JP2009191207A - Method for producing diorganopolysiloxane having both terminals each blocked with (meth)acryloxypropyl group - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for efficiently producing a highly pure diorganopolysiloxane having both terminals each blocked with a (meth)acryloxypropyl group. <P>SOLUTION: The method for producing a diorganopolysiloxane having both terminals each blocked with a (meth)acryloxypropyl group is based on a hydrosilylation reaction between a diorganopolysiloxane having both terminals each blocked with a diorganohydrogensiloxy group and an allyl (meth)acrylate. In this method, a diorganopolysiloxane as a by-product wherein one terminal is blocked with a (meth)acryloxypropyl group while the other terminal is blocked with a (meth)acryloxy group, and a diorganopolysiloxane as a by-product having both terminals each blocked with a (meth)acryloxy group are hydrolyzed, and formed diorganopolysiloxanes having silanol terminals are condensed mutually. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

The present invention relates to a method for producing a bi-terminal (meth) acryloxypropyl group-blocked diorganopolysiloxane. In more detail, in the method for producing a diorganopolysiloxane having both ends (meth) acryloxypropyl group blocked by hydrosilylation reaction of both ends diorganohydrogensiloxy group-blocked diorganopolysiloxane and allyl (meth) acrylate, by-products Hydrolysis of diorganopolysiloxane with one end blocked with a (meth) acryloxypropyl group and the other end blocked with a (meth) acryloxy group, and both ends with a (meth) acryloxy group blocked diorganopolysiloxane In addition, the present invention relates to a method for producing a highly pure both-end (meth) acryloxypropyl group-blocked diorganopolysiloxane by dehydrating condensation of the generated silanol-terminated diorganopolysiloxanes. Further, the present invention relates to a method for producing a diorganopolysiloxane having a higher degree of polymerization at both terminals (meth) acryloxypropyl group blocked.

Both end (meth) acryloxypropyl group-blocked diorganopoly by the equilibrium polymerization of octamethylcyclotetrasiloxane in the presence of acid catalyst using 1,3-di (methacryloxypropyl) tetramethyldisiloxane as the end-blocking agent The manufacturing method of siloxane is well-known (for example, nonpatent literature 1).

The 1,3-di (methacryloxypropyl) tetramethyldisiloxane used in this production method is usually produced by hydrolysis of methacryloxypropyldimethylchlorosilane. Methacryloxypropyldimethylchlorosilane is produced by a hydrosilylation reaction of allyl methacrylate and dimethylhydrogenchlorosilane, but this reaction has a problem in production that gelation is very likely to occur. Distillation purification is essential to obtain high-purity products, but it is difficult to mass-produce industrially 1,3-di (methacryloxypropyl) tetramethyldisiloxane because it is very easy to gel during distillation. Was accompanied.

On the other hand, a method for producing a diorganopolysiloxane having both ends (meth) acryloxypropyl group blocked by hydrosilylation reaction between both ends diorganohydrogensiloxy group-blocked diorganopolysiloxane and allyl (meth) acrylate has also been reported. In this case, however, the reaction of propene and (meth) acryloxysiloxy group-blocked diorganopolysiloxane occurs as a by-product, and the desired end (meth) acryloxypropyl group-blocked diorganopolysiloxane in the reaction product occurs. There is a problem that the content of siloxane is about 50% (Non-patent document 2, Non-patent document 3, Patent document 1).

In order to prevent the above-mentioned side reaction, Patent Document 1 proposes a production method by hydrosilylation reaction of hydrogensiloxy group-blocked diorganopolysiloxane and allyloxyethyl methacrylate. However, allyloxyethyl methacrylate is difficult to obtain from allyl methacrylate, and since it has a high boiling point, it is difficult to remove it under heating and reduced pressure after the hydrosilylation reaction.

Gol'din, G.S .; Muzychenko, T.A .; Averbakh, K.O .; Fedotov, N.S .; Mironov, V.F. USSR. Zhurnal Obshchei Khimii (1975), 45 (11), 2451-4) Speier, J.L.et al., J.Am.Chem.Soc., 79, 1974 (1957) Ryan, J.W.et al., J.Am.Chem.Soc., 82,3601 (1960) Japanese Patent Laid-Open No. 61-50988

For this reason, as a result of earnest research to develop a novel production method free from such problems, the present inventor has produced high-purity both end (meth) acryloxypropyl group-capped diorganopolysiloxane with high productivity. Invented a novel production method capable of
The object of the present invention is to provide a by-product (meth) acryloxy group-capped diorgano- gen by a hydrosilylation reaction between a readily available allyl (meth) acrylate and a diorganohydrogensiloxy group-capped diorganopolysiloxane having both ends. An object of the present invention is to provide a method for producing a highly pure both-end (meth) acryloxypropylsiloxy group-capped diorganopolysiloxane with high productivity by effectively using polysiloxane. It is another object of the present invention to provide a method for producing a bi-terminal (meth) acryloxypropyl group-capped diorganopolysiloxane having a higher degree of polymerization with high productivity.

The said subject is achieved by the following manufacturing method.
[1] Structural formula (1): H (R) ₂ SiO [(R ¹ ) ₂ SiO] _n Si (R) ₂ H
(Wherein R is a monovalent hydrocarbon group having no aliphatic unsaturated bond, R ¹ is a monovalent hydrocarbon group having no aliphatic unsaturated bond, and n is 0 to 50) Diorganohydrogensiloxy group-blocked diorganopolysiloxane and formula (2): CH ₂ = C (R ² ) COOCH ₂ CH = CH ₂
(Wherein, R ² is a hydrogen atom or a methyl group) and hydrosilylation reaction with allyl (meth) acrylate represented by
Structural formula (3): CH ₂ = C (R ² ) COOCH ₂ CH ₂ CH ₂ (R) ₂ SiO [(R ¹ ) ₂ SiO] _n Si (R) ₂ CH ₂ CH ₂ CH ₂ OOC (R ² ) C = CH ₂
(Wherein R, R ¹ , R ² and n are as defined above), in the method for producing a diorganopolysiloxane having both ends (meth) acryloxypropyl group blocked,
(1) By-product structural formula (4):
CH ₂ = C (R ² ) COOCH ₂ CH ₂ CH ₂ (R) ₂ SiO [(R ¹ ) ₂ SiO] _n Si (R) ₂ OOC (R ² ) C = CH ₂
(Wherein R, R ¹ , R ² , and n are as defined above) and one end (meth) acryloxy group-capped diorganopolysiloxane and structural formula (5):
CH ₂ = C (R ² ) COO (R) ₂ SiO [(R ¹ ) ₂ SiO] _n Si (R) ₂ OOC (R ² ) C = CH ₂
(Wherein R, R ¹ , R ² and n are as defined above) (2) Structural formula (6) produced by hydrolyzing a diorganopolysiloxane having both ends (meth) acryloxy group blocked: CH ₂ = C (R ² ) COOCH ₂ CH ₂ CH ₂ (R) ₂ SiO [(R ¹ ) ₂ SiO] _n Si (R) ₂ OH
(Wherein R, R ¹ , R ² , and n are as defined above) and a single-end silanol-blocked diorganopolysiloxane represented by the structural formula (7): HO (R) ₂ SiO [(R ¹ ) ₂ SiO] _n Si (R) ₂ OH
(In the formula, R, R ¹ , R ² and n are as defined above) Condensed diorganopolysiloxane having both ends silanol groups blocked by the both ends (meth) acryloxy represented by Structural Formula (3) A method for producing a diorganopolysiloxane having both ends (meth) acryloxypropyl groups blocked, which is converted into a propyl group-blocked diorganopolysiloxane.
[2] The production method according to [1], wherein the equivalent ratio of allyl group / silicon atom-bonded hydrogen atom is 1 or more in the hydrosilylation reaction.
[3] The hydrosilylation reaction, the hydrolysis reaction of the hydrosilylation reaction product, and the dehydration condensation reaction of both end silanol-blocked diorganopolysiloxane are carried out in the presence of a polymerization inhibitor and / or an organic solvent. The production method according to [1] or [2].
[4] A hydrosilylation reaction is carried out in the presence of a hydrosilylation reaction catalyst, a polymerization inhibitor and, if necessary, an organic solvent. In this case, allyl (meth) acrylate, a hydrosilylation reaction catalyst, a polymerization inhibitor, and an organic solvent as required. The production method according to [1] or [2], wherein both ends of the diorganohydrogensiloxy group-capped diorganopolysiloxane are put into the mixture.

[5] The production method according to any one of [1] to [4], wherein a diorganohydrogenacyloxysilane coexists in the hydrosilylation reaction.
[6] The production method according to [5], wherein the diorganohydrogenacyloxysilane is dimethylhydrogenacetoxysilane.

[7] The hydrosilylation reaction product is hydrolyzed in the presence of an alkali metal hydroxide or carbonate, or an alkaline earth metal hydroxide or carbonate. [1] The manufacturing method as described in.
[8] The production method according to [1] or [7], wherein the dehydration condensation reaction of the silanol group-blocked diorganopolysiloxane is performed in the presence of an acid catalyst.

[9] Both ends diorganohydrogensiloxy group-blocked diorganopolysiloxane is both ends dimethylhydrogensiloxy group-blocked dimethylpolysiloxane, allyl (meth) acrylate is allyl methacrylate, both ends (meth) The production method according to [1] or [6], wherein the acryloxypropyl group-capped diorganopolysiloxane is a both-end (meth) acryloxypropyl group-capped dimethylpolysiloxane.

The above object is further achieved by the following production method.
[10] Both end (meth) acryloxypropyl group-blocked diorganopolysiloxane and diorganocyclooligosiloxane and / or both ends silanol group-blocked diorganopolysiloxane obtained by the production method of [1] are used as an acid catalyst. A process for producing a diorganopolysiloxane having both ends (meth) acryloxypropyl group-blocked diorganopolysiloxane having an increased degree of polymerization, characterized in that equilibration copolymerization is carried out.
[11] Both ends (meth) acryloxypropyl group-blocked diorganopolysiloxane is both ends (meth) acryloxypropyl group-blocked dimethylpolysiloxane, diorganocyclooligosiloxane is dimethylcyclooligosiloxane, both ends silanol [10] The production method according to [10], wherein the blocked diorganopolysiloxane is a silanol group blocked dimethylpolysiloxane at both ends.

According to the production method of the present invention, both ends (meth) of high purity can be obtained by hydrosilylation reaction between allyl (meth) acrylate and diorganohydrogensiloxy group-blocked diorganopolysiloxane which can be easily obtained. Acryloxypropyl group-blocked diorganopolysiloxane can be produced with good productivity. Also, the obtained terminal (meth) acryloxypropyl group-capped diorganopolysiloxane is polymerized using an end-capping agent to produce a higher degree of polymerization (terminal) (meth) acryloxypropyl group-capped diorganopolysiloxane. Can be manufactured well.

The production method of the present invention has the following structural formula (1): H (R) ₂ SiO [(R ¹ ) ₂ SiO] _n Si (R) ₂ H
(Wherein R is a monovalent hydrocarbon group having no aliphatic unsaturated bond, R ¹ is a monovalent hydrocarbon group having no aliphatic unsaturated bond, and n is 0 to 50) Diorganohydrogensiloxy group-blocked diorganopolysiloxane and formula (2): CH ₂ = C (R ² ) COOCH ₂ CH = CH ₂
(Wherein R ² is a hydrogen atom or a methyl group) and hydrosilylation reaction with allyl (meth) acrylate represented by
Structural formula (3): CH ₂ = C (R ² ) COOCH ₂ CH ₂ CH ₂ (R) ₂ SiO [(R ¹ ) ₂ SiO] _n Si (R) ₂ CH ₂ CH ₂ CH ₂ OOC (R ² ) C = CH ₂
(Wherein R, R ¹ , R ² and n are as defined above), in the method for producing a diorganopolysiloxane having both ends (meth) acryloxypropyl group blocked,
(1) By-product structural formula (4):
CH ₂ = C (R ² ) COOCH ₂ CH ₂ CH ₂ (R) ₂ SiO [(R ¹ ) ₂ SiO] _n Si (R) ₂ OOC (R ² ) C = CH ₂
(Wherein R, R ¹ , R ² , and n are as defined above) and one end (meth) acryloxy group-capped diorganopolysiloxane and structural formula (5):
CH ₂ = C (R ² ) COO (R) ₂ SiO [(R ¹ ) ₂ SiO] _n Si (R) ₂ OOC (R ² ) C = CH ₂
(Wherein R, R ¹ , R ² , n are as defined above) and hydrolyzing a diorganopolysiloxane blocked at both ends (meth) acryloxy group blocked,
(2) Generated structural formula (6): CH ₂ = C (R ² ) COOCH ₂ CH ₂ CH ₂ (R) ₂ SiO [(R ¹ ) ₂ SiO] _n Si (R) ₂ OH
(Wherein R, R ¹ , R ² , and n are as defined above) and a single-end silanol-blocked diorganopolysiloxane represented by the structural formula (7): HO (R) ₂ SiO [(R ¹ ) ₂ SiO] _n Si (R) ₂ OH
(In the formula, R, R ¹ , R ² and n are as defined above) By condensing a diorganopolysiloxane having both ends silanol groups blocked, the both ends (meth) represented by the structural formula (3) It is characterized by being converted to acryloxypropyl group-blocked diorganopolysiloxane.

Structural formula (1): H (R) ₂ SiO [(R ¹ ) ₂ SiO] _n Si (R) ₂ H
(Wherein R is a monovalent hydrocarbon group having no aliphatic unsaturated bond, R ¹ is a monovalent hydrocarbon group having no aliphatic unsaturated bond, and n is 0 to 50) Diorganohydrogensiloxy group-blocked diorganopolysiloxane has the structural formula (3):
CH ₂ = C (R ² ) COOCH ₂ CH ₂ CH ₂ (R) ₂ SiO [(R ¹ ) ₂ SiO] _n Si (R) ₂ CH ₂ CH ₂ CH ₂ OOC (R ² ) C = CH ₂
(Wherein R, R ¹ , R ² , and n are as defined above) (terminal) (meth) acryloxypropyl groups (that is, acryloxypropyl groups or methacryloxypropyl groups) blocked diorganopolysiloxane Is the main raw material for manufacturing. Usually, it is produced by an equilibration polymerization method. Therefore, n in the structural formula (1) is an average value.
Formula (2): CH ₂ = C (R ² ) COOCH ₂ CH = CH ₂
(Wherein R ² is a hydrogen atom or a methyl group) allyl groups of (meth) acrylates (that is, allyl acrylate or allyl methacrylate) are bonded to both ends of the molecular chain by hydrosilylation reaction. Add to hydrogen-bonded silicon atom. As a result, a (meth) acryl propoxy group represented by the formula: CH ₂ = C (R ² ) COOCH ₂ CH ₂ CH ₂ is bonded to the silicon atom at the end of the diorganopolysiloxane.

In the structural formula (1), R is a monovalent hydrocarbon group that does not have the same or different aliphatic unsaturated bond, that is, a monovalent hydrocarbon group that does not have an aliphatic unsaturated bond. Specifically, alkyl groups such as methyl group, ethyl group, propyl group, butyl group, pentyl group and hexyl group; cycloalkyl groups such as cyclopentyl group and cyclohexyl group; aryl groups such as phenyl group, tolyl group and xylyl group; Examples include aralkyl groups such as benzyl group and phenethyl group. From the viewpoint of ease of production, an alkyl group having 8 or less carbon atoms and then a phenyl group are preferable, and a methyl group is most preferable among alkyl groups having 8 or less carbon atoms.

In the structural formula (1), R ¹ is a monovalent hydrocarbon group that does not have the same or different aliphatic unsaturated bond. Specifically, alkyl groups such as methyl group, ethyl group, propyl group, butyl group, pentyl group and hexyl group; cycloalkyl groups such as cyclopentyl group and cyclohexyl group; aryl groups such as phenyl group, tolyl group and xylyl group; Examples include aralkyl groups such as benzyl group and phenethyl group. From the viewpoint of ease of production, it is preferred that ^one of R ¹ bonded to the same silicon atom is a methyl group, and the other of R ¹ is an alkyl group or phenyl group having 8 or less carbon atoms. Of the 8 or less alkyl groups, those that are methyl groups are most preferred.

As the main chain in the structural formula (1), dimethylpolysiloxane, methylalkyl (excluding methyl) polysiloxane, methylphenylpolysiloxane, dimethylsiloxane / methylalkyl (excluding methyl) siloxane copolymer, dimethylsiloxane / methylphenylsiloxane copolymer Is exemplified. The same applies to the main chain in the structural formula (3).

N in the structural formula (1) is 0-50. In order to suppress the radical polymerization reaction of the (meth) acryloxy group generated as a side reaction when adding allyl (meth) acrylate to the hydrogen atom-bonded silicon atoms at both ends of the molecular chain, it is preferable that n is large. However, when hydrolyzing the terminal (meth) acryloxy group-capped diorganopolysiloxane, which is a by-product after the hydrosilylation reaction, the reactivity of the hydrolysis reaction is improved, and the organic layer and water are added after the hydrolysis reaction. In order to improve the separation from the layer, n is preferably smaller. Considering these, it is 0 or more and 50 or less, and preferably 0 or more and 20 or less.

Hydrosilylation reaction catalyst is used to hydrosilylate diorganopolysiloxane blocked with diorganohydrogensiloxy group blocked at both ends represented by structural formula (1) and allyl (meth) acrylate represented by formula (2) .
The catalyst is not particularly limited as long as it is a catalyst for hydrosilylation reaction, and examples thereof include Group VIII transition metals such as platinum, ruthenium, rhodium, palladium, iridium, nickel, and compounds thereof. Specific examples of such compounds include Group VIII transition metal chloro complexes, olefin complexes, aldehyde complexes, ketone complexes, phosphine complexes, sulfide complexes, nitrile complexes, and the like.

Of these, platinum-based catalysts are preferred, and zero-valent platinum olefin complexes, zero-valent platinum vinyl siloxane complexes, divalent platinum olefin complexes, aldehyde complexes or ketone complexes, divalent platinum halides, chloroplatinic acid, Examples include carbon-supported platinum fine powder, silica-supported platinum fine powder, and platinum black. Among these, in terms of reaction activity, 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex of platinum, 1,3-divinyl-1,1,3,3- Tetramethyldisiloxane complexes, platinum olefin complexes, and chloroplatinic acid are more preferred.

In order to prevent polymerization reaction of (meth) acryloxy group which occurs as a side reaction in this hydrosilylation reaction stage, polymerization inhibitors such as phenothiazine, hindered phenol compounds, amine compounds and quinone compounds are added to the reaction system. It is preferable to keep it. The kind and amount of such a polymerization inhibitor are particularly limited as long as the addition of them can prevent the polymerization reaction of (meth) acryloxy groups, that is, acryloxy groups or methacryloxy groups, without hindering the progress of the hydrosilylation reaction. Not. In order to suppress this polymerization reaction, the hydrosilylation reaction is preferably performed in a nitrogen gas atmosphere containing a trace amount of oxygen gas.

This hydrosilylation reaction can be performed without a solvent, but can also be performed in the presence of a solvent. Solvents that can be used include aromatic hydrocarbons such as benzene, toluene and xylene; aliphatic hydrocarbons such as hexane, heptane and cyclohexane; ethers such as tetrahydrofuran and diethyl ether; ketones such as acetone and methyl ethyl ketone; Examples thereof include carboxylic acid esters such as butyl acetate.

Equivalent ratio of allyl group of allyl (meth) acrylate represented by formula (2) and hydrosilyl group of diorganohydrogensiloxy group-blocked diorganopolysiloxane represented by structural formula (1) ([allyl] / [SiH]) is very preferably 1.0 or more. When this value is less than 1.0, diorganopolysiloxane containing a hydrosilyl group at one end and a (meth) acryloxypropyl group at the other end is mixed. Even if there is too much allyl (meth) acrylate, since it will be useless, 1.1-1.3 are preferable for the applicable amount ratio.
To ensure that allyl groups of allyl (meth) acrylate are added to the hydrosilyl groups at both ends of the diorganohydrogensiloxy group-blocked diorganopolysiloxane, the (meth) acrylic is in excess of the stoichiometric amount. A diorganohydrogensiloxy group-capped diorganopolyol represented by the structural formula (1) is prepared by preparing a solution comprising an acid allyl, a polymerization inhibitor, a hydrosilylation reaction catalyst, and, if necessary, stirring. A method of dropping siloxane is desirable.

This is because when a hydrosilylation catalyst is added to a mixture of diorganohydrogensiloxy group-blocked diorganopolysiloxane and allyl (meth) acrylate, the hydrosilylation reaction starts at once, making it difficult to control the reaction temperature. This is because it is extremely dangerous and a side reaction (meth) acryloxy group polymerization reaction is likely to occur, and the reaction system is easily gelled. In addition, when allyl (meth) acrylate was added dropwise to a mixture of diorganohydrogensiloxy group-blocked diorganopolysiloxane and hydrosilylation reaction catalyst while heating, it was by-produced by a depropenation reaction as a side reaction. This is because diorganohydrogensiloxy group-blocked diorganopolysiloxane is added to propene, and propyl group-blocked diorganopolysiloxane is by-produced, which is not preferable.

The (meth) acryloxy group-blocked diorganopolysiloxane generated as a by-product in this hydrosilylation reaction is converted to the corresponding silanol group in the subsequent hydrolysis reaction, and the final production by this production method It is not introduced into things. Therefore, by suppressing side reactions in this hydrosilylation reaction as much as possible and reducing the production rate of (meth) acryloxy group-capped diorganopolysiloxane, the yield of both end (meth) acryloxy group-capped diorganopolysiloxane is improved. Is important for.

As an additive for this purpose, diorganohydrogenacyloxysilane as described in JP-A-2000-256374, particularly, the formula (8): R ³ ₂ Si (H) OOCR ⁴ (wherein R ³ is an alkyl group, a phenyl group or an alkoxy group, and R ⁴ is a hydrogen atom, an alkyl group, a haloalkyl group or a phenyl group), and diorganohydrogenacyloxysilane is effective.

Specific examples include diorganohydrogenformyloxysilane, diorganohydrogenacetoxysilane, diorganohydrogenpropionyloxysilane, diorganohydrogenbutyryloxysilane, diorganohydrogenlauroyloxysilane, diorganohydrogen stea Examples include leuoxysilane, diorganohydrogenbenzoyloxysilane, diorganohydrogenchloroacetoxysilane, diorganohydrogendichloroacetoxysilane, diorganohydrogentrifluoroacetoxysilane, and diorganohydrogenbenzoyloxysilane.

More specifically, as the diorganohydrogenformyloxysilane, for example, dimethylhydrogenformyloxysilane, diethylhydrogenformyloxysilane, methylphenylhydrogenformyloxysilane, methylmethoxyhydrogenformyloxysilane, methylethoxyhydro There are genformyloxysilane, methylisopropoxyhydrogenformyloxysilane, and diphenylhydrogenformyloxysilane.

Examples of the diorganohydrogenacetoxysilane include dimethylhydrogenacetoxysilane, diethylhydrogenacetoxysilane, methylphenylhydrogenacetoxysilane, methylmethoxyhydrogenacetoxysilane, methylethoxyhydrogenacetoxysilane, methylisopropoxyhydrogenacetoxysilane And diphenylhydrogenacetoxysilane.

Examples of diorganohydrogenpropionyloxysilane include dimethylhydrogenpropionyloxysilane, diethylhydrogenpropionyloxysilane, methylphenylhydrogenpropionyloxysilane, methylmethoxyhydrogenpropionyloxysilane, methylethoxyhydrogenpropionyloxysilane, methyl There are isopropoxyhydrogenpropionyloxysilane and diphenylhydrogenpropionyloxysilane.

Examples of the diorganohydrogenbutyryloxysilane include dimethylhydrogenbutyryloxysilane, diethylhydrogenbutyryloxysilane, methylphenylhydrogenbutyryloxysilane, methylmethoxyhydrogenbutyryloxysilane, and methylethoxyhydrogen. There are butyryloxysilane, methylisopropoxyhydrogenbutyryloxysilane, diphenylhydrogenbutyryloxysilane.

In addition, examples of the diorganohydrogenlauroyloxysilane include dimethylhydrogenlauroyloxysilane, methylphenylhydrogenlauroyloxysilane, diphenylhydrogenlauroyloxysilane, methylmethoxyhydrogenlauroyloxysilane, methyl There is ethoxyhydrogen lauroyloxysilane.

Examples of the diorganohydrogen stearoyloxy silane include dimethyl hydrogen stearoyloxy silane, methylphenyl hydrogen stearoyloxy silane, diphenyl hydrogen stearoyloxy silane, methyl methoxy hydrogen stearoyloxy silane, methyl ethoxy hydrogen. There is stearoyloxysilane.

Examples of the diorganohydrogenbenzoyloxysilane include dimethylhydrogenbenzoyloxysilane, methylphenylhydrogenbenzoyloxysilane, diphenylhydrogenbenzoyloxysilane, methylmethoxyhydrogenbenzoyloxysilane, and methylethoxyhydrogenbenzoyloxysilane. .

Examples of the diorganohydrogenchloroacetoxysilane include dimethylhydrogenchloroacetoxysilane, methylphenylhydrogenchloroacetoxysilane, diphenylhydrogenchloroacetoxysilane, methylmethoxyhydrogenchloroacetoxysilane, and methylethoxyhydrogenchloroacetoxysilane. .

Examples of diorganohydrogendichloroacetoxysilane include dimethylhydrogendichloroacetoxysilane, methylphenylhydrogendichloroacetoxysilane, diphenylhydrogendichloroacetoxysilane, methylmethoxyhydrogendichloroacetoxysilane, methylethoxyhydrogendichloroacetoxysilane, methyl Examples include phenyl hydrogen trichloroacetoxy silane, diphenyl hydrogen trichloroacetoxy silane, methyl methoxy hydrogen trichloroacetoxy silane, and methyl ethoxy hydrogen trichloroacetoxy silane.

Examples of the diorganohydrogen trifluoroacetoxy silane include dimethyl hydrogen trifluoroacetoxy silane, methylphenyl hydrogen trifluoroacetoxy silane, diphenyl hydrogen trifluoroacetoxy silane, methyl methoxy hydrogen trifluoroacetoxy silane, and methyl ethoxy hydrogen trifluoroacetoxy silane. .

Examples of the diorganohydrogenbenzoyloxysilane include dimethylhydrogenbenzoyloxysilane, methylphenylhydrogenbenzoyloxysilane, diphenylhydrogenbenzoyloxysilane, methylmethoxyhydrogenbenzoyloxysilane, and methylethoxyhydrogenbenzoyloxysilane. .

The above additive may be added to the diorganopolysiloxane having both ends diorganohydrogensiloxy group blocked by the structural formula (1), or added to allyl (meth) acrylate represented by the formula (2). Or may be added to both. The amount added is not particularly limited as long as it is an appropriate amount for exhibiting the effect. However, since the effect cannot be exhibited in a small amount, specifically, it is preferably 0.1 mol% or more and 50 mol% or less, preferably 1 mol% or more and 50 mol% or less with respect to the number of moles of allyl (meth) acrylate used. More preferably, it is not more than mol%.

Diorganohydrogenacyloxysilane itself undergoes a hydrosilylation reaction with allyl (meth) acrylate to produce (meth) acryloxypropyl diorganoacyloxysilane. However, it is converted to (meth) acryloxypropyl diorganosilanol in the next hydrolysis step, and is taken into diorganopolysiloxane having both ends (meth) acryloxypropyl group blocked in the final condensation reaction step. However, it does not reduce the purity of the product.

Hydrosilyl reaction temperature is 30-120 degreeC normally, Preferably it is 40-80 degreeC. This is because the polymerization reaction of the methacryloxy group tends to occur at a temperature higher than 120 ° C., and the hydrosilylation reaction itself is remarkably slow at a temperature lower than 30 ° C. In this reaction, a low boiling point product such as excess unreacted allyl (meth) acrylate and the used organic solvent are removed from the reaction mixture obtained as described above under heating and reduced pressure to produce a hydrosilylation reaction product. Is isolated. In order to prevent the polymerization reaction of the (meth) acryloxypropyl group that occurs as a side reaction in this heating and decompression step, it is preferable to add a polymerization inhibitor as described above to the reaction system.

The hydrosilylation reaction product obtained as described above is mainly composed of a bi-terminal (meth) acryloxypropyl group-blocked diorganopolysiloxane represented by the structural formula (1) and a single terminal represented by the structural formula (4). From a diorganopolysiloxane blocked with a (meth) acryloxypropyl group and the other end blocked with a (meth) acryloxy group, a (meth) acryloxy group blocked diorganopolysiloxane represented by the structural formula (5) Become.
When diorganohydrogenacyloxysilane is added as a selectivity improver for the hydrosilylation reaction, (meth) acryloxypropyl diorganoacyloxysilane is also generated in addition to the above.

In order to remove the (meth) acryloxy group from the hydrosilylation reaction product, one end represented by the structural formula (4) is blocked with a (meth) acryloxypropyl group and the other end is a (meth) acryloxy group. Hydrolysis reaction of the blocked diorganopolysiloxane and the both end (meth) acryloxy group blocked diorganopolysiloxane represented by the structural formula (5) is carried out.

At that time, the hydrosilylation reaction product is preferably hydrolyzed in the presence of an alkali metal hydroxide or carbonate or an alkaline earth metal hydroxide or carbonate. Specific examples of the alkali metal hydroxide include lithium hydroxide, sodium hydroxide, potassium hydroxide, and cesium hydroxide. Specific examples of the alkaline earth metal hydroxide include calcium hydroxide, hydroxide Magnesium is exemplified. Specific examples of the alkali metal carbonate include sodium hydrogen carbonate, sodium carbonate, potassium carbonate and lithium carbonate, and specific examples of the alkaline earth metal carbonate include magnesium carbonate, calcium carbonate and barium carbonate. Is exemplified.

These alkali metal hydroxides or carbonates, or alkaline earth metal hydroxides or carbonates are 1 to 3 with respect to the (meth) acryloxysiloxy group produced by the side reaction during the hydrosilylation reaction. It is preferable to coexist with 5 times equivalent, and more preferably coexist with 1 to 3 times equivalent.
Further, as a catalyst for promoting this hydrolysis reaction, an amine compound such as triethylamine, pyridine, piperidine, quinoline, diethylhydroxylamine and the like may be present.

In order to prevent the polymerization reaction of the (meth) acryloxy group that occurs as a side reaction in this hydrolysis reaction stage, it is preferable that a polymerization inhibitor as described above is present in the reaction system.

This hydrolysis reaction proceeds even in the absence of a solvent, but aliphatic hydrocarbons such as hexane, heptane and cyclohexane; aromatic hydrocarbons such as toluene and xylene; ethers such as diethyl ether and tetrahydrofuran; chloroform and tetrachloride You may carry out in presence of organic solvents, such as carbon, chlorinated hydrocarbons, such as a methylene chloride.

The hydrolysis reaction temperature is preferably −10 to 100 ° C., and more preferably 0 to 80 ° C.

The progress of the hydrolysis reaction can be confirmed by disappearance of the (meth) acryloxysiloxy group by an analytical method such as nuclear magnetic resonance (NMR) analysis, but when the molecular weight of the hydrosilylation reaction product is relatively small. Can also be confirmed by gas chromatography.

The above hydrolysis reaction is performed in the presence of a strong acid catalyst such as hydrochloric acid, sulfuric acid, trifluoroacetic acid, p-toluenesulfonic acid, trifluoromethanesulfonic acid, etc., and (meth) acrylic acid by-produced, that is, acrylic acid or methacrylic The acid may be neutralized with the above alkali metal hydroxide or carbonate, or alkaline earth metal hydroxide or carbonate. The (meth) acrylic acid by-produced by this operation is converted into the corresponding salt, transferred from the organic layer to the aqueous layer, and can be easily removed by a liquid separation operation.

The hydrolyzed product obtained as described above has a structural formula (6) in addition to the bi-terminal (meth) acryloxypropyl group-blocked diorganopolysiloxane represented by the structural formula (3) as the target product. It consists of a single-end silanol-blocked diorganopolysiloxane shown and a bi-terminal silanol-blocked diorganopolysiloxane represented by the structural formula (7). When diorganohydrogenacyloxysilane is added as a selectivity improver for the hydrosilylation reaction, (meth) acryloxypropyl diorganosilanol is also generated in addition to the above compound.

Dehydration condensation reaction of silanol groups to remove silanol groups in one-end silanol-blocked diorganopolysiloxane represented by structural formula (6) and both-end silanol-blocked diorganopolysiloxane represented by structural formula (7) I do. In order to promote this dehydration condensation reaction, an acid catalyst is usually added. As the acid catalyst, strong acids such as methanesulfonic acid, p-toluenesulfonic acid, trifluoromethanesulfonic acid, sulfuric acid and hydrochloric acid are preferred.

In order to prevent the polymerization reaction of the (meth) acryloxy group that occurs as a side reaction in this condensation reaction stage, it is preferable that a polymerization inhibitor as described above coexists in the reaction system.

This condensation reaction proceeds even in the absence of a solvent, but it is preferably carried out in a non-reactive organic solvent that forms an azeotrope with water. Water produced as a by-product by heating under normal pressure or reduced pressure is azeotroped. It is preferable to dehydrate. Specific examples of the organic solvent that can be used include aliphatic hydrocarbons such as hexane, heptane, and cyclohexane; and aromatic hydrocarbons such as toluene and xylene.

The hydrolysis reaction temperature is preferably −10 to 100 ° C., more preferably 30 to 80 ° C.

The progress of the condensation reaction can be monitored by monitoring the amount of condensed water produced. Further, disappearance of silanol groups may be monitored (monitored) by NMR analysis. If the hydrolyzate has a relatively small molecular weight, it can also be monitored by gas chromatography.

After the condensation reaction, a basic compound is added to the reaction mixture to neutralize the acid catalyst used in the condensation reaction.
As basic compounds therefor, basic inorganic salts such as sodium bicarbonate, sodium carbonate and potassium carbonate; organic bases such as triethylamine, tributylamine, ammonia and pyridine can be used. From the viewpoint of filterability and safety of the produced salt, sodium hydrogen carbonate or sodium carbonate is desirable. The amount of these basic compounds used is not less than the neutralization equivalent, and is exemplified by 1 equivalent to 10 equivalents relative to the acid catalyst used in the condensation reaction. In this case, the temperature and time of the neutralization reaction are not particularly limited.

After the neutralization reaction, the produced neutralized salt and excess basic compound are separated by filtration, and then the low boiling point substances and the solvent in the filtrate are removed under heating and reduced pressure. Alternatively, the generated neutralized salt and excess basic compound are removed by washing with water, and then the low-boiling substances and solvent are removed from the organic layer under heating and reduced pressure to block the desired both-end (meth) acryloxypropyl group. Diorganopolysiloxane can be obtained.

In order to prevent the polymerization reaction of the (meth) acryloxy group that occurs as a side reaction in this heating and depressurization stage, it is preferable that a polymerization inhibitor as described above coexists in the reaction system.

The both-end (meth) acryloxypropyl group-capped diorganopolysiloxane synthesized in this way is produced by the equilibration polymerization reaction of both terminals (meth) acryloxypropyl group-capped diorganopolysiloxane having a higher degree of polymerization. In particular, it is useful as a terminal blocking agent.

The terminal (meth) acryloxypropyl group-blocked diorganopolysiloxane thus synthesized was used as a terminal blocker, and an acid catalyst was used to prepare diorganocyclooligosiloxane and / or both ends silanol group-blocked diorganopolysiloxane. Equilibrium polymerization synthesizes both end (meth) acryloxypropyl group-capped diorganopolysiloxanes with a higher degree of polymerization than both end (meth) acryloxypropyl group-capped diorganopolysiloxanes used as end-capping agents. can do. However, when the above-mentioned silanol group-blocked diorganopolysiloxane is used as a polymerization reaction raw material, it is necessary to dehydrate and condense the silanol group in the presence of a catalyst so that the silanol group does not remain at the molecular chain terminal.

The diorganocyclooligosiloxane for that purpose may be one suitable for acid-catalyzed ring-opening polymerization, and is not particularly limited. The cyclic | annular body shown with the following general formula is illustrated.

In the formula, Me is a methyl group, R ⁵ is a hydrogen atom, a hydroxyl group, a monovalent alkyl group having 2 to 30 carbon atoms, an alkenyl group, a cycloalkyl group, an aryl group having 6 to 10 carbon atoms, or the number of carbon atoms. It is a group selected from 2 to 30 monovalent fluorinated alkyl groups, amino-substituted alkyl groups and alkoxy groups.

R ⁵ is specifically hydrogen atom; hydroxyl group; monovalent alkyl group such as ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, decyl group, dodecyl group; vinyl group, Monovalent alkenyl groups such as allyl group and hexenyl group; Monovalent cycloalkyl groups such as cyclopentyl group and cyclohexyl group; Monovalent aryl groups such as phenyl group, tolyl group and naphthyl group; Bonded to carbon atoms of these hydrocarbon groups Examples thereof include monovalent hydrocarbon groups in which the hydrogen atom is partially substituted with a halogen atom, an epoxy group, a carboxyl group, an amino group, a methacryl group or a mercapto group.

Since p and q are integers of 0 to 8 and are numbers satisfying 3 ≦ p + q, 3 ≦ p + q ≦ 16 is satisfied, but 4 ≦ p + q ≦ 10 is preferable.
Examples of such diorganocyclopolysiloxanes include hexamethylcyclotrisiloxane (D3), octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), dodecamethylcyclohexasiloxane (D6), 1,1- Diethylhexamethylcyclotetrasiloxane, phenylheptamethylcyclotetrasiloxane, 1,1-diphenylhexamethylcyclotetrasiloxane, 1,3,5,7-tetravinyltetramethylcyclotetrasiloxane, 1,3,5,7-tetra Examples include methylcyclotetrasiloxane and 1,3,5,7-tetracyclohexyltetramethylcyclotetrasiloxane.

Further, tris (3,3,3-trifluoropropyl) trimethylcyclotrisiloxane, 1,3,5,7-tetra (3-aminopropyl) tetramethylcyclotetrasiloxane, 1,3,5,7-tetra ( N- (2-aminoethyl) 3-aminopropyl) tetramethylcyclotetrasiloxane, 1,3,5,7-tetra (3-mercaptopropyl) tetramethylcyclotetrasiloxane, 1,3,5,7-tetra ( 3-glycidoxypropyl) tetramethylcyclotetrasiloxane, 1,3,5,7-tetra (3-methacryloxypropyl) tetramethylcyclotetrasiloxane, 1,3,5,7-tetra (3-acryloxypropyl) ) Tetramethylcyclotetrasiloxane, 1,3,5,7-tetra (3-carboxypropyl) tetrame Le cyclotetrasiloxane are exemplified.

Furthermore, 1,3,5,7-tetra (3-vinyloxypropyl) tetramethylcyclotetrasiloxane, 1,3,5,7-tetra (p-vinylphenyl) tetramethylcyclotetrasiloxane, 1,3,5 , 7-tetra [3- (p-vinylphenyl) propyl] tetramethylcyclotetrasiloxane, 1,3,5,7-tetra [3- (p-isopropenylbenzoylamino) propyl] tetramethylcyclotetrasiloxane, 1 , 3,5,7-tetra (N-methacryloyl-N-methyl-3-aminopropyl) tetramethylcyclotetrasiloxane, 1,3,5,7-tetra (N-lauroyl-N-methyl-3-aminopropyl) ) Tetramethylcyclotetrasiloxane, 1,3,5,7-tetra (N-acryloyl-N-methyl-3-aminopropyl) ) Tetramethylcyclotetrasiloxane, 1,3,5,7-tetra (N, N-bis (methacryloyl) -3-aminopropyl) tetramethylcyclotetrasiloxane, 1,3,5,7-tetra (N, N -Bis (lauroyl) -3-aminopropyl) tetramethylcyclotetrasiloxane is exemplified.

式中、Ｒ^５は前記同様の基であり、ｍ及びｎは０以上の数であり、（ｍ＋ｎ）は、２５℃における上記ジオルガノポリシロキサンの粘度が０.６５〜１００，０００ｍＰａ・ｓとなる数である。 The silanol group-blocked diorganopolysiloxane for that purpose may be one suitable for equilibration polymerization with an acid catalyst, and is not particularly limited. A linear diorganopolysiloxane having a viscosity at 25 ° C. of 0.65 to 100,000 mm ² / s is preferred, but it may be slightly branched. Examples of the linear both-end silanol-blocked diorganopolysiloxane include those represented by the following formula.

In the formula, R ⁵ is the same group as described above, m and n are numbers of 0 or more, and (m + n) is a viscosity of the diorganopolysiloxane at 25 ° C. of 0.65 to 100,000 mPa · s. It is a number.

More specifically, 1,3-dihydroxytetramethyldisiloxane, 1,7-dihydroxyoctamethyltetrasiloxane, α, ω-dihydroxypolydimethylsiloxane having a viscosity at 25 ° C. of 0.65 to 100,000 mPa · s, Examples include α, ω-dihydroxymethyl vinyl polysiloxane, α, ω-dihydroxymethylphenyl polysiloxane, and α, ω-dihydroxymethyl (3,3,3-trifluoropropyl) polysiloxane.

The acid catalyst may be one suitable for equilibration polymerization of the above-mentioned diorganocyclooligosiloxane or both-end silanol-blocked diorganopolysiloxane, and is not particularly limited. Examples of the acid catalyst include inorganic acids, sulfonic acids, carboxylic acids, and solid acids.

Preferred acid catalysts include inorganic strong acids such as hydrochloric acid, sulfuric acid, and nitric acid; trifluoromethanesulfonic acid; trifluoromethanesulfonic acid trimethylsilyl ester, trifluoromethanesulfonic acid triethylsilyl ester, and the like, trifluoromethanesulfonic acid trialkylsilyl ester, p- Toluene sulfonic acid, acid-treated clay (also called activated clay), sulfonic acid type ion exchange resin and the like can be mentioned. Of these, sulfuric acid, trifluoromethanesulfonic acid, and sulfonic acid type ion exchange resin are preferable because of high polymerization reactivity. Most preferred is sulfuric acid. The sulfonic acid type ion exchange resin that is a solid acid catalyst is preferably a porous high porous type sulfonic acid type ion exchange resin.

The amount of the acid catalyst used is not particularly limited as long as it is sufficient to promote the equilibration polymerization, but is preferably about 0.0001 to 5.0% by weight of the total amount. The polymerization reaction temperature is not particularly limited as long as it is a temperature sufficient to promote equilibration polymerization, but it may be performed at about 0 to 150 ° C, particularly preferably about 20 to 100 ° C. The polymerization reaction time is not particularly limited as long as it is sufficient to complete the equilibration polymerization, but it may be about 30 minutes to 20 hours, and preferably about 1 to 5 hours.

In order to reduce the viscosity of the polymerization reaction system, the raw material may be diluted with an organic solvent for polymerization. The organic solvent is not particularly limited as long as it does not inhibit the polymerization reaction. Aliphatic hydrocarbons such as hexane, heptane, octane, aromatic hydrocarbons such as benzene, toluene, xylene, alcohols such as methanol, ethanol, isopropyl alcohol, methoxyethanol, ethoxyethanol, dimethoxyethanol, diethoxyethanol, Examples include ethers such as methoxymethanol acetate, ethoxyethanol acetate, tetrahydrofuran and dioxane, ketones such as acetone and methyl ethyl ketone, esters such as ethyl acetate, and amides such as dimethylformamide.

After completion of the polymerization reaction, the acid catalyst residue used is neutralized with a base, the formed neutralized salt is filtered off, and the filtrate is evaporated to dryness, and the desired both-end (meth) acryloxypropyl group-capped diorganopolyester is obtained. Siloxane can be obtained. The degree of polymerization is based on both end (meth) acryloxypropyl group-blocked diorganopolysiloxane used as the end-blocking agent, diorganocyclooligosiloxane as a raw material, and both ends silanol group-blocked diorganopolysiloxane as a raw material. Has a high degree of polymerization. The viscosity is naturally larger than the viscosity of the end-capping agent and raw material siloxane. The upper limit value of the degree of polymerization of the aimed bi-terminal (meth) acryloxypropyl group-capped diorganopolysiloxane is usually about 730, and the upper limit value of the viscosity is about 10,000 mPa · s. However, it is not limited to these upper limit values.

The diorganopolysiloxane that is the main chain of the end-terminated (meth) acryloxypropyl group-blocked diorganopolysiloxane is the same diorganosiloxane unit as the diorganosiloxane unit constituting the raw material diorganocyclooligosiloxane. The same diorganosiloxane unit as the diorganosiloxane unit constituting the silanol group-blocked diorganopolysiloxane as the raw material, or the diorganosiloxane constituting the diorganocyclooligosiloxane as the raw material It consists of a unit and a diorganosiloxane unit constituting a diorganopolysiloxane having both ends silanol groups blocked as a raw material.

[Example 1]
In a 0.2 liter four-necked flask equipped with a stirrer, a thermometer, and a condenser tube, 75 g (594.5 mmol) of allyl methacrylate and 3,5-di-t-butyl-4-hydroxyphenylmethyldimethylammonium chloride were added. (Polymerization inhibitor) 0.05 gram was added, and platinum 1,1,3,3-tetramethyl-1,3-divinyldisiloxane complex was added in 5 ppm by weight with respect to platinum metal being allyl methacrylate. Was added and stirred. While stirring this reaction system, it was heated to 95 ° C. in a nitrogen gas atmosphere containing 2% oxygen gas, and a small amount of 1,1,3,3-tetramethyldisiloxane was added dropwise. After confirming the start of the hydrosilylation reaction, a total amount of 33.2 grams (247.7 mmol) of 1,1,3,3-tetramethyl was maintained while maintaining the reaction system at 90 to 100 ° C. by heat, water or air cooling. Disiloxane was added dropwise ([allyl] / [SiH] equivalent ratio = 1.20). After completion of dropping, the mixture was stirred at 85 ° C to 100 ° C for 1 hour. When the infrared absorption (IR) analysis of the flask contents was performed, the characteristic absorption of the hydrosilyl group (SiH group) at 2130 cm ⁻¹ disappeared.

Subsequently, the low boiling point thing in a flask was distilled off under heating and pressure reduction, and 76.6 g of hydrosilylation reaction products were obtained. When this hydrosilylation reaction product was analyzed by gas chromatography and NMR, the mass ratio of various products contained in the hydrosilylation reaction product, 1,3-di (methacryloxypropyl) tetramethyldisiloxane: 1- Methacryloxypropyl-3-methacryloxytetramethyldisiloxane: 1,3-di (methacryloxy) tetramethyldisiloxane was found to be about 50: 44: 6.

Into a 0.2 liter four-necked flask equipped with a stirrer, thermometer and condenser, 20 grams of this hydrosilylation reaction product, 5 grams of sodium bicarbonate powder (59.6 mmol), 20 grams of toluene and 40 grams of water And stirred at 60 ° C. for 3 hours. Next, 2 grams of isopropyl alcohol and 4 grams of sodium chloride powder were added, allowed to stand and phase-separated, and then separated to extract the lower layer (aqueous solution layer). To the remaining upper layer (organic solvent layer), 0.03 g of sulfuric acid was added and stirred, and it was confirmed to be acidic with a pH test paper. The organic solvent layer to which this sulfuric acid was added was subjected to azeotropic dehydration at 70-80 ° C. for about 2 hours while reducing the pressure. After about 2 hours, no more condensed water was observed. The flask was returned to normal pressure and the weight of the contents was measured to be 31 grams.

This content was divided into two equal parts, and the target product was isolated by the following two methods.
(1) 0.05 g of sodium hydrogen carbonate powder and 15 g of water were added to a flask containing 15.5 g of the above contents, and the mixture was stirred and neutralized, and allowed to stand for phase separation. The lower layer (aqueous solution layer) was separated and removed, and the upper layer (organic solvent layer) was further washed with water. From this organic solvent layer, low-boiling substances and solvent were removed by heating under reduced pressure, and 7.2 g of dimethyloligosiloxane blocked with both ends of methacryloxypropyldimethylsiloxy group, which was the target transparent liquid (total conversion yield: 58% )

(2) 0.8 g of sodium hydrogen carbonate powder was put into a flask containing 15.5 g of the above contents and stirred at 40 to 50 ° C. for 7 hours. After confirming that the neutralization reaction was completed using pH test paper, the neutralized salt and excess sodium hydrogen carbonate powder were filtered off, and the low-boiling substances and solvent were removed from the filtrate under reduced pressure by heating. 6.9 gm (total conversion yield 56%) of both ends methacryloxypropyldimethylsiloxy group-blocked dimethyloligosiloxane was obtained.
According to NMR analysis, this dimethyl oligosiloxane had an average degree of polymerization of 3.0. The both-end methacryloxypropyl dimethylsiloxy group-capped dimethyl oligosiloxane can be expressed as both-end methacryloxypropyl group-capped dimethylpolysiloxane (the same applies hereinafter).

[Example 2]
The hydrolysis reaction and the condensation reaction were carried out under the same conditions as in Example 1 except that 20 grams of the hydrosilylation reaction product synthesized in Example 1 was used and the solvent used in the hydrolysis reaction was changed from toluene to the same amount of hexane. Then, by performing the isolation operation of (1) above, 7.5 grams (total conversion yield 60%) of dimethyloligosiloxane blocked with both ends methacryloxypropyldimethylsiloxy group was obtained. Moreover, 7.0 g (total conversion yield 56%) of both ends methacryloxypropyl dimethylsiloxy group blocked dimethyl oligosiloxane was obtained by performing the isolation operation of (2) above. According to NMR analysis, this dimethyl oligosiloxane had an average degree of polymerization of 3.0.

[Example 3]
In a 0.2 liter four-necked flask equipped with a stirrer, a thermometer and a condenser tube, 36.9 g (292.7 mmol) of allyl methacrylate and 3,5-di-t-butyl-4-hydroxyphenylmethyldimethyl were added. 0.05 g of ammonium chloride (polymerization inhibitor) is added, and 1,1,3,3-tetramethyl-1,3-divinyldisiloxane complex of platinum is added in weight units with respect to allyl methacrylate. An amount of 5 ppm was added. While stirring this reaction system, it was heated to 95 ° C. in a nitrogen gas atmosphere containing 2% oxygen gas, and a small amount of dimethylpolysiloxane blocked with dimethylhydrogensiloxy groups at both ends having an average degree of polymerization of 6.5 was dropped. After confirming the start of the hydrosilylation reaction, the reaction system was kept at 90 to 95 ° C. by heat, water or air cooling, and a total amount of 75 grams (122.0 mmol) of the above-mentioned dimethylhydrogensiloxy group-blocked dimethylpolysiloxanes at both ends. Was added dropwise ([allyl] / [SiH] equivalent ratio = 1.20). After completion of dropping, the mixture was stirred at 85 ° C. to 90 ° C. for 1 hour. When IR analysis was performed on the contents of the flask, the characteristic absorption of the hydrosilyl group (SiH group) at 2130 cm ⁻¹ disappeared.

Subsequently, 95.6 g of a hydrosilylation reaction product was obtained by distilling off the low-boiling product under reduced pressure under heating. According to NMR analysis, the mass ratio of various products contained in the hydrosilylation reaction product was determined as follows: both end methacryloxypropyldimethylsiloxy group-capped dimethylpolysiloxane: one end methacryloxypropyldimethylsiloxy other end methacryloxydimethylsiloxy group-capped dimethyl Polysiloxane: both ends methacryloxydimethylsiloxy group-blocked dimethylpolysiloxane was found to be about 49: 42: 9.

Into a 0.1 liter three-necked flask equipped with a stirrer, thermometer and condenser, 20 grams of the hydrosilylation reaction product, 1.9 grams (23.1 mmol) of sodium bicarbonate powder, 20 grams of toluene, triethylamine 0.07 grams and 40 grams of water were added and stirred at 60 ° C. for 6 hours. Next, 4 grams of sodium chloride powder was added, allowed to stand and phase-separated, and then separated to extract the lower layer (aqueous solution layer). To the remaining upper layer (organic solvent layer), 0.03 g of sulfuric acid was added, and it was confirmed to be acidic with a pH test paper.

The organic solvent layer to which this sulfuric acid was added was subjected to azeotropic dehydration at 50 to 70 ° C. under reduced pressure for about 0.5 hours. After about 0.5 hours, no more condensed water was observed. The flask was returned to normal pressure, 0.05 g of sodium hydrogen carbonate powder and 30 g of water were added, and the mixture was stirred and neutralized, and allowed to stand for phase separation. The lower layer (aqueous solution layer) was separated and removed, and the upper layer (organic solvent layer) was washed with water. From this organic solvent layer, low-boiling substances and solvent were removed by heating under reduced pressure, and 16.7 g of a dimethylpolysiloxane having both ends of methacryloxypropyldimethylsiloxy group-blocked dimethylpolysiloxane as a transparent liquid of interest (total yield 71%) ) According to NMR analysis, this dimethylpolysiloxane had an average degree of polymerization of 13.9.

[Example 4]
Into a 0.5 liter four-necked flask equipped with a stirrer, a thermometer, and a condenser tube, 70 grams of the hydrosilylation reaction product synthesized in Example 3, 7 grams (80.9 millimoles) of sodium bicarbonate powder, 70 Gram and 140 grams of water were added and stirred at 60 ° C. for 6 hours. Next, 14 grams of sodium chloride powder was added, allowed to stand and phase-separated, and then separated to extract the lower layer (aqueous solution layer). To the remaining upper layer (organic solvent layer), 0.12 g of sulfuric acid was added, and it was confirmed to be acidic with a pH test paper. Azeotropic dehydration was carried out at 50 to 55 ° C. for about 1 hour under reduced pressure. In about 1 hour, no more condensed water was observed.

Return the flask to normal pressure, add 0.3 grams of sodium bicarbonate powder and 105 grams of water, stir to neutralize, let stand and phase separate, remove the lower layer (aqueous solution layer) The upper layer (organic solvent layer) was washed with water. By removing low-boiling substances and solvent from the organic solvent layer under reduced pressure by heating, 62 g of both ends methacryloxypropyl dimethylsiloxy group-blocked dimethylpolysiloxane which is the target transparent liquid (total conversion yield 75%) Got. According to NMR, this dimethylpolysiloxane had an average degree of polymerization of 13.5.

[Example 5]
In Example 3, 184.5 g (1463.4 mmol) of allyl methacrylate and 0,3,5-di-t-butyl-4-hydroxyphenylmethyldimethylammonium chloride (polymerization inhibitor) were added during the hydrosilylation reaction. 25 grams, 375 grams (609.8 mmol) of dimethylhydrogensiloxy-blocked polydimethylsiloxane having an average degree of polymerization of 6.5 (equivalent ratio of [allyl] / [SiH] = 1.20), 1 of platinum , 1,3,3-Tetramethyl-1,3-divinyldisiloxane complex in an amount of 5 ppm by weight of platinum metal relative to allyl methacrylate, and 43.7% of sodium hydrogen carbonate during the hydrolysis reaction Gram (519.7 mmol), 450 grams of toluene, 1.6 grams of triethylamine and 900 grams of water, using a condensation reaction The reaction was carried out under the same conditions as in Example 3 except that 0.6 g of sulfuric acid was used, and 397 g of the dimethylpolysiloxane blocked with methacryloxypropyldimethylsiloxy group-blocked dimethylpolysiloxane (total conversion yield). 75%). According to NMR analysis, this dimethylpolysiloxane had an average degree of polymerization of 14.4.

[Example 6]
To a 0.1 liter three-necked flask equipped with a stirrer, a thermometer and a condenser tube, 20 g (158.5 mmol) of allyl methacrylate, 0.21 g (1.73 mmol) of dimethylacetoxysilane, 3,5- Di-t-butyl-4-hydroxyphenylmethyldimethylammonium chloride (polymerization inhibitor) (0.015 g) was added and platinum 1,1,3,3-tetramethyl-1,3-divinyldisiloxane complex was added. The amount of platinum metal was 5 ppm by weight with respect to allyl methacrylate. This system was heated to 95 ° C. in a nitrogen gas atmosphere containing 2% oxygen gas, and 8.62 grams (64.3 millimoles) of 1,1,3,3-tetramethyldisiloxane prepared separately and 0.8 ml of dimethylacetoxysilane were prepared. A small amount of 21 grams (1.73 mmol) of the mixture was added dropwise. After confirming the start of the hydrosilylation reaction, the remaining mixture was added dropwise while maintaining the reaction system at 90 to 95 ° C. by heat insulation, water cooling or air cooling (equivalent ratio of [allyl] / [SiH] = 1. 23). After completion of the dropwise addition, the mixture was stirred at 75 ° C. to 90 ° C. for 1 hour, and the contents of the flask were subjected to infrared absorption (IR) analysis. As a result, the characteristic absorption of the hydrosilyl group (SiH group) at 2130 cm ⁻¹ disappeared.

Subsequently, 22.7 grams of a hydrosilylation reaction product was obtained by distilling off the low boiling point product under heating and reduced pressure. According to gas chromatography analysis and NMR analysis, the mass ratio of various products contained in the hydrosilylation reaction product was 1,3-di (methacryloxypropyl) tetramethyldisiloxane: 1-methacryloxypropyl-3-methacryloxy. Tetramethyldisiloxane: 1,3-di (methacryloxy) tetramethyldisiloxane was found to be about 69: 29: 2.

To the total amount of the hydrosilylation reaction product (22.7 grams), 2.7 grams (32.3 mmol) of sodium hydrogen carbonate powder, 20 grams of toluene and 40 grams of water were added and stirred at 60 ° C. for 3 hours. After allowing to stand and phase separation, liquid separation was performed to extract a lower layer (aqueous solution layer). To the remaining upper layer (organic solvent layer), 0.03 g of sulfuric acid was added, and it was confirmed to be acidic with a pH test paper. Azeotropic dehydration was carried out at 70-80 ° C. for about 0.5 hours while reducing the pressure. The formation of condensed water was no longer observed at about 0.5 hours.

After the inside of the flask was returned to normal pressure, 0.05 g of sodium hydrogen carbonate powder and 40 g of water were added, and the mixture was stirred and neutralized, and allowed to stand for phase separation. The lower layer (aqueous solution layer) was separated and removed, and the upper layer (organic solvent layer) was washed with water. Low boiling point substances and solvents were removed from the organic solvent layer under heating and reduced pressure, and 18.8 g of a dimethyloligosiloxane blocked with both ends of methacryloxypropyldimethylsiloxy group, which was the target transparent liquid (total conversion yield: 76%) Got. According to NMR analysis, this dimethyl oligosiloxane had an average degree of polymerization of 2.7.

[Example 7]
Into a 0.2 liter four-necked flask equipped with a stirrer, thermometer, and condenser, 19.4 grams (13.4 mmol) of the polysiloxane prepared in Example 5 and 80.5 grams of octamethylcyclotetrasiloxane ( 272 mmol), 0.05 gram of water and 0.1 gram of trifluoromethanesulfonic acid were added, and when the mixture was stirred at 70 ° C. for 3 hours, thickening was observed. After cooling to room temperature, neutralization reaction was performed by blowing ammonia gas, and it was confirmed that the neutralization reaction was completed with pH test paper. Low boilers and solvent were removed under heating and reduced pressure, and after cooling to room temperature, 78 grams of transparent liquid polysiloxane was obtained by filtering off the ammonium salt of trifluoromethanesulfonic acid (yield 78%). According to NMR analysis, this polysiloxane was a dimethylpolysiloxane blocked with methacryloxypropyldimethylsiloxy groups at both ends, and the average degree of polymerization was 180.

The method for producing a both-end (meth) acryloxypropyl group-capped diorganopolysiloxane of the present invention is useful for producing a high-purity both-end (meth) acryloxypropyl group-capped diorganopolysiloxane with high productivity. .
The method for producing a bi-terminal (meth) acryloxypropyl group-capped diorganopolysiloxane of the present invention produces a bi-terminal (meth) acryloxypropyl group-capped diorganopolysiloxane having a higher degree of polymerization than the raw material siloxane with high productivity. Useful for.

Claims (11)

Structural formula (1): H (R) ₂ SiO [(R ¹ ) ₂ SiO] _n Si (R) ₂ H
(Wherein R is a monovalent hydrocarbon group having no aliphatic unsaturated bond, R ¹ is a monovalent hydrocarbon group having no aliphatic unsaturated bond, and n is 0 to 50) Diorganohydrogensiloxy group-blocked diorganopolysiloxane and formula (2): CH ₂ = C (R ² ) COOCH ₂ CH = CH ₂
(Wherein, R ² is a hydrogen atom or a methyl group) and hydrosilylation reaction with allyl (meth) acrylate represented by
Structural formula (3): CH ₂ = C (R ² ) COOCH ₂ CH ₂ CH ₂ (R) ₂ SiO [(R ¹ ) ₂ SiO] _n Si (R) ₂ CH ₂ CH ₂ CH ₂ OOC (R ² ) C = CH ₂
(Wherein R, R ¹ , R ² and n are as defined above), in the method for producing a diorganopolysiloxane having both ends (meth) acryloxypropyl group blocked,
(1) By-product structural formula (4):
CH ₂ = C (R ² ) COOCH ₂ CH ₂ CH ₂ (R) ₂ SiO [(R ¹ ) ₂ SiO] _n Si (R) ₂ OOC (R ² ) C = CH ₂
(Wherein R, R ¹ , R ² , and n are as defined above) and one end (meth) acryloxy group-capped diorganopolysiloxane and structural formula (5):
CH ₂ = C (R ² ) COO (R) ₂ SiO [(R ¹ ) ₂ SiO] _n Si (R) ₂ OOC (R ² ) C = CH ₂
(Wherein R, R ¹ , R ² and n are as defined above) (2) Structural formula (6) produced by hydrolyzing a diorganopolysiloxane having both ends (meth) acryloxy group blocked: CH ₂ = C (R ² ) COOCH ₂ CH ₂ CH ₂ (R) ₂ SiO [(R ¹ ) ₂ SiO] _n Si (R) ₂ OH
(Wherein R, R ¹ , R ² , and n are as defined above) and a single-end silanol-blocked diorganopolysiloxane represented by the structural formula (7): HO (R) ₂ SiO [(R ¹ ) ₂ SiO] _n Si (R) ₂ OH
(In the formula, R, R ¹ , R ² and n are as defined above) Condensed diorganopolysiloxane having both ends silanol groups blocked by the both ends (meth) acryloxy represented by Structural Formula (3) A method for producing a diorganopolysiloxane having both ends (meth) acryloxypropyl groups blocked, which is converted into a propyl group-blocked diorganopolysiloxane. 2. The production method according to claim 1, wherein an equivalent ratio of allyl group / silicon atom-bonded hydrogen atom is set to 1 or more in the hydrosilylation reaction. The hydrosilylation reaction, the hydrolysis reaction of the hydrosilylation reaction product, and the dehydration condensation reaction of both ends silanol-blocked diorganopolysiloxane are carried out in the presence of a polymerization inhibitor and / or an organic solvent, The manufacturing method of Claim 1 or Claim 2. The hydrosilylation reaction is carried out in the presence of a hydrosilylation reaction catalyst, a polymerization inhibitor and, if necessary, an organic solvent. In this case, allyl (meth) acrylate, hydrosilylation reaction catalyst, polymerization inhibitor, and if necessary in a mixture of organic solvents The production method according to claim 1 or 2, wherein both ends of the diorganohydrogensiloxy group-capped diorganopolysiloxane are introduced. 5. The production method according to claim 1, wherein diorganohydrogenacyloxysilane coexists in the hydrosilylation reaction. 6. The production method according to claim 5, wherein the diorganohydrogenacyloxysilane is dimethylhydrogenacetoxysilane. The hydrosilylation reaction product is hydrolyzed in the presence of an alkali metal hydroxide or carbonate or an alkaline earth metal hydroxide or carbonate according to claim 1. Production method. The production method according to claim 1 or 7, wherein the dehydration condensation reaction of the silanol group-blocked diorganopolysiloxane is performed in the presence of an acid catalyst. Both ends diorganohydrogensiloxy group-blocked diorganopolysiloxane is both ends dimethylhydrogensiloxy group-blocked dimethylpolysiloxane, allyl (meth) acrylate is allyl methacrylate, both ends (meth) acryloxypropyl The production method according to claim 1 or 6, wherein the base-capped diorganopolysiloxane is a both-end (meth) acryloxypropyl group-capped dimethylpolysiloxane. The both-end (meth) acryloxypropyl group-capped diorganopolysiloxane and diorganocyclooligosiloxane and / or both-end silanol group-capped diorganopolysiloxane obtained by the production method of claim 1 are used using an acid catalyst. A method for producing a diorganopolysiloxane having both ends (meth) acryloxypropyl group-blocked diorganopolysiloxane having an increased degree of polymerization, characterized by carrying out equilibration copolymerization. Both ends (meth) acryloxypropyl group-blocked diorganopolysiloxane is both ends (meth) acryloxypropyl group-blocked dimethylpolysiloxane, diorganocyclooligosiloxane is dimethylcyclooligosiloxane, and both ends silanol group-blocked diorganopolysiloxane 11. The production method according to claim 10, wherein the organopolysiloxane is a dimethylpolysiloxane blocked with silanol groups at both ends.