° C. for 3 hours with stirring. After the polymerization is complete, unreacted vinyl acetate and diethylchlorohydrosilane are distilled off under vacuum.
Obtained 12 parts of polymer. This polymer has a polymerization degree of 405
It was found that it had diethylchlorosilane at the end. This polymer is dehydrated toluene 100%
It was dissolved in parts. This polymer solution was added dropwise to 200 parts of a toluene solution containing 90 parts of polydimethylsiloxane sodium silanolate at both ends (degree of polymerization: 350) while stirring. After the dropwise addition was completed, stirring was continued for 2 hours at 30°C, then 5 parts of a toluene solution containing 1 part of trimethylchlorosilane was added, and the mixture was further stirred for 1 hour. The liquid from which the precipitated crystals were separated was evaporated in vacuo, the remaining polymer was washed with petroleum ether, and then the polymer was dried. As a result, 15 parts of polymer were obtained.
As a result of analyzing the polymer using the same method as in Example 1,
It was found to be a block copolymer of polyvinyl acetate and polydimethylsiloxane containing 45 mol% of dimethylsiloxane units and having a molecular weight of 60,000. Prepare a 10% toluene solution of this polymer,
When it was cast and dried, a beautiful film was obtained, and the strength was high and excellent. On the other hand, as a control, a toluene solution of a mixture of polyvinyl acetate with a polymerization degree of 405 and polydimethylsiloxane (polymerization degree 350) such that the polydimethylsiloxane was 45 mol% was cast, and the dried film showed a phase separation of both polymers. However, it was sticky and had poor transparency. Example 4 Instead of vinyl acetate in Example 3, a mixed monomer of vinyl acetate and vinyl versatate in a molar ratio of 5:1 was used, and 0.25 parts of 2,2'-azobis-2,4-dimethylparellonitrile was added. Polymerization was carried out under the same conditions as in Example 3 except for the use of a copolymer of polyvinyl acetate and vinyl versatate in a molar ratio of 5:1.
I got 12 copies. The resulting polymer and the terminal sodium silanolate of polydimethylsiloxane were reacted in the same manner as in Example 3, and a poly(vinyl acetate/vinyl versatate) copolymer with a molecular weight of 50,000 and a dimethylsiloxane unit content of 55 mol% and polydimethyl 16 parts of a block copolymer with siloxane was obtained. Example 5 1,000 parts of vinyl acetate, 2 parts of azobisisobutyronitrile, and 35 parts of dimethylbromohydrosilane were placed in a pressure-resistant polymerization tank, the atmosphere was replaced with nitrogen, and then ethylene gas was added.
The mixture was sealed under pressure up to 50 kg/cm ² and polymerized at 60°C for 7 hours. After the polymerization was completed, the reaction solution was drained, and unreacted vinyl acetate, ethylene, and dimethylbromohydrosilane were distilled off under vacuum to obtain 195 parts of polymer. NMR,
Ethylene content 40% by GPC and chemical analysis
It was recognized as a vinyl acetate/ethylene copolymer having a mole% degree of polymerization of 300 and -Si( _CH3 ) _2Cl at the terminal.
A solution was prepared by dissolving 100 parts of this polymer in 500 parts of benzene. This solution was added dropwise with stirring to 1000 parts of a tetrahydrofuran solution kept at 40°C containing 500 parts of polydimethylsiloxane with ethoxy terminals (degree of polymerization 270) and 20 parts of a 10% aqueous solution of sodium hydroxide, and the mixture was further stirred for 1 hour. After this time, an additional 200 parts of a benzene solution containing 30 parts of trimethylchlorosilane was added dropwise and stirring continued for 1 hour. After separating the precipitated crystals, the liquid was evaporated in vacuo, and the remaining solids were thoroughly washed with hexane and dried to obtain 200 parts of polymer. As a result of polymer analysis, the molecular weight was 39,000.
It was a block copolymer of poly(vinyl acetate/ethylene) copolymer containing 51 mol% of dimethylsiloxane units and polydimethylsiloxane. Examples 6-8 Example 1 except that methyl methacrylate, ethyl acrylate, and styrene are used instead of vinyl acetate.
A vinyl polymer having -Si(CH ₃ ) ₂ Cl at the terminal was synthesized according to the method described in 1. I got a polymer. The reaction conditions and properties of the block copolymer obtained are shown in Tables 1 and 2.

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【table】

Claims (1)

[Claims] 1. A polyvinyl polymer having a [Formula] group (X is a halogen atom, R ¹ and R ² are hydrocarbon groups) at the end of the polymer, and a [Formula] group {Y are OM, OH, OR, X ¹ (M is an alkali metal,
R represents an alkyl group having 1 to 6 carbon atoms, and X ¹ represents a halogen atom. ), R ³ and R ⁴ represent a hydrocarbon group. } A method for producing a block copolymer of a polyvinyl polymer and a polysiloxane, the method comprising reacting the copolymer with a polysiloxane having the following properties. 2 A polyvinyl polymer having a [Formula] group at the end of the polymer is a polymer obtained by radical polymerization of an olefinic unsaturated monomer in the coexistence of a dialkylhydrohalosilane represented by R ¹ R ² Si(H)X. A method for producing a block copolymer according to claim 1. 3. The method for producing a block copolymer according to claim 1 or 2, wherein the polyvinyl polymer is a polyvinyl ester polymer. 4. The method for producing a block copolymer according to claim 1 or 2, wherein the polyvinyl polymer is a polyvinyl acetate polymer. 5. The method for producing a block copolymer according to claims 1 to 4, wherein the polysiloxane having a [formula] group at the end is a polydimethylsiloxane having a [formula] group at the end.