JP4782476B2 - Method for producing SiH group-containing compound - Google Patents

Description

The present invention relates to a method for producing a SiH group-containing compound. More specifically, the present invention relates to a method for producing a low-viscosity SiH group-containing compound without requiring the recycling of the SiH group-containing polyorganosiloxane raw material and without causing gelation.

A production method in which 1,3,5,7-tetramethylcyclotetrasiloxane and allyl glycidyl ether are subjected to a hydrosilylation reaction using a platinum catalyst has been proposed (for example, Patent Document 1). However, after completion of the reaction, a large amount of 1,3,5,7-tetramethylcyclotetrasiloxane was present in the reaction solution in an unreacted state, and it was necessary to recycle.
In addition, a production method in which 1,3,5,7-tetramethylcyclotetrasiloxane and triallyl isocyanurate are hydrosilylated with a platinum catalyst has been proposed (for example, Patent Document 2). However, an excess amount of 1,3,5,7-tetramethylcyclotetrasiloxane is used with respect to triallyl isocyanurate, and 1,3,5,7-tetramethylcyclotetrasiloxane reacts after completion of the reaction. It was present in the liquid in an unreacted state and needed to be recycled. On the other hand, when an allyl group of triallyl isocyanurate is reacted with an equimolar amount of 1,3,5,7-tetramethylcyclotetrasiloxane, a highly viscous reaction product is obtained or gelation occurs during the reaction. there is a possibility.
JP 2003-26183A JP 2002-317048 A

An object of the present invention is to provide a method for producing a compound having at least two SiH groups in one molecule having a low viscosity and without gelation without requiring recycling of a polyorganosiloxane raw material having SiH groups. Is to provide.

As a result of investigations, the present inventors have studied (A) a linear and / or cyclic polyorganosiloxane compound having at least three SiH groups in one molecule, and (B) a carbon-carbon reactive with SiH groups. After reacting a compound containing one double bond in one molecule in the presence of (D) a hydrosilylation catalyst, the obtained reaction product and (C) a carbon-reactive with SiH group The present inventors have found that the above problem can be solved by reacting a compound containing at least two carbon double bonds in one molecule in the presence of (D) a hydrosilylation catalyst.

That is, the present invention comprises (A) a linear and / or cyclic polyorganosiloxane compound having at least 3 SiH groups in one molecule, and (B) a carbon-carbon double bond having reactivity with SiH groups. Is reacted in the presence of a hydrosilylation catalyst, and then the resulting reaction product is further reacted with (C) a carbon-carbon double compound having reactivity with SiH groups. The present invention relates to a method for producing a compound containing at least two SiH groups in one molecule, wherein a compound containing at least two bonds in one molecule is reacted in the presence of (D) a hydrosilylation catalyst. .

The present invention also provides:
(A) The average number of SiH groups in one molecule of the component (α), the average number of molecules (β) of the component (B) that undergoes a hydrosilylation reaction with the component (A), and the hydrosilylation reaction of the component (A) (C ) If the average number of allyl groups in the component is 1, the production method of the SiH group-containing compound is characterized in that (α−β) ≦ 3.5;
(A) component is the following general formula (I)

(In the formula, R ¹ represents an organic group having 1 to 6 carbon atoms, and each R ¹ may be different or the same. N represents a number of 3 to 10). A process for producing the SiH group-containing compound, characterized in that it is a cyclic polyorganosiloxane compound having
(B) The manufacturing method of the said SiH group containing compound characterized by the molecular weight of a component being 500 or less;
(B) The manufacturing method of the said SiH group containing compound characterized by the component being allyl glycidyl ether;
The component (C) contains 2 to 3 carbon-carbon double bonds reactive with SiH groups in one molecule and has a molecular weight of less than 900. Production method;
(C) The manufacturing method of the said SiH group containing compound characterized by the component being triallyl isocyanurate;
(C) Component is diallyl monoglycidyl isocyanurate, The manufacturing method of the said SiH group containing compound characterized by the above-mentioned;
(C) Component is the diallyl ether of bisphenol S, The manufacturing method of the said SiH group containing compound characterized by the above-mentioned;
About.

Below, the manufacturing method of this invention is demonstrated.
The method for producing a compound containing at least two SiH groups in one molecule of the present invention comprises: (A) a linear and / or cyclic polyorganosiloxane compound having at least three SiH groups in one molecule; (B) a compound containing one carbon-carbon double bond reactive with a SiH group in one molecule is reacted in the presence of (D) a hydrosilylation catalyst; (C) A compound containing at least two carbon-carbon double bonds reactive with a SiH group in one molecule is reacted in the presence of (D) a hydrosilylation catalyst. .

((A) component)
First, the component (A) of the present invention will be described.
The component (A) of the present invention is a linear and / or cyclic polyorganosiloxane compound having at least 3 SiH groups in one molecule.

The component (A) is not particularly limited as long as it is a linear and / or cyclic polyorganosiloxane compound having at least 3 SiH groups in one molecule, and is described in, for example, International Publication No. WO96 / 15194. A compound having at least three SiH groups in one molecule can be used.
Specifically, for example

Etc.
Among these, from the viewpoint of availability, a linear and / or cyclic organopolysiloxane having at least 3 SiH groups in one molecule is preferable. Further, from the viewpoint of good hydrosilylation reactivity with the carbon-carbon double bond of the component (B) and / or the component (C) and the storage stability of the reaction product is good, the following general formula ( I)

(Wherein R ¹ represents an organic group having 1 to 6 carbon atoms, and each R ¹ may be different or the same. N represents a number of 3 to 10). Cyclic organopolysiloxanes having at least 3 SiH groups per molecule are preferred.
The substituent R ¹ in the compound represented by the general formula (I) is preferably composed of C, H, and O, more preferably a hydrocarbon group, and a methyl group. Further preferred. Each substituent R ¹ may be different or the same.
From the viewpoint of availability, the compound represented by the general formula (I) is preferably 1,3,5,7-tetramethylcyclotetrasiloxane.
(A) A component can be used individually or in mixture of 2 or more types.

((B) component)
Next, (B) component of this invention is demonstrated.
The component (B) is not particularly limited as long as it is an organic compound containing one carbon-carbon double bond having reactivity with the SiH group in one molecule, but the component (A) is combined with the component (B) and hydrosilyl. The component (B) is a siloxane unit (Si-O-Si) such as a polysiloxane-organic block copolymer or a polysiloxane-organic graft copolymer. It is preferable not to include but to include only C, H, N, O, S, and halogen as constituent elements.
The bonding position of the carbon-carbon double bond having reactivity with the component (B) SiH group is not particularly limited, and may be present anywhere in the molecule.

The compound of the component (B) can be classified into a polymer compound and a monomer compound.
Examples of the polymer compound include polysiloxane, polyether, polyester, polyarylate, polycarbonate, saturated hydrocarbon, unsaturated hydrocarbon, polyacrylate ester, polyamide, phenol-formaldehyde (Phenol resin type) and polyimide type compounds can be used.
Examples of the monomer compound include aromatic hydrocarbon compounds such as phenol, bisphenol, benzene, and naphthalene; aliphatic hydrocarbon compounds such as linear and alicyclic; heterocyclic compounds; silicon Compounds; and mixtures thereof.

(B) Although it does not specifically limit as a carbon-carbon double bond reactive with SiH group of a component, The following general formula (II)

A group represented by the formula (wherein R ² represents a hydrogen atom or a methyl group) is preferable from the viewpoint of reactivity. In addition, from the availability of raw materials,

The groups shown are particularly preferred.
As the carbon-carbon double bond having reactivity with the SiH group of the component (B), the following general formula (III)

(In the formula, R ³ represents a hydrogen atom or a methyl group. Each R ³ may be different or the same), and the alicyclic group having a partial structure in the ring is cured. This is preferable because the heat resistance of the object is high. Moreover, from the ease of acquisition of a raw material, the alicyclic group which has the partial structure represented by a following formula in a ring is suitable.

The carbon-carbon double bond having reactivity with the SiH group may be directly bonded to the skeleton portion of the component (B) or may be covalently bonded via a divalent or higher valent substituent.
The divalent or higher valent substituent is not particularly limited as long as it is a substituent having 0 to 10 carbon atoms. However, the component (A) is hydrosilylated with the component (B) to increase the polarity of the reaction product. In terms of points, elements containing only C, H, N, O, S, and halogen as constituent elements are preferable. Examples of these substituents include

Etc. Moreover, two or more of these divalent or higher valent substituents may be connected by a covalent bond to constitute one divalent or higher valent substituent.

Examples of the group covalently bonded to the skeleton as described above include vinyl group, allyl group, methallyl group, acrylic group, methacryl group, 2-hydroxy-3- (allyloxy) propyl group, 2-allylphenyl group, 3 -Allylphenyl group, 4-allylphenyl group, 2- (allyloxy) phenyl group, 3- (allyloxy) phenyl group, 4- (allyloxy) phenyl group, 2- (allyloxy) ethyl group, 2,2-bis (allyl) Oxymethyl) butyl group, 3-allyloxy-2,2-bis (allyloxymethyl) propyl group,

Etc.
Specific examples of the component (B) include ethylene, propene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-dodecene, 1- Undecene, linearene manufactured by Idemitsu Petrochemical Co., Ltd., 4,4-dimethyl-1-pentene, 2-methyl-1-hexene, 2,3,3-trimethyl-1-butene, 2,4,4-trimethyl-1-pentene Chain aliphatic hydrocarbon compounds such as cyclohexene, methylcyclohexene, methylenecyclohexane, norbornylene, ethylidenecyclohexane, vinylcyclohexane, allylcyclohexane, camphene, carene, α-pinene, β-pinene, etc. Styrene, α-methylstyrene, indene, phenylacetylene, 4-ethynyltoluene, a Aromatic hydrocarbon compounds such as rubenzene and 4-phenyl-1-butene; allyl ethers such as alkyl allyl ether and allyl phenyl ether, glycerin monoallyl ether, ethylene glycol monoallyl ether, 4-vinyl-1,3- Aliphatic compounds such as dioxolan-2-one; Aromatic compounds such as 1,2-dimethoxy-4-allylbenzene, allylanisole, o-allylphenol; monoallyl dibenzyl isocyanurate, monoallyl diglycidyl Substituted isocyanurates such as isocyanurate; silicon compounds such as vinyltrimethylsilane, vinyltrimethoxysilane, and vinyltriphenylsilane. Furthermore, polyether resins such as one-end allylated polyethylene oxide and one-end allylated polypropylene oxide; hydrocarbon resins such as one-end allylated polyisobutylene; one-end allylated polybutyl acrylate, one-end allylated polymethyl methacrylate Examples thereof also include polymers or oligomers having a vinyl group at one end, such as acrylic resins.

The structure of component (B) may be linear or branched.
The molecular weight of the component (B) is not particularly limited, and various types can be used.
The molecular weight of the component (B) is preferably 500 or less, more preferably 300 or less, from the viewpoint that the viscosity is easy to handle.
In addition, from the point that the component (B) undergoes a hydrosilylation reaction stochastically with respect to four SiH groups of 1,3,5,7-tetramethylcyclotetrasiloxane, the molecular weight of the component (B) is 200 or less is preferable and 100 or less is more preferable.
On the contrary, the component (B) is a component (B) from the viewpoint that two components are preferentially reacted with respect to four SiH groups of 1,3,5,7-tetramethylcyclotetrasiloxane. The molecular weight of is preferably 100 or more, more preferably 200 or more.

The molecular weight distribution of the component (B) is not particularly limited, but the molecular weight distribution is preferably 3 or less, more preferably 2 or less in that the viscosity of the reaction product tends to be low. More preferably, it is 5 or less.

When the glass transition temperature of (B) component exists, there is no limitation and various things are used.
The glass transition temperature is preferably 100 ° C. or lower, more preferably 50 ° C. or lower, and further preferably 0 ° C. or lower in that the obtained cured product is likely to be tough. Examples of preferred resins include polybutyl acrylate resins.
On the contrary, the glass transition temperature is preferably 100 ° C. or higher, more preferably 120 ° C. or higher, and further preferably 150 ° C. or higher in that the heat resistance of the resulting cured product is increased. Most preferably, it is 170 ° C. or higher.
The glass transition temperature can be determined as a temperature at which tan δ exhibits a maximum in dynamic viscoelasticity measurement.

The component (B) is preferably an aliphatic hydrocarbon compound from the viewpoint that the light resistance of the resulting cured product is increased. In this case, the lower limit of the preferable carbon number is 2, and the upper limit of the preferable carbon number is 10.
The component (B) is preferably an aromatic hydrocarbon compound in that the cured product to be obtained has high heat resistance. In this case, the lower limit of the preferable carbon number is 7, and the upper limit of the preferable carbon number is 10.

The component (B) may have other reactive groups.
Examples of the reactive group include an epoxy group, an amino group, a radical polymerizable unsaturated group, a carboxyl group, an isocyanate group, a hydroxyl group, an alkoxysilyl group, a vinyloxyl group, and an acid anhydride group. When it has these functional groups, the adhesiveness of the resulting curable composition tends to be high, and the strength of the resulting cured product tends to be high. Of these functional groups, an epoxy group is preferable from the viewpoint that the adhesiveness can be further increased. Moreover, it is preferable to have 1 or more reactive groups in one molecule on average from the point that the heat resistance of the obtained cured product tends to be high.

Specific examples of the component (B) include monoallyl diglycidyl isocyanurate, allyl glycidyl ether, allyl vinyl ether, allyl methacrylate, allyloxyethyl methacrylate, allyl acrylate, allyloxyethyl acrylate, vinyltrimethoxysilane, 4- Examples include vinylcyclohexene-1-oxide. Of these, allyl glycidyl ether is particularly preferable.
As the above component (B), a single component may be used, or a plurality of components may be used in combination.

((C) component)
The component (C) of the present invention will be described.
The component (C) is not particularly limited as long as it is an organic compound containing at least two carbon-carbon double bonds having reactivity with the SiH group in one molecule, but the component (A) and the component (B) In terms of increasing the polarity of the SiH group-containing compound obtained by hydrosilylating the component (C) after the hydrosilylation reaction, the component (C) may be a polysiloxane-organic block copolymer or polysiloxane-organic. It is preferable not to contain a siloxane unit (Si—O—Si) like a graft copolymer but to contain only C, H, N, O, S, and halogen as constituent elements.
The bonding position of the carbon-carbon double bond having reactivity with the SiH group is not particularly limited, and may be present anywhere in the molecule.

The organic compound (C) can be classified into an organic polymer compound and an organic monomer compound.
Examples of organic polymer compounds include polyether-based, polyester-based, polyarylate-based, polycarbonate-based, saturated hydrocarbon-based, unsaturated hydrocarbon-based, polyacrylate ester-based, polyamide-based, phenol-formaldehyde-based (phenolic resin). System), polyimide compounds, and the like.
Examples of organic monomer compounds include aromatic hydrocarbons such as phenols, bisphenols, benzene, and naphthalene, linear hydrocarbons, aliphatic hydrocarbons such as alicyclics, heterocyclic compounds, and the like. A mixture etc. are mentioned.

Although it does not specifically limit as a carbon-carbon double bond which has reactivity with SiH group of (C) component, The following general formula (II)

A group represented by the formula (wherein R ² represents a hydrogen atom or a methyl group) is preferable from the viewpoint of reactivity. In addition, from the availability of raw materials,

Is particularly preferred.
As the carbon-carbon double bond having reactivity with the SiH group of component (C), the following general formula (III)

(In the formula, R ³ represents a hydrogen atom or a methyl group. Each R ³ may be different or the same), and the alicyclic group having a partial structure in the ring is cured. This is preferable because the heat resistance of the object is high. Moreover, from the ease of acquisition of a raw material, the alicyclic group which has the partial structure represented by a following formula in a ring is suitable.

The carbon-carbon double bond having reactivity with the SiH group may be directly bonded to the skeleton portion of the component (C) or may be covalently bonded via a divalent or higher valent substituent.
The divalent or higher valent substituent is not particularly limited as long as it is a substituent having 0 to 10 carbon atoms, but preferably includes only C, H, N, O, S, and halogen as constituent elements. Examples of these substituents include

Etc. Moreover, two or more of these divalent or higher valent substituents may be connected by a covalent bond to constitute one divalent or higher valent substituent.

Examples of the group covalently bonded to the skeleton as described above include vinyl group, allyl group, methallyl group, acrylic group, methacryl group, 2-hydroxy-3- (allyloxy) propyl group, 2-allylphenyl group, 3 -Allylphenyl group, 4-allylphenyl group, 2- (allyloxy) phenyl group, 3- (allyloxy) phenyl group, 4- (allyloxy) phenyl group, 2- (allyloxy) ethyl group, 2,2-bis (allyl) Oxymethyl) butyl group, 3-allyloxy-2,2-bis (allyloxymethyl) propyl group,

Etc.
Specific examples of the component (C) include diallyl phthalate, triallyl trimellitate, diethylene glycol bisallyl carbonate, trimethylolpropane diallyl ether, pentaerythritol triallyl ether, 1,1,2,2-tetraallyloxyethane. Diarylidene pentaerythritol, triallyl cyanurate, triallyl isocyanurate, 1,2,4-trivinylcyclohexane, divinylbenzenes (having a purity of 50 to 100%, preferably having a purity of 80 to 100%) , Divinylbiphenyl, 1,3-diisopropenylbenzene, 1,4-diisopropenylbenzene, diallyl monoglycidyl isocyanurate, diallyl ether of bisphenol A, diallyl ether of bisphenol S, and oligos thereof Chromatography, 1,2-polybutadiene (1,2 ratio 10-100% of those, preferably 1,2 ratio 50-100% of those), allyl ether of novolak phenol, allylated polyphenylene oxide,

In addition, there may be mentioned those in which part or all of the glycidyl group of a conventionally known epoxy resin is replaced with an allyl group.

As the component (C), it is also possible to use low molecular weight compounds that are difficult to express separately as described above for the skeleton and alkenyl groups.
Specific examples of the low molecular weight compounds include aliphatic chain polyene compound systems such as butadiene, isoprene, octadiene and decadiene; aliphatics such as cyclopentadiene, cyclohexadiene, cyclooctadiene, dicyclopentadiene, tricyclopentadiene and norbornadiene. Cyclic polyene compound systems; substituted aliphatic cyclic olefin compound systems such as vinylcyclopentene and vinylcyclohexene.

The number of carbon-carbon double bonds that are reactive with the SiH group of component (C) should be at least two on average per molecule, but curing can be carried out using the SiH-containing compound obtained by this production method. When creating a product, if it is desired to further improve the mechanical strength, the number is preferably more than 2, more preferably 3 or more. When the number of carbon-carbon double bonds reactive with the SiH group of the component (C) is 1 or less per molecule, even if it reacts with the component (A), it will only become a graft structure but not a crosslinked structure. .

As the component (C), from the viewpoint of good reactivity, it is preferable that one or more vinyl groups are contained in one molecule, and two or more vinyl groups are contained in one molecule. It is more preferable. Further, from the viewpoint that the storage stability tends to be good, it is preferable that 6 or less vinyl groups are contained in one molecule, and it is more preferable that 4 or less vinyl groups are contained in one molecule.

As the component (C), the number of carbon-carbon double bonds having reactivity with SiH groups in one molecule from the viewpoint that the SiH-containing compound obtained by this production method is difficult to gel and has low viscosity. Is preferably 4 or less, more preferably 2 to 3.
As the component (C), when a cured product is prepared using the SiH-containing compound obtained by the present production method, from the viewpoint of high mechanical heat resistance and a viscosity with good handleability, The molecular weight is preferably less than 900, more preferably less than 700, and even more preferably less than 500.
Of these, the component (C) having 2 to 3 carbon-carbon double bonds having reactivity with SiH groups in one molecule and having a molecular weight of less than 900 is preferable. Furthermore, the component (C) having 2 to 3 carbon-carbon double bonds having reactivity with SiH groups in one molecule and having a molecular weight of less than 500 is particularly preferable.

As the component (C), when a cured product is prepared using the SiH-containing compound obtained by the present production method, in order to obtain uniform mixing properties with other components and good workability, the viscosity thereof is used. However, at 23 ° C., those less than 100 Pa · s are preferred, those less than 30 Pa · s are more preferred, and those less than 3 Pa · s are even more preferred.
The viscosity can be measured with an E-type viscometer.

As the component (C), when a cured product is prepared using the SiH-containing compound obtained by the present production method, from the viewpoint of suppressing the coloring of the cured product, particularly yellowing, a phenolic hydroxyl group and / or phenol. A compound having a low content of a compound having a derivative of a phenolic hydroxyl group is preferred, and a compound having no phenolic hydroxyl group and / or a compound having a derivative of a phenolic hydroxyl group is preferred.
The phenolic hydroxyl group in the present invention refers to a hydroxyl group directly bonded to an aromatic hydrocarbon nucleus exemplified by a benzene ring, naphthalene ring, anthracene ring, etc., and the phenolic hydroxyl group derivative refers to the hydrogen of the above-mentioned phenolic hydroxyl group. A group in which an atom is substituted with an alkyl group such as a methyl group or an ethyl group, an alkenyl group such as a vinyl group or an allyl group, an acyl group such as an acetoxy group, or the like is shown.

As the component (C), when a cured product is prepared using the SiH-containing compound obtained by the present production method, vinylcyclohexene and dicyclopentadiene are used from the viewpoint that the cured product is less colored and has high light resistance. , Triallyl isocyanurate, diallyl monoglycidyl isocyanurate, diallyl ether of 2,2-bis (4-hydroxycyclohexyl) propane, 1,2,4-trivinylcyclohexane, triallyl isocyanurate, diallyl monoglycidyl isocyanurate 2,2-bis (4-hydroxycyclohexyl) propane diallyl ether and 1,2,4-trivinylcyclohexane are particularly preferred.

The component (C) may have other reactive groups.
Examples of the reactive group include an epoxy group, an amino group, a radical polymerizable unsaturated group, a carboxyl group, an isocyanate group, a hydroxyl group, an alkoxysilyl group, and an acid anhydride group. When these functional groups are included, when a cured product is prepared using the SiH-containing compound obtained by the present production method, the adhesive property of the resulting curable composition is likely to be high and obtained. The strength of the cured product tends to increase. Of these functional groups, an epoxy group is preferable from the viewpoint that the adhesiveness can be further increased. Moreover, it is preferable to have 1 or more reactive groups in one molecule on average from the point that the heat resistance of the obtained cured product tends to be high.
In addition, as the component (C), from the viewpoint of high heat resistance and light resistance, the following general formula (IV)

(Wherein R ⁴ represents a monovalent organic group having 1 to 50 carbon atoms, and each R ⁴ may be different or the same) and is preferably a triallyl isocyanurate. And its derivatives are particularly preferred.

R ^{4 in the} general formula (IV) is preferably a monovalent organic group having 1 to 20 carbon atoms from the viewpoint that the heat resistance of the obtained cured product can be further increased. 10 monovalent organic groups are more preferable, and monovalent organic groups having 1 to 4 carbon atoms are more preferable. Examples of these preferable R ⁴ are methyl group, ethyl group, propyl group, butyl group, phenyl group, benzyl group, phenethyl group, vinyl group, allyl group, glycidyl group,

Etc.
R ^{4 in the} general formula (IV) is a carbon in which at least one of the three R ^{4 s} contains one or more epoxy groups from the viewpoint that adhesion of the obtained cured product to various materials can be improved. A monovalent organic group of 1 to 50 is preferable,

It is more preferable that it is a C1-C50 monovalent organic group containing 1 or more of epoxy groups represented by these. Examples of these preferred R ⁴ include glycidyl group,

Etc.
As R ^{4 in the} general formula (IV), from the viewpoint that the chemical thermal stability of the resulting cured product can be improved, it contains 2 or less oxygen atoms and contains C, H, O as constituent elements. It is preferably a monovalent organic group having 1 to 50 carbon atoms, and more preferably a monovalent hydrocarbon group having 1 to 50 carbon atoms. Examples of these preferable R ⁴ are methyl group, ethyl group, propyl group, butyl group, phenyl group, benzyl group, phenethyl group, vinyl group, allyl group, glycidyl group,

Etc.
As R ^{4 in the} above general formula (IV), at least one of the three R ⁴ is selected from the viewpoint of good reactivity.

It is preferable that it is a C1-C50 monovalent organic group containing 1 or more groups represented by general formula (V) below.

(Wherein R ⁵ represents a hydrogen atom or a methyl group), and more preferably a monovalent organic group having 1 to 50 carbon atoms and containing at least one group represented by:
At least two of the three R ⁴ are represented by the following general formula (VI)

(Wherein R ⁶ represents a direct bond or a divalent organic group having 1 to 48 carbon atoms, and R ⁷ represents a hydrogen atom or a methyl group. The plurality of R ⁶ and R ⁷ may be the same even if they are different from each other. It is more preferable that it is a C1-C50 monovalent organic group containing 1 or more groups represented by this.

R ^{6 in the} general formula (VI) is a direct bond or a divalent organic group having 1 to 48 carbon atoms. From the viewpoint that the obtained cured product can have higher heat resistance, the direct bond or carbon It is preferably a divalent organic group having 1 to 20 carbon atoms, more preferably a direct bond or a divalent organic group having 1 to 10 carbon atoms, and a direct bond or a divalent organic group having 1 to 4 carbon atoms. More preferably, it is a group. Examples of these preferred R ⁶ include

Etc.
As R ^{6 in the} general formula (VI), from the viewpoint that the chemical thermal stability of the resulting cured product can be improved, it is a direct bond or contains two or less oxygen atoms and contains C as a constituent element. It is preferably a C1-C48 divalent organic group containing only H and O, more preferably a direct bond or a C1-C48 divalent hydrocarbon group. Examples of these preferred R ⁶ include

Etc.
R ^{7 in the} general formula (VI) is a hydrogen atom or a methyl group, and a hydrogen atom is preferable from the viewpoint of good reactivity.

However, in the preferred examples of the organic compound represented by the general formula (IV) as described above, it is necessary to contain at least two carbon-carbon double bonds having reactivity with the SiH group in one molecule. is there. From the viewpoint that heat resistance can be further improved, an organic compound containing three or more carbon-carbon double bonds having reactivity with SiH groups in one molecule is more preferable.
Preferred specific examples of the organic compound represented by the above general formula (IV) include triallyl isocyanurate,

Etc.
In order to improve the adhesiveness of the cured product, as the component (C), diallyl monoglycidyl isocyanurate and diallyl ether of bisphenol S are preferable.
Component (C) can be used alone or in combination of two or more.

((D) component)
The hydrosilylation catalyst that is the component (D) of the present invention will be described.
The hydrosilylation catalyst is not particularly limited as long as it has a catalytic activity for the hydrosilylation reaction. For example, a platinum simple substance, a support made of alumina, silica, carbon black or the like on which solid platinum is supported, chloroplatinic acid, platinum chloride Complexes of acids with alcohols, aldehydes, ketones, etc., platinum-olefin complexes (eg, Pt (CH ₂ ═CH ₂ ) ₂ (PPh ₃ ) ₂ , Pt (CH ₂ ═CH ₂ ) ₂ Cl ₂ ), platinum-vinyl Siloxane complexes (eg, Pt (ViMe ₂ SiOSiMe ₂ Vi) _n , Pt [(MeViSiO) ₄ ] _m ), platinum-phosphine complexes (eg, Pt (PPh ₃ ) ₄ , Pt (PBu ₃ ) ₄ ), platinum-phos Fight complexes _{(e.g., Pt [P (OPh) 3} ] 4, Pt [P (OBu) 3] 4) ( in the formula, Me represents a methyl group, u represents a butyl group, Vi represents a vinyl group, Ph represents a phenyl group, and n and m represent an integer.), dicarbonyldichloroplatinum, Karstedt catalyst, Ashby U.S. Pat. No. 3,159,601 and And platinum-hydrocarbon composites described in US Pat. No. 3,159,662, and platinum alcoholate catalysts described in US Pat. No. 3,220,972 to Lamoreaux. In addition, platinum chloride-olefin complexes described in Modic US Pat. No. 3,516,946 are also useful in the present invention.

Examples of catalysts other than platinum compounds include RhCl (PPh) ₃ , RhCl ₃ , RhAl ₂ O ₃ , RuCl ₃ , IrCl ₃ , FeCl ₃ , AlCl ₃ , PdCl ₂ .2H ₂ O, NiCl ₂ , TiCl _4. Etc.
Of these, chloroplatinic acid, platinum-olefin complexes, platinum-vinylsiloxane complexes and the like are preferable from the viewpoint of catalytic activity.
Moreover, these catalysts may be used independently and may be used together 2 or more types.

The addition amount of the hydrosilylation catalyst is not particularly limited, but has sufficient hydrosilylation reactivity, improves the storage stability of the resulting SiH group-containing compound, and lowers the cost in producing the SiH group-containing compound. The preferable amount of the catalyst added to suppress it is that X / Y is 10 when the number of moles of Pt atoms to be added is (X) and the number of moles of carbon-carbon double bonds reactive with SiH groups is (Y). ⁻³ or less, more preferably X / Y is 10 ⁻⁴ or less, and further preferably X / Y is 10 ⁻⁵ or less.

In addition, a cocatalyst can be used in combination with the catalyst.
Co-catalysts include phosphorus compounds such as triphenylphosphine, 1,2-diester compounds such as dimethyl malate, acetylene alcohol compounds such as 2-hydroxy-2-methyl-1-butyne, single sulfur, etc. And sulfur compounds.
The addition amount of the cocatalyst is not particularly limited, but the lower limit of the preferable addition amount is 10 ⁻² mol, more preferably 10 ⁻¹ mol, and the upper limit of the preferable addition amount is 10 ^{2 with} respect to 1 mol of the hydrosilylation catalyst. Mol, more preferably 10 mol.

The obtained SiH group-containing compound can be stored at room temperature or lower without removing the hydrosilylation catalyst added in the present production method, and can be used for preparing a cured product.

(Reaction of (A) component, (B) component and (C) component)
The hydrosilylation reaction of the component (A), the component (B), and the component (C) will be described.
The SiH group-containing compound obtained by this production method is (A) a chain and / or cyclic polyorganosiloxane compound having at least three SiH groups in one molecule, and (B) has reactivity with SiH groups. Hydrosilylation reaction of a compound containing one carbon-carbon double bond in one molecule and (C) a compound containing at least two carbon-carbon double bonds reactive with SiH group in one molecule If it is a compound which contains at least 2 SiH group in 1 molecule obtained by making it do, it will not specifically limit. The hydrosilylation reaction of the component (A), the component (B), and the component (C) is performed in the presence of the hydrosilylation catalyst of the component (D).
The SiH group-containing compound obtained by this production method is a mixture of a plurality of compounds including a compound obtained by hydrosilylation reaction of the component (A) and the component (B). From there, the component (A) and the component (B) The mixture can be used as a curable composition as it is without separation of the compound obtained by hydrosilylation reaction of the components.

The preferred component (A), component (B) and component (C) vary depending on the combination of component (B) and component (C) used, but more preferred component (A) is represented by the following general formula (I):

(Wherein R ¹ represents an organic group having 1 to 6 carbon atoms, and each R ¹ may be different or the same. N represents a number of 3 to 10). It is a cyclic organopolysiloxane having at least 3 SiH groups in one molecule. A more preferable component (B) has a molecular weight of 500 or less, more preferably a molecular weight of 300 or less and a carbon-carbon double bond reactive with a SiH group in one molecule in terms of viscosity with good handleability. It is an organic compound containing a single component. More preferred component (C) is the following general formula (IV) from the viewpoint of high heat resistance and light resistance.

(Wherein R ⁴ represents a monovalent organic group having 1 to 50 carbon atoms, and each R ⁴ may be different or the same).

Examples of the SiH group-containing compound that is a hydrosilylation reaction product of the components (A), (B), and (C) as described above include 1-hexene and divinylbenzene, 1,3,5,7- Reaction product of tetramethylcyclotetrasiloxane, reaction product of α-methylstyrene and divinylbenzene and 1,3,5,7-tetramethylcyclotetrasiloxane, allyl glycidyl ether and divinylbenzene and 1,3,5,7-tetramethyl Reaction product of cyclotetrasiloxane, reaction product of 1-hexene and bisphenol A diallyl ether and 1,3,5,7-tetramethylcyclotetrasiloxane, α-methylstyrene and bisphenol A diallyl ether and 1,3,5,7- Reactants of tetramethylcyclotetrasiloxane, allyl glycidyl ether and bisphenol Reaction product of diol A diallyl ether and 1,3,5,7-tetramethylcyclotetrasiloxane, reaction product of 1-hexene and bisphenol S diallyl ether and 1,3,5,7-tetramethylcyclotetrasiloxane, α-methyl Reaction product of styrene and bisphenol S diallyl ether with 1,3,5,7-tetramethylcyclotetrasiloxane, reaction product of allyl glycidyl ether and bisphenol S diallyl ether with 1,3,5,7-tetramethylcyclotetrasiloxane, Reaction product of 1-hexene and vinylcyclohexene and 1,3,5,7-tetramethylcyclotetrasiloxane, reaction product of α-methylstyrene and vinylcyclohexene and 1,3,5,7-tetramethylcyclotetrasiloxane, allyl glycidyl Ether and vinyl Reaction product of chlorhexene and 1,3,5,7-tetramethylcyclotetrasiloxane, reaction product of 1-hexene and dicyclopentadiene and 1,3,5,7-tetramethylcyclotetrasiloxane, α-methylstyrene and dicyclohexane Reaction product of pentadiene and 1,3,5,7-tetramethylcyclotetrasiloxane, reaction product of allyl glycidyl ether and dicyclopentadiene and 1,3,5,7-tetramethylcyclotetrasiloxane, 1-hexene and triallyl Reaction product of isocyanurate and 1,3,5,7-tetramethylcyclotetrasiloxane, reaction product of α-methylstyrene and triallyl isocyanurate and 1,3,5,7-tetramethylcyclotetrasiloxane, allyl glycidyl ether and Triallyl isocyanurate and 1,3,5,7- Reactant of tetramethylcyclotetrasiloxane, 1-hexene and diallyl monoglycidyl isocyanurate with 1,3,5,7-tetramethylcyclotetrasiloxane, α-methylstyrene and diallyl monoglycidyl isocyanurate with 1,3,3 Examples thereof include a reaction product of 5,7-tetramethylcyclotetrasiloxane, a reaction product of allyl glycidyl ether and diallyl monoglycidyl isocyanurate and 1,3,5,7-tetramethylcyclotetrasiloxane.

From the point of light resistance of the cured product, a reaction product of 1-hexene and divinylbenzene and 1,3,5,7-tetramethylcyclotetrasiloxane, 1-hexene and triallyl isocyanurate and 1,3,5,7-tetra A reaction product of methylcyclotetrasiloxane is preferred. Further, from the viewpoint of heat resistance, light resistance and adhesiveness, a reaction product of allyl glycidyl ether and triallyl isocyanurate and 1,3,5,7-tetramethylcyclotetrasiloxane, allyl glycidyl ether and diallyl monoglycidyl isocyanurate and 1 , 3,5,7-tetramethylcyclotetrasiloxane reactant is preferred.

The ratio of each component when the component (B) and the component (C) are subjected to a hydrosilylation reaction with the component (A) is not particularly limited, but in the reaction system, the average number of SiH groups in one molecule of the component (A) ( When the average number of molecular groups (β) of the component (B) that undergoes hydrosilylation reaction with the component (A) and (A) and the number of allyl groups of the component (C) that undergoes hydrosilylation reaction with the component (A) is one on average. The relationship between (α) and (β) can be obtained without gelation of the SiH group-containing compound obtained by the present production method and with low viscosity, and in the reaction solution in the unreacted state after completion of the hydrosilylation reaction. From the point that the component (A) remaining in (5) is 5.0% or less of the component (A) used in the reaction, it is preferable that (α−β) ≦ 3.5, and (α−β) ≦ 3. 0 is more preferable, and (α−β) ≦ 2.5 is most preferable. Arbitrariness. (Α) and (β) can be determined from the weighed values when each component is charged.

Various methods can be used as a method of mixing the (A) component, (B) component, (C) component, and (D) component catalyst during the reaction. Preferably, the mixture of the component (B) with the catalyst is mixed with the component (A) and reacted, and the reaction product of the component (A) and the component (B) thus obtained is converted into the component (C). This is a method of mixing a mixture of catalysts. The catalyst may or may not be removed once after the reaction between the component (A) and the component (B). However, if the catalyst is not removed, the catalyst can be used as it is for the next reaction.
On the other hand, if the catalyst is mixed with the mixture of the component (A) and the component (B) or the mixture of the reaction product of the components (A) and (B) and the component (C), it is difficult to control the reaction. There is a tendency to become. Further, in the case of mixing the component (A) and the catalyst and the method of mixing the component (B), in the presence of the catalyst, the component (A) is reactive with the moisture mixed therein, and therefore the quality is changed. Sometimes.

Although the reaction temperature can be variously set in the entire reaction, the lower limit of the preferable temperature range is 30 ° C, more preferably 50 ° C, and the upper limit of the preferable temperature range is 200 ° C, more preferably 150 ° C. If the reaction temperature is lower than 30 ° C, the reaction time for sufficient reaction tends to be long, and if the reaction temperature is higher than 200 ° C, it tends to be impractical. The reaction may be performed at a constant temperature, but the temperature may be changed in multiple steps or continuously as required.
Also, the reaction time and the pressure during the reaction can be variously set as necessary.

Oxygen can be used during the hydrosilylation reaction. The hydrosilylation reaction can be promoted by adding oxygen to the gas phase portion of the reaction vessel. From the point of setting the amount of oxygen to be below the lower limit of explosion limit, the oxygen volume concentration in the gas phase must be controlled to 3% or less. The oxygen volume concentration in the gas phase is preferably 0.1% or more, more preferably 1% or more, from the viewpoint that the effect of promoting the hydrosilylation reaction by addition of oxygen is observed.

A solvent may be used during the hydrosilylation reaction.
The solvent is not particularly limited as long as it does not inhibit the hydrosilylation reaction. Specifically, hydrocarbon solvents such as benzene, toluene, hexane, heptane; tetrahydrofuran, 1,4-dioxane, 1, 3 -Ether solvents such as dioxolane and diethyl ether; ketone solvents such as acetone and methyl ethyl ketone; halogen solvents such as chloroform, methylene chloride and 1,2-dichloroethane can be preferably used.
The said solvent may be used independently and can also be used as 2 or more types of mixed solvents.
Of the above solvents, toluene, tetrahydrofuran, 1,3-dioxolane and chloroform are preferred. The amount of solvent to be used can also be set as appropriate.

After the component (A) is hydrosilylated with the component (B) and the component (C), the solvent, the unreacted component (A), the component (B), and the component (C) can be removed. By removing these volatile components, the resulting SiH group-containing compound does not have volatile components. Therefore, when creating a cured product using this SiH group-containing compound, voids and cracks due to volatilization of volatile components are eliminated. Problems are less likely to occur.
Examples of the removing method include treatment with activated carbon, aluminum silicate, silica gel and the like in addition to devolatilization under reduced pressure.
When devolatilizing under reduced pressure, it is preferable to treat at a low temperature. The upper limit of the preferable temperature in this case is 100 ° C, more preferably 80 ° C. When it is processed at a temperature higher than 100 ° C., it tends to be accompanied by alteration such as thickening.

In the production method of the present invention, various additives can be used depending on the purpose.
(Gelling retarder)
For the purpose of improving the storage stability of the SiH group-containing compound obtained by this production method, or after subjecting the (A) component to the hydrosilylation reaction of the (B) component and the (C) component, the solvent, unreacted (A) A gelation retarder can be used for the purpose of suppressing alterations such as thickening due to heat treatment during vacuum devolatilization when removing the component, the component (B), and the component (C).
Examples of the gel retarder include a compound containing an aliphatic unsaturated bond, an organic phosphorus compound, an organic sulfur compound, a nitrogen-containing compound, a tin compound, an organic peroxide, etc., and these may be used in combination. .

Examples of the compound containing an aliphatic unsaturated bond include propargyl alcohols such as 3-hydroxy-3-methyl-1-butyne, 3-hydroxy-3-phenyl-1-butyne and 1-ethynyl-1-cyclohexanol. And maleate esters such as ene-yne compounds and dimethyl malate.
Examples of the organophosphorus compound include triorganophosphine, diorganophosphine, organophosphon, and triorganophosphite.
Examples of organic sulfur compounds include organomercaptans, diorganosulfides, hydrogen sulfide, benzothiazole, thiazole, benzothiazole disulfide and the like.
Examples of the nitrogen-containing compound include benzothiazole, thiazole, benzothiazole disulfide and the like.
Examples of tin compounds include stannous halide dihydrate and stannous carboxylate.
Examples of the organic peroxide include di-t-butyl peroxide, dicumyl peroxide, benzoyl peroxide, and t-butyl perbenzoate.

Among these gelation retarders, benzothiazole, thiazole, dimethyl malate, 3-hydroxy-3-methyl-1-butyne, 1-ethynyl-1 are used from the viewpoint of good retarding activity and good raw material availability. -Cyclohexanol and triphenylphosphine are preferred.

The addition amount of the gelation retarder can be variously set, but the lower limit of the preferable addition amount with respect to 1 mol of the hydrosilylation catalyst to be used is 10 ⁻¹ mol, more preferably 1 mol, and the upper limit of the preferable addition amount is 10 ³ mol. Preferably it is 50 mol.
These gelation retarders may be used alone or in combination of two or more.

(solvent)
When the SiH group-containing compound obtained by this production method has a high viscosity, it can be dissolved in a solvent and used.
Solvents that can be used are not particularly limited, and specific examples include hydrocarbon solvents such as benzene, toluene, hexane, and heptane; tetrahydrofuran, 1,4-dioxane, 1,3-dioxolane, diethyl ether, and the like. Ether solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, etc .; ketone solvents such as propylene glycol-1-monomethyl ether-2-acetate, ethylene glycol diethyl ether; chloroform, methylene chloride, 1,2-dichloroethane A halogen-based solvent such as can be suitably used.
Of these, toluene, tetrahydrofuran, 1,3-dioxolane, propylene glycol-1-monomethyl ether-2-acetate, and chloroform are preferable.

These solvents may be used alone or as a mixed solvent of two or more types.
Although the usage-amount of a solvent can be set suitably, the minimum of the preferable usage-amount is 0.1 mL with respect to 1g of SiH group containing compounds to be used, and the upper limit of a preferable usage-amount is 10 mL. If the amount used is less than 0.1 mL, there is a tendency that the effect of using a solvent such as viscosity reduction is difficult to obtain, and if the amount used is more than 10 mL, the solvent remains in the material, causing thermal cracks, etc. It tends to be a problem and is disadvantageous in terms of cost, and the industrial utility value tends to decrease.

By using the production method of the present invention, a low-viscosity compound having at least two SiH groups can be obtained without gelation without requiring recycling of a polyorganosiloxane raw material having SiH groups. Can be manufactured.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited thereto.

(Analysis method)
In the following examples and comparative examples, each physical property was measured as follows.
(NMR)
A 300 MHz NMR apparatus manufactured by Varian Technologies Japan Limited was used. The reaction rate of the allyl group was measured by adding the reaction solution diluted to about 1% with deuterated chloroform to the NMR tube and measuring the peak of the methylene group derived from the unreacted allyl group and the methylene group derived from the reacted allyl group. Obtained from the peak. As for the functional group value of the SiH group-containing compound obtained by this production method, 0.02 ± 0.005 g of the SiH group-containing compound, 0.02 ± 0.005 g of dibromoethane, and about 1.5 g of deuterated chloroform are placed in an appropriate sample tube. Were weighed and made uniform, and then added to the NMR tube to prepare the SiH group value (mmol / g) and allyl group value (mmol / g) in terms of dibromoethane.

(GC)
SHIMADZU GAS CHROMATOGRAPH GC-14B / C-R5A manufactured by Shimadzu Corporation was used. As the column, SHIMADZU CBP1-M25-025 was used. The split ratio was 20. The injection temperature was 250 ° C., the column temperature was 50 ° C. for 6 minutes, the temperature was raised 20 ° C./minute, and the temperature was 250 ° C. for 10 minutes. The implantation amount was 0.2 to 0.8 μl.
In order to determine the composition of unreacted 1,3,5,7-tetramethylcyclotetrasiloxane in the reaction solution, LS-8660 manufactured by Shin-Etsu Silicone Co., Ltd. was used as an internal standard substance, dehydrated toluene manufactured by Wako Pure Chemical Industries, Ltd., A calibration curve was prepared using KF-9902 manufactured by Shin-Etsu Silicone Co., Ltd. For sample preparation, 0.20 g of LS-8660 was weighed with respect to 2.0 g of the reaction solution, and the sample was made uniform.
In order to determine the amount of residual volatile components in the SiH group-containing compound obtained by this production method, LS-8660 manufactured by Shin-Etsu Silicone Co., Ltd. was used as an internal standard substance, and cyclohexane manufactured by Wako Pure Chemical Industries, Ltd. was used as a solvent. A calibration curve was prepared using dehydrated toluene manufactured by Kojun Pharmaceutical Co., Ltd., KF-9902 manufactured by Shin-Etsu Silicone Co., Ltd., and allyl glycidyl ether manufactured by Wako Pure Chemical Industries, Ltd. For sample preparation, a 0.20 wt% cyclohexane solution of LS-8660 was prepared in advance, and a uniform mixture of this preparation solution and an equivalent amount of the SiH group-containing compound obtained by this production method was used. It was.

(GPC)
Prepare a 1% by weight toluene solution and use LC MODULE 1 manufactured by WATERS, flow rate of 1 ml / min with toluene solvent, column temperature 40 ° C., polystyrene conversion, connecting columns are 4 columns (KF806L / KF804L / Using a KF8025 / KF802), measurement was performed with an RI detector.

(viscosity)
An E-type viscometer manufactured by Tokyo Keiki Co., Ltd. was used. Measurement was performed at a measurement temperature of 23.0 ° C. and an EHD type 48φ 1-fold cone.

(Comparative Example 1)
696 g of toluene and 463 g of 1,3,5,7-tetramethylcyclotetrasiloxane were placed in a 2 L autoclave, the gas phase was replaced with nitrogen, and then heated and stirred at a jacket temperature of 105 ° C. A mixed solution of 80 g of triallyl isocyanurate, 80 g of toluene, and 0.050 g of a xylene solution of platinum vinylsiloxane complex (containing 3 wt% as platinum) was added dropwise over 40 minutes. Three hours after the completion of the dropwise addition, it was confirmed by ¹ H-NMR that the reaction rate of the allyl group was 95% or more, and the reaction was terminated by cooling. The unreacted rate of 1,3,5,7-tetramethylcyclotetrasiloxane was 57%. Unreacted 1,3,5,7-tetramethylcyclotetrasiloxane and toluene were distilled off under reduced pressure to a total of 5,000 ppm or less to obtain a colorless and transparent liquid.

The viscosity of this product was 3.0 Pa · s. When this product was measured by GPC, a multimodal chromatogram was obtained, suggesting a mixture. This product is a product in which a part of the SiH group of 1,3,5,7-tetramethylcyclotetrasiloxane has reacted with the allyl group of triallyl isocyanurate (the following structural formula), as determined by ¹ H-NMR. Yes, it was found to contain 8.8 mmol / g SiH groups.

Example 1
A 2 L autoclave was charged with 600 g of toluene and 200 g of 1,3,5,7-tetramethylcyclotetrasiloxane, the gas phase portion was replaced with nitrogen, and the mixture was heated and stirred at a jacket temperature of 50 ° C. A mixed solution of 96 g of allyl glycidyl ether, 96 g of toluene, and 0.027 g of a xylene solution of platinum vinylsiloxane complex (containing 3 wt% as platinum) was added dropwise over 60 minutes. After completion of dropping, the jacket temperature was raised to 60 ° C. and reacted for 40 minutes, and it was confirmed by ¹ H-NMR that the allyl group reaction rate was 95% or more. After dropwise addition of a mixed solution of 14 g of triallyl isocyanurate and 14 g of toluene, the jacket temperature was raised to 105 ° C., and 56 g of triallyl isocyanurate, 56 g of toluene and a xylene solution of a platinum vinylsiloxane complex (containing 3 wt% as platinum) 017 g of the mixed solution was dropped over 30 minutes. Four hours after the completion of the dropwise addition, it was confirmed by ¹ H-NMR that the reaction rate of the allyl group was 95% or more, and the reaction was terminated by cooling. The unreacted rate of 1,3,5,7-tetramethylcyclotetrasiloxane was 3.9%. A total of 5,000 ppm or less of unreacted 1,3,5,7-tetramethylcyclotetrasiloxane, toluene and allyl glycidyl ether by-product (inner transition products of allylic glycidyl ether vinyl group (cis isomer and trans isomer)) The solution was distilled off under reduced pressure to obtain a colorless and transparent liquid.

The viscosity of this product was 2.3 Pa · s. From the measurement of ¹ H-NMR, this product was obtained by reacting a part of the SiH group of 1,3,5,7-tetramethylcyclotetrasiloxane with the allyl group of allyl glycidyl ether and triallyl isocyanurate, It was found to contain 5.1 mmol / g SiH groups. When this product is subjected to GPC measurement, a multimodal chromatogram is obtained, and a group of compounds in which 1,3,5,7-tetramethylcyclotetrasiloxane, allyl glycidyl ether and triallyl isocyanurate are reacted (the following structural formula) And a mixture of reactant groups of only 1,3,5,7-tetramethylcyclotetrasiloxane and allyl glycidyl ether.

(Example 2)
720 g of toluene and 240 g of 1,3,5,7-tetramethylcyclotetrasiloxane were placed in a 2 L autoclave, the gas phase was replaced with nitrogen, and then heated and stirred at a jacket temperature of 50 ° C. A mixed solution of 171 g of allyl glycidyl ether, 171 g of toluene, and 0.049 g of a xylene solution of platinum vinylsiloxane complex (containing 3 wt% as platinum) was added dropwise over 90 minutes. After completion of dropping, the jacket temperature was raised to 60 ° C. and reacted for 40 minutes, and it was confirmed by ¹ H-NMR that the allyl group reaction rate was 95% or more. After dropwise addition of 17 g of triallyl isocyanurate and 17 g of toluene, the jacket temperature was raised to 105 ° C., and 66 g of triallyl isocyanurate, 66 g of toluene and a xylene solution of a platinum vinylsiloxane complex (containing 3 wt% as platinum) 033 g of the mixed solution was added dropwise over 30 minutes. Four hours after the completion of the dropwise addition, it was confirmed by ¹ H-NMR that the reaction rate of the allyl group was 95% or more, and the reaction was terminated by cooling. The unreacted rate of 1,3,5,7-tetramethylcyclotetrasiloxane was 0.8%. A total of 5,000 ppm or less of unreacted 1,3,5,7-tetramethylcyclotetrasiloxane, toluene and allyl glycidyl ether by-product (inner transition products of allylic glycidyl ether vinyl group (cis isomer and trans isomer)) The solution was distilled off under reduced pressure to obtain a colorless and transparent liquid.

The viscosity of this product was 1.8 Pa · s. From the measurement of ¹ H-NMR, this product was obtained by reacting a part of the SiH group of 1,3,5,7-tetramethylcyclotetrasiloxane with the allyl group of allyl glycidyl ether and triallyl isocyanurate, It was found to contain 3.9 mmol / g SiH groups. When this product is subjected to GPC measurement, a multimodal chromatogram is obtained, and a group of compounds in which 1,3,5,7-tetramethylcyclotetrasiloxane, allyl glycidyl ether and triallyl isocyanurate are reacted (the following structural formula) And a mixture of reactant groups of only 1,3,5,7-tetramethylcyclotetrasiloxane and allyl glycidyl ether.

(Example 3)
A 2 L autoclave was charged with 600 g of toluene and 200 g of 1,3,5,7-tetramethylcyclotetrasiloxane, the gas phase portion was replaced with nitrogen, and the mixture was heated and stirred at a jacket temperature of 50 ° C. A mixed liquid of 190 g of allyl glycidyl ether, 190 g of toluene, and 0.033 g of a xylene solution of platinum vinylsiloxane complex (containing 3 wt% as platinum) was added dropwise over 90 minutes. After completion of dropping, the jacket temperature was raised to 60 ° C. and reacted for 120 minutes, and it was confirmed by ¹ H-NMR that the reaction rate of allyl group was 95% or more. After dropwise addition of a mixed solution of 14 g of triallyl isocyanurate and 14 g of toluene, the jacket temperature was raised to 105 ° C., and 56 g of triallyl isocyanurate, 56 g of toluene and a xylene solution of a platinum vinylsiloxane complex (containing 3 wt% as platinum) 028 g of the mixed solution was added dropwise over 30 minutes. The reaction rate of the allyl group by ¹ H-NMR 9 hours after the completion of dropping was 90%. The reaction was terminated by cooling. There was no unreacted 1,3,5,7-tetramethylcyclotetrasiloxane. By-products of toluene and allyl glycidyl ether (internally transferred products of vinyl groups of allylic glycidyl ether (cis- and trans-isomers)) were distilled off under reduced pressure to a total of 5,000 ppm or less to obtain a colorless and transparent liquid.

The viscosity of this product was 1.0 Pa · s. From the measurement of ¹ H-NMR, this product was obtained by reacting a part of the SiH group of 1,3,5,7-tetramethylcyclotetrasiloxane with the allyl group of allyl glycidyl ether and triallyl isocyanurate, It was found to contain 2.8 mmol / g SiH groups. When this product is subjected to GPC measurement, a multimodal chromatogram is obtained, and a group of compounds in which 1,3,5,7-tetramethylcyclotetrasiloxane, allyl glycidyl ether and triallyl isocyanurate are reacted (the following structural formula) And a mixture of reactant groups of only 1,3,5,7-tetramethylcyclotetrasiloxane and allyl glycidyl ether.

(Comparative Example 2)
After putting 362 g of toluene and 362 g of 1,3,5,7-tetramethylcyclotetrasiloxane in a 2 L autoclave and replacing the gas phase with nitrogen, the mixture was heated and stirred at a jacket temperature of 105 ° C. A mixed liquid of 100 g of diallyl monoglycidyl isocyanurate, 100 g of toluene, and 0.049 g of a xylene solution of platinum vinylsiloxane complex (containing 3 wt% as platinum) was added dropwise over 90 minutes. Two hours after the completion of the dropwise addition, it was confirmed by ¹ H-NMR that the reaction rate of the allyl group was 95% or more, and the reaction was terminated by cooling. The unreacted rate of 1,3,5,7-tetramethylcyclotetrasiloxane was 55%. Unreacted 1,3,5,7-tetramethylcyclotetrasiloxane and toluene were distilled off under reduced pressure to a total of 5,000 ppm or less to obtain a colorless and transparent liquid.

The viscosity of this product was 8.1 Pa · s. When this product was measured by GPC, a multimodal chromatogram was obtained, suggesting a mixture. This product was obtained by measuring a part of the SiH group of 1,3,5,7-tetramethylcyclotetrasiloxane and reacting with the allyl group of diallylmonoglycidyl isocyanurate from the ¹ H-NMR measurement (the following structural formula) And found to contain 7.4 mmol / g SiH groups.

Example 4
500 g of toluene and 200 g of 1,3,5,7-tetramethylcyclotetrasiloxane were placed in a 2 L autoclave, the gas phase was replaced with nitrogen, and then heated and stirred at a jacket temperature of 50 ° C. A mixed solution of 95 g of allyl glycidyl ether, 95 g of toluene, and 0.027 g of a xylene solution of platinum vinylsiloxane complex (containing 3 wt% as platinum) was added dropwise over 80 minutes. After completion of dropping, the jacket temperature was raised to 60 ° C. and reacted for 60 minutes, and it was confirmed by ¹ H-NMR that the allyl group reaction rate was 95% or more. After dropping 1/5 of a mixture of 110 g of diallyl monoglycidyl isocyanurate, 110 g of toluene and 0.243 g of a xylene solution of platinum vinylsiloxane complex (containing 3 wt% as platinum), the jacket temperature was raised to 105 ° C., The remaining 4/5 amount was added dropwise over 30 minutes. Two hours after the completion of the dropwise addition, it was confirmed by ¹ H-NMR that the reaction rate of the allyl group was 95% or more, and the reaction was terminated by cooling. The unreacted rate of 1,3,5,7-tetramethylcyclotetrasiloxane was 4.0%. A total of 5,000 ppm or less of unreacted 1,3,5,7-tetramethylcyclotetrasiloxane, toluene and allyl glycidyl ether by-product (inner transition products of allylic glycidyl ether vinyl group (cis isomer and trans isomer)) The solution was distilled off under reduced pressure to obtain a colorless and transparent liquid.

The viscosity of this product was 2.8 Pa · s. This product is a product in which a part of the SiH group of 1,3,5,7-tetramethylcyclotetrasiloxane has reacted with the allyl group of allyl glycidyl ether and diallyl monoglycidyl isocyanurate from ¹ H-NMR measurement. It was found to contain 4.3 mmol / g SiH groups. When this product was subjected to GPC measurement, a multimodal chromatogram was obtained, and a compound group in which 1,3,5,7-tetramethylcyclotetrasiloxane, allyl glycidyl ether and diallyl monoglycidyl isocyanurate reacted (the following structural formula) ) And 1,3,5,7-tetramethylcyclotetrasiloxane and allyl glycidyl ether reaction group.

(Example 5)
A 2 L autoclave was charged with 600 g of toluene and 200 g of 1,3,5,7-tetramethylcyclotetrasiloxane, the gas phase portion was replaced with nitrogen, and the mixture was heated and stirred at a jacket temperature of 50 ° C. A mixed solution of 142 g of allyl glycidyl ether, 142 g of toluene and 0.041 g of a xylene solution of platinum vinylsiloxane complex (containing 3 wt% as platinum) was added dropwise over 90 minutes. After completion of dropping, the jacket temperature was raised to 60 ° C. and reacted for 60 minutes, and it was confirmed by ¹ H-NMR that the allyl group reaction rate was 95% or more. After dropping 1/5 amount of a mixed solution of 110 g of diallyl monoglycidyl isocyanurate, 110 g of toluene and 0.230 g of platinum vinylsiloxane complex in xylene (containing 3 wt% as platinum), the jacket temperature was raised to 105 ° C., The remaining 4/5 amount was added dropwise over 30 minutes. Two hours after the completion of the dropwise addition, it was confirmed by ¹ H-NMR that the reaction rate of the allyl group was 95% or more, and the reaction was terminated by cooling. The unreacted rate of 1,3,5,7-tetramethylcyclotetrasiloxane was 1.0%. A total of 5,000 ppm or less of unreacted 1,3,5,7-tetramethylcyclotetrasiloxane, toluene and allyl glycidyl ether by-product (inner transition products of allylic glycidyl ether vinyl group (cis isomer and trans isomer)) The solution was distilled off under reduced pressure to obtain a colorless and transparent liquid.

The viscosity of this product was 2.0 Pa · s. This product is a product in which a part of the SiH group of 1,3,5,7-tetramethylcyclotetrasiloxane has reacted with the allyl group of allyl glycidyl ether and diallyl monoglycidyl isocyanurate from ¹ H-NMR measurement. It was found to contain 3.3 mmol / g SiH groups. When this product was subjected to GPC measurement, a multimodal chromatogram was obtained, and a compound group in which 1,3,5,7-tetramethylcyclotetrasiloxane, allyl glycidyl ether and diallyl monoglycidyl isocyanurate reacted (the following structural formula) ) And 1,3,5,7-tetramethylcyclotetrasiloxane and allyl glycidyl ether reaction group.

(Comparative Example 3)
A 500 ml four-necked flask was charged with 218 g of toluene and 109 g of 1,3,5,7-tetramethylcyclotetrasiloxane, and the gas phase was replaced with nitrogen, and then heated and stirred at an oil bath temperature of 90 ° C. 10 g of diallyl ether of bisphenol S in the form of white powder was added with 3 g of toluene, followed by dropwise addition of 3.93 g of a solution obtained by diluting a platinum vinylsiloxane complex xylene solution (containing 3 wt% of platinum) 1000 times with toluene. . The diallyl ether of bisphenol S dissolved in a few minutes. After 60 minutes, 10 g of diallyl ether of bisphenol S was added with 3 g of toluene, and then 2.62 g of a solution obtained by diluting a xylene solution of platinum vinylsiloxane complex (containing 3 wt% as platinum) 1000 times with toluene was dropped with a syringe. . After 60 minutes, 10 g of diallyl ether of bisphenol S was added with 3 g of toluene, and then 1.31 g of a solution obtained by diluting a xylene solution of platinum vinylsiloxane complex (containing 3 wt% of platinum) 1000 times with toluene was dropped with a syringe. did. Three hours after the completion of the dropwise addition, it was confirmed by ¹ H-NMR that the reaction rate of the allyl group was 95% or more, and the reaction was terminated by cooling. The unreacted rate of 1,3,5,7-tetramethylcyclotetrasiloxane was 60%. As a gelation retarder, 1.58 g of a solution obtained by diluting triphenylphosphine with toluene 100 times was added to the reaction solution. Unreacted 1,3,5,7-tetramethylcyclotetrasiloxane and toluene were distilled off under reduced pressure to a total of 5,000 ppm or less to obtain a slightly yellow transparent liquid.

The viscosity of this product was 11.3 Pa · s. When this product was measured by GPC, a multimodal chromatogram was obtained, suggesting a mixture. This product ^is from the measurement of 1 H-NMR, 1,3,5,7-that part of the SiH groups of tetramethylcyclotetrasiloxane were reacted with allyl groups of diallyl ether of bisphenol S (following structural formula) And found to contain 6.9 mmol / g SiH groups.

(Example 6)
Into a 1 L four-necked flask, 365 g of toluene and 146 g of 1,3,5,7-tetramethylcyclotetrasiloxane were placed, and the gas phase portion was replaced with nitrogen, followed by heating and stirring at a jacket temperature of 55 ° C. A mixed solution of 104 g of allyl glycidyl ether, 104 g of toluene, and 0.030 g of a xylene solution of platinum vinylsiloxane complex (containing 3 wt% as platinum) was added dropwise over 120 minutes. After 60 minutes, it was confirmed by ¹ H-NMR that the reaction rate of the allyl group was 95% or more. 20 g of diallyl ether of bisphenol S was added with 20 g of toluene, and diallyl ether of bisphenol S attached to the glass wall was poured with 4 g of toluene. The jacket temperature was changed to 95 ° C. When the internal temperature was stabilized at 95 ° C., 20 g of diallyl ether of bisphenol S, 20 g of toluene and 0.493 g of a xylene solution of platinum vinylsiloxane complex (containing 3 wt% of platinum) diluted 100 times with toluene were added, and glass was added. Diallyl ether of bisphenol S attached to the wall was poured into 4 g of toluene. This operation was performed 4 times every 20 minutes (100 g of diallyl ether of bisphenol S used in Example 6). Two hours after the completion of the dropwise addition, it was confirmed by ¹ H-NMR that the reaction rate of the allyl group was 95% or more, and the reaction was terminated by cooling. The unreacted rate of 1,3,5,7-tetramethylcyclotetrasiloxane was 0.4%. As a gelation retarder, 0.199 g of a solution obtained by diluting triphenylphosphine with toluene 100 times was added to the reaction solution. A total of 5,000 ppm or less of unreacted 1,3,5,7-tetramethylcyclotetrasiloxane, toluene and allyl glycidyl ether by-product (inner transition products of allylic glycidyl ether vinyl group (cis isomer and trans isomer)) Until the pressure was reduced, a slightly yellow transparent liquid was obtained.

The viscosity of this product was 5.8 Pa · s. This product is a product in which a part of the SiH group of 1,3,5,7-tetramethylcyclotetrasiloxane has reacted with the allyl group of allyl glycidyl ether and diallyl ether of bisphenol S from ¹ H-NMR measurement. It was found to contain 3.1 mmol / g SiH groups. When this product was subjected to GPC measurement, a multimodal chromatogram was obtained. A compound group in which 1,3,5,7-tetramethylcyclotetrasiloxane, allyl glycidyl ether and diallyl ether of bisphenol S were reacted (the following structural formula) ) And 1,3,5,7-tetramethylcyclotetrasiloxane and allyl glycidyl ether reaction group.

Tables 1 to 6 and Comparative Examples 1 to 3 show the results of the unreacted ratio of 1,3,5,7-tetramethylcyclotetrasiloxane after completion of the hydrosilylation reaction and the viscosity of the resulting SiH group-containing compound. It was shown in 1.

By using the production method of the present invention, a low-viscosity compound having at least two SiH groups can be obtained without gelation without requiring recycling of a polyorganosiloxane raw material having SiH groups. Can be manufactured.

Claims (8)

(A) A linear and / or cyclic polyorganosiloxane compound having at least three SiH groups in one molecule, and (B) one carbon-carbon double bond having reactivity with SiH groups in one molecule. After reacting the compound containing the compound in the presence of (D) a hydrosilylation catalyst, a further obtained reaction product and (C) a carbon-carbon double bond having reactivity with the SiH group are contained in one molecule. A method for producing a compound containing at least two SiH groups in one molecule, characterized by reacting a compound containing at least two in the presence of (D) a hydrosilylation catalyst ,
Component (B) is monoallyl diglycidyl isocyanurate, allyl glycidyl ether, allyl vinyl ether, allyl methacrylate, allyloxyethyl methacrylate, allyl acrylate, allyloxyethyl acrylate, vinyltrimethoxysilane, or 4-vinylcyclohexene-1-oxide And
Component (C) is diallyl phthalate, triallyl trimellitate, diethylene glycol bisallyl carbonate, trimethylolpropane diallyl ether, pentaerythritol triallyl ether, 1,1,2,2-tetraallyloxyethane, diarylidenepentaeri Slit, triallyl cyanurate, triallyl isocyanurate, 1,2,4-trivinylcyclohexane, divinylbenzene, divinylbiphenyl, 1,3-diisopropenylbenzene, 1,4-diisopropenylbenzene, diallyl monoglycidyl isocyanate Nurate, diallyl ether of bisphenol A, diallyl ether of bisphenol S, oligomers thereof, 1,2-polybutadiene, allyl ether of novolak phenol, allylated polyphenyle Oxide, the following formula

A method for producing a compound containing at least two SiH groups in one molecule, which is a compound represented by the formula: an aliphatic chain polyene compound, an aliphatic cyclic polyene compound, or a substituted aliphatic cyclic olefin compound . (A) The average number of SiH groups in one molecule of the component (α), the average number of molecules (β) of the component (B) that undergoes a hydrosilylation reaction with the component (A), and the hydrosilylation reaction of the component (A) (C 2) The method for producing a SiH group-containing compound according to claim 1, wherein the average number of allyl groups in the component is one (α−β) ≦ 3.5. (A) component is the following general formula (I)

(In the formula, R ¹ represents an organic group having 1 to 6 carbon atoms, and each R ¹ may be different or the same. N represents a number of 3 to 10). The method for producing a SiH group-containing compound according to claim 1, wherein the SiH group-containing compound is a cyclic polyorganosiloxane compound. (B) A component is allyl glycidyl ether, The manufacturing method of the SiH group containing compound as described in any one of Claims 1-3 characterized by the above-mentioned. Component (C), carbon reactive with a SiH group in each molecule - carbon double bond and containing 2 to 3, and, according to claim 1-4, wherein the molecular weight is less than 900 The manufacturing method of the SiH group containing compound as described in any one. (C) A component is triallyl isocyanurate, The manufacturing method of the SiH group containing compound as described in any one of Claims 1-5 characterized by the above-mentioned. (C) A component is diallyl monoglycidyl isocyanurate, The manufacturing method of the SiH group containing compound as described in any one of Claims 1-5 characterized by the above-mentioned. (C) A component is diallyl ether of bisphenol S, The manufacturing method of the SiH group containing compound as described in any one of Claims 1-5 characterized by the above-mentioned.