JPH11116586A - Production of organosilicon compound and silane coupling agent - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject compound useful as a silane coupling agent, a silicon modifying agent for special uses or the like by adding an unsaturated compound having at least one terminal unsaturated group to a specific α,ω- dihydrosiloxane. SOLUTION: An unsaturated compound having at least one terminal unsaturated group (e.g. allyl acrylate) is added to an α,ω-dihydrosiloxane, expressed by a structural formula represented by formula I [R<1> to R<3> are each an alkyl, a cycloalkyl or an aryl; X is an alkoxy, an aryloxy, an alkyl, a cycloalkyl or an aryl ; (n) is a positive number of 1-10,000] to thereby afford the objective organosilicon compound, represented by formula II (R<0> is a residue formed as a result of addition reaction of the unsaturated compound and a carbon functional group bindable to an organic compound) and useful as a silane coupling agent capable of manifesting good coupling performances for calcium carbonate or the like, a silicone modifying agent for special uses or the like capable of manifesting high-level functions.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing an organosilicon compound and a silane coupling agent, and more particularly, to a method for producing an organosilicon compound having a siloxane bond in the main chain and a polysiloxane type silane coupling agent. About. The method for producing an organosilicon compound of the present invention is suitably used as a method for producing a silane coupling agent in the present invention, and is also useful as a method for producing various other organosilicon compounds.

[0002]

2. Description of the Related Art Various organosilicon compounds having a structure in which another compound is introduced into both ends of a siloxane chain (hereinafter referred to as "both-terminal modified silicone") are known. This double-terminal modified silicone is useful because it can exhibit the functions of the above-mentioned "other compounds" in addition to the so-called "characteristics of silicone" such as releasability, surface lubricity and water / oil repellency. As an example of this double-terminal modified silicone, there is one represented by the following structural formula (III). Note that R ′ represents a terminal group introduced by the other compound.

[0003]

Embedded image (Where R ¹ , R ² , and R ³ are an alkyl group, a cycloalkyl group, or an aryl group, X is an alkoxy group, an aryloxy group, an alkyl group, a cycloalkyl group, or an aryl group, and n is a positive number. Is.)

[0004]

In the above formula (III), R ¹ is an ethyl group, both R ² and R ³ are methyl groups, X is an ethoxy group, and the other compound is polyethylene. A conventional method for producing this double-terminal-modified silicone will be described by taking the case of an oxide-modified triacrylate as an example. [First method] An alkoxysilane having an acryloyl group is produced by a hydrosilylation reaction of the following formula (1), and then, as shown in the following formula (2), the alkoxysilane and polysiloxane-α, ω- React with diol.

[0005]

Embedded image

[Second Method] An alkoxychlorosilane having an acryloyl group is reacted with polysiloxane-α, ω-diol.

However, according to the first method, it is necessary to use a catalyst such as p-toluenesulfonic acid and a solvent for the dealcoholization in the step of the above formula (2). With such use of the acid catalyst, in addition to the dealcoholization reaction of interest, because the Si-OH What was the dehydration reaction as a side reaction can occur, thereby by-product H ₂ O and the alkoxy group in an acidic atmosphere As a result, a condensation reaction between the alkoxy groups may occur, resulting in an undesirable compound or gelling of the reaction solution. In addition, since a step of removing the catalyst and the solvent is required after the reaction, the production process becomes complicated. Further, there is a problem that an α-adduct is partially generated in the hydrosilylation of the above formula (1), and in the subsequent stage of the above-mentioned formula (2), this α-adduct is decomposed by silanol to produce an alkyl ester as a by-product. is there. On the other hand, according to the second method, it is difficult to remove hydrogen chloride by-produced during the reaction, and there is a problem that the hydrogen chloride causes corrosion of the apparatus.

On the other hand, a silane coupling agent is generally an organic silicon compound having a hydrolyzable group for bonding to an inorganic compound and a carbon functional group for bonding to an organic compound on a silicon atom. It has a function of bonding a compound and an inorganic compound. For this reason, it is widely used as a composite material comprising an organic compound and an inorganic compound, for example, a glass fiber surface treatment agent in the production of reinforced plastics. At this time, depending on the use of the composite material to be produced, in addition to the function as a normal silane coupling agent for binding an organic compound and an inorganic compound, the obtained composite material has properties due to the silane coupling agent, for example, peelability. In some cases, it is preferable to impart so-called “silicone properties” such as surface lubricity and water / oil repellency. However, many of the conventional silane coupling agents had only a single silicon atom in the molecule.
Was difficult to impart. Further, according to the conventional silane coupling agent having one silicon atom in the molecule, there is a problem that it is difficult to obtain a coupling effect with respect to inorganic compounds such as calcium carbonate.

It is an object of the present invention to provide a method for producing a double-terminal modified silicone as an organosilicon compound, in which the above-mentioned problems have been solved. Another object of the present invention is to
An object of the present invention is to provide a method for producing a polysiloxane-type silane coupling agent, which has a function of imparting silicone properties in addition to a function as a normal silane coupling agent.

[0010]

Means for Solving the Problems The present inventors have found that the above-mentioned problems in the conventional method can be solved by using a predetermined intermediate material when producing a double-ended silicone. Further, this method is suitable as a method for producing a silane coupling agent in which the main chain is composed of a siloxane bond and both silicon atoms at both ends have an alkoxyl group and a carbon functional group, and the obtained silane coupling agent is The present invention has been found to have a function of imparting the properties of silicone in addition to the function as a silane coupling agent, and to show an excellent coupling effect even to inorganic compounds such as calcium carbonate. It is.

That is, the method for producing an organosilicon compound according to the first aspect of the present invention provides an α, ω-dihydrosiloxane represented by the following structural formula (I) having at least one terminal unsaturated group. It is characterized by adding an unsaturated compound (hereinafter referred to as “terminal unsaturated compound”).

[0012]

Embedded image (Provided that R ¹ , R ² , and R ³ are each an alkyl group, a cycloalkyl group, or an aryl group, X is an alkoxy group, an aryloxy group, an alkyl group, a cycloalkyl group, or an aryl group; It is a positive number of 10,000.)

Here, the “terminal unsaturated group” in the first invention refers to a group having a carbon-carbon unsaturated bond at a terminal. Specific examples of the terminal unsaturated group include a vinyl group, an allyl group, a methallyl group, an ethynyl group, a propargyl group, an isopropenyl group and a (meth) acryloyl group.

The method for producing a silane coupling agent according to the second to fourth aspects of the present invention will be described below. This corresponds to the case where a compound having a compound binding group (hereinafter, referred to as “functional unsaturated compound”) is used. Further, the organosilicon compound obtained by adding a functional unsaturated compound to the compound represented by the above formula (I) by this production method is not limited to a silane coupling agent, and may be, for example, a curable resin, a resin modifier, a phase modifier. It is also useful as a solubilizer, dispersant, and the like.

Further, the above terminal unsaturated compound is not limited to the above functional unsaturated compound, and may be, for example, a polystyrene macromer, a polymethyl methacrylate macromer, or the like.
A polymer having an unsaturated group at the terminal may be used. In this case, a polymer having a siloxane chain introduced at the center is obtained, and this polymer is useful as a resin modifier, a compatibilizer, a release agent, a lubricant, and the like.

The method for producing a silane coupling agent according to the second aspect of the present invention is a method for producing a silane coupling agent represented by the following formula (II):
Α, represented by the structural formula shown in the formula (I) according to claim 1,
An unsaturated compound having at least one terminal unsaturated group is added to ω-dihydrosiloxane.

[0017]

Embedded image (Where R ⁰ is a residue formed as a result of an addition reaction of an unsaturated compound and is a carbon functional group capable of bonding to an organic compound, and the meanings of R ¹ , R ² , R ³ , X and n are as defined above. Formula (I)
Is the same as that shown in FIG. )

In the silane coupling agent produced by the method of the second invention, since the silicon atoms at both ends have at least one hydrolyzable group and a carbon functional group, an organic compound and an inorganic compound are combined at both ends. It has a function to combine And between these two terminal silicon atoms,
That is, the main chain of this compound is composed of siloxane bonds. By this siloxane bond, releasability, surface lubricity and water repellency
"Silicone properties" such as oil repellency can be imparted. Here, the “carbon functional group” refers to a structural part containing a carbon atom and having at least a functional group capable of bonding to an organic compound. The type of the “functional group capable of binding to an organic compound (hereinafter, referred to as“ organic compound binding group ”)” is not particularly limited. ) An acryloyl group,
It is preferably a vinyl group, an epoxy group, an amino group, a mercapto group or a halogen atom.

Further, as in the fourth invention, R ¹ , R ² and R ³ in the above formula (I) are each an alkyl group having 1 to 3 carbon atoms, and X in the above formula (I) is 1 carbon atom. ~ 3
Is preferred. In this case,
Since the silicon atoms at both ends each have two alkoxy groups and the alkoxy groups have high hydrolyzability, the binding property between the silane coupling agent of the present invention and the inorganic compound is improved. Further, the silane coupling agent produced by the method of the fourth invention is characterized in that the carbon functional group has an acryloyl group as an organic compound binding group. Since the acryloyl group has high reactivity with an organic compound, the silane coupling agent produced by the method of the fourth invention has good coupling properties with both the organic compound and the inorganic compound. Excellent.

The silane coupling agent produced by the method of the present invention binds the organic compound and the inorganic compound in the composite material, and imparts "silicone properties" to the composite material by the silane coupling agent. There is action. This makes it possible to omit or reduce the amount of other additives conventionally used for imparting the properties of silicone. In addition, when silicone properties are imparted by blending of silicone oil or the like, there is a problem that the silicone oil easily bleeds, but silicone properties are imparted by the silane coupling agent manufactured by the method of the present invention. In this case, there is an advantage that bleeding is prevented since both ends of the silicone chain are bonded to the composite material.

[0021]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail.
In this specification, acrylate and / or methacrylate are referred to as (meth) acrylate, and acryloyl and / or methacryloyl groups are referred to as (meth) acryloyl group. First, examples of the “terminal unsaturated compound” to be added to the α, ω-dihydrosiloxane represented by the above formula (I) in the first invention include the following.

[1] Examples of compounds in which the terminal unsaturated group is an alkenyl group: ethylene, propylene, butylene, 1-hexene and 1
Olefins such as octene; aromatic compounds such as styrene, α-methylstyrene, allylbenzene and methallylbenzene; ethers such as methyl vinyl ether, allyl methyl ether, allyl phenyl ether, allyl glycidyl ether and methallyl glycidyl ether; vinyl acetate Esters such as vinyl, vinyl propionate, allyl (meth) acrylate, methallyl (meth) acrylate and allyl phthalate; nitrogen-containing compounds such as allylamine, methallylamine, diallylamine and triallylamine; sulfur-containing compounds such as allylmethylthioether and allylglycidylthioether Compounds; Halogen-containing compounds such as vinyl chloride, allyl chloride and methallyl chloride; vinyl trimethylsilane and allyltrimethylsilane Silicon compounds, and the like. Further, compounds having two or more unsaturated terminal groups, such as diallyl phthalate, can also be used.

[2] Examples of compounds in which the terminal unsaturated group is a (meth) acryloyl group [2-1] Methyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate , 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-hydroxyethyl (meth)
Acrylate, 2-hydroxypropyl (meth) acrylate, perfluoroalkyl (meth) acrylate,
(Meth) acrylates such as glycidyl (meth) acrylate and N, N-diethylaminoethyl (meth) acrylate.

[2-2] Phenol ethylene oxide (hereinafter referred to as "EO") modified (meth) acrylate, phenol propylene oxide (hereinafter referred to as "PO")
That. ) Modified (meth) acrylate, Nonylphenol EO Modified (meth) acrylate, Nonylphenol P
O-modified (meth) acrylate, 2-ethylhexyl carbitol (meth) acrylate, isobornyl (meth)
Acrylate, tetrahydrofurfuryl (meth) acrylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, hydroxyhexyl (meth)
Acrylate, diethylene glycol mono (meth) acrylate, dipropylene glycol mono (meth) acrylate, triethylene glycol mono (meth) acrylate, tripropylene glycol mono (meth) acrylate, tetraethylene glycol mono (meth) acrylate, 1,4-butane Diol mono (meth) acrylate, 1,5-pentanediol mono (meth) acrylate, 1,6-hexanediol mono (meth) acrylate, 1,9-nonanediol mono (meth) acrylate, neopentyl glycol mono (meth) Acrylate, neopentyl glycol EO-modified mono (meth) acrylate, neopentyl glycol PO-modified mono (meth) acrylate, bisphenol A EO-modified mono (meth) acrylate, bis Phenol A PO-modified mono (meth) acrylate, hydrogenated bisphenol A EO
(Meth) such as modified mono (meth) acrylate and hydrogenated bisphenol A PO modified mono (meth) acrylate
A (meth) acrylate compound having one acryloyl group.

[2-3] Diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate
Acrylate, tetraethylene glycol di (meth) acrylate, nonaethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, tetrapropylene glycol di (meth) acrylate, polypropylene glycol di (Meth) acrylate, 1,4-butanediol di (meth) acrylate,
1,5-pentanediol di (meth) acrylate,
1,6-hexanediol di (meth) acrylate,
1,9-nonanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, neopentyl glycol ethylene oxide (hereinafter, “ethylene oxide” is referred to as EO) modified di (meth) acrylate, neopentyl glycol propylene oxide (hereinafter, referred to as EO) , “Propylene oxide” is referred to as PO.) Modified di (meth) acrylate, bisphenol AEO-modified di (meth) acrylate, bisphenol A PO-modified di (meth) acrylate, hydrogenated bisphenol A EO-modified di (meth) acrylate, hydrogenated Bisphenol A P
O-modified di (meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolpropane E
O-modified di (meth) acrylate, trimethylolpropane PO-modified di (meth) acrylate, glycerin di (meth) acrylate, glycerin EO-modified di (meth) acrylate, glycerin PO-modified di (meth) acrylate, trimethylolpropane tri (meth) A) acrylate, trimethylolpropane EO modified tri (meth) acrylate, trimethylolpropane PO modified tri (meth) acrylate, glycerin tri (meth) acrylate, glycerin EO modified tri (meth) acrylate, glycerin PO modified tri (meth) acrylate, Pentaerythritol EO-modified tetra (meth) acrylate, pentaerythritol PO-modified tetra (meth) acrylate, ditrimethylolpropanetetra (meth) acrylate, pentaerythritol (Meth) acrylates such as tri (meth) acrylate, pentaerythritol EO-modified tri (meth) acrylate, pentaerythritol PO-modified tri (meth) acrylate, dimethylolpropane tri (meth) acrylate, and trimethylolpropane allyl ether di (meth) acrylate. ) Polyfunctional (meth) acrylate compounds having two or more acryloyl groups.

When the production method of the first invention is applied to the production method of the silane coupling agent of the second invention to the fourth invention, allyl (meth) acrylate, methallyl (meth) acrylate, Or the above [2-
By using the “polyfunctional (meth) acrylate compound having two or more (meth) acryloyl groups” shown in 3], a silane coupling agent in which the organic compound bonding group is a (meth) acryloyl group can be obtained. . Similarly, when manufacturing a silane coupling agent in which the organic compound bonding group is a vinyl group, acetylene or diallyl phthalate is used as the terminal unsaturated compound, and when the organic compound bonding group is an epoxy group, allyl glycidyl ether is used. , Methallyl glycidyl ether or glycidyl (meth) acrylate, etc., when the organic compound binding group is an amino group, allylamine or methallylamine, and when the organic compound binding group is a mercapto group, allyl methyl thioether, etc. When the organic compound bonding group is a halogen atom, vinyl chloride, allyl chloride, methallyl chloride, or the like may be used as the terminal unsaturated compound.

Next, a method of "adding" a terminal unsaturated compound to the compound represented by the formula (I) will be described. This is a hydrosilylation reaction between Si-H groups at both ends of the compound represented by the formula (I) and the terminal unsaturated group of the terminal unsaturated compound, and proceeds in the presence of a Group VIII metal catalyst or the like. . Examples of the “Group 8 metal catalyst” include simple substances of Group 8 metals such as cobalt, nickel, ruthenium, rhodium, palladium, iridium and platinum, organometallic complexes, metal salts and metal oxides. Of these, simple platinum metals, organometallic complexes, metal salts and metal oxides are preferred, and organic platinum complexes are particularly preferred, for reasons such as high catalytic activity and ease of handling. This catalyst is preferably used in an amount of 10 to 1,000 ppm by weight based on the total amount of the compound represented by the formula (II) and the terminal unsaturated compound. Other reaction conditions in the hydrosilylation reaction are not particularly limited,
The preferred reaction temperature is 20-80 ° C, and the preferred reaction time is 2-10 hours.

The compound represented by the formula (I) can be suitably produced, for example, by a condensation reaction of a compound represented by the following formula (IV) with a compound represented by the following formula (V). This reaction is preferably carried out under conditions in which the compound represented by the following formula (V) becomes excessive (preferably large excess). Further, at the time of the reaction, a transesterification catalyst such as p-toluenesulfonic acid or trifluoroacetic acid may be used, or a transesterification catalyst may not be used, but under a neutral atmosphere without using these catalysts. It is preferred that the above condensation reaction proceeds.

[0029]

Embedded image (However, R ² and R ³ are an alkyl group, a cycloalkyl group or an aryl group, respectively, and n is 0 to 10,000.
Is a positive number. )

[0030]

Embedded image (Where R ¹ is an alkyl group, a cycloalkyl group or an aryl group, X is an alkoxy group, an aryloxy group,
It is an alkyl group, a cycloalkyl group or an aryl group. )

Here, regarding the advantages of the production method of the first invention, R ¹ , R ² and R ³ are all ethyl groups, X is an ethoxy group, and the terminal unsaturated compound is a PO-modified triacrylate. A case will be described as an example. The following formulas (3) to (4) schematically show reaction formulas for producing this organosilicon compound from the step of producing the compound represented by formula (I) by the above method. At this time, the reaction of the above formula (3) can proceed without a catalyst and without a solvent.

[0032]

Embedded image

According to the methods of the above formulas (3) to (4) using the organosilicon compound of the present invention as an intermediate raw material, unlike the first method described as the conventional production method, the use of an acid catalyst is required. Since the dealcoholation reaction can proceed without the reaction, the condensation reaction between the alkoxy groups is suppressed. Further, the production process is simplified because the removal of the catalyst and the solvent is unnecessary. Further, unlike the second method, the production method of the present invention is excellent in that no hydrogen chloride is generated.

The second to fourth inventions relate to a method for producing the silane coupling agent represented by the formula (II) by applying the method of the first invention. Here, in the above formula (II), R ¹ , R ² and R ³ are each an alkyl group, a cycloalkyl group or an aryl group. This "alkyl group"
Examples thereof include a methyl group, an ethyl group, n- and i-propyl groups, n-, i- and t-butyl groups. Examples of the “cycloalkyl group” include a cyclohexyl group, and examples of the “aryl group” include a phenyl group. One molecule of the compound represented by the above formula (II) contains two R ^{1 s,} which may be the same or different. Further, R ² and R ³ may be the same group or different groups. Furthermore, may be an n-number of R ² is also different for two or more be all the same radical groups contained in one molecule is the same for R ^3.

In the above formula (II), X is an alkoxy group, an aryloxy group, an alkyl group, a cycloalkyl group or an aryl group. Examples of the “alkoxy group” include a methoxy group, an ethoxy group, n- and i-propoxy groups, n-, i- and t-butoxy groups. Examples of the "aryloxy group" include a phenoxy group. As the “alkyl group”, “cycloalkyl group” and “aryl group”, R ¹ , R ²
And the like can be used those exemplified respectively in the description of R ^3. Here, two Xs contained in one molecule
May be the same or different groups.

Among them, as in the fourth invention, it is preferable that R ¹ is an alkyl group having 1 to 3 carbon atoms and X is an alkoxy group having 1 to 3 carbon atoms. That is, R ¹ is preferably a methyl group, an ethyl group, an n-propyl group or an i-propyl group, and X is preferably a methoxy group, an ethoxy group, an n-propoxy group or an i-propoxy group. In this case, silicon atoms each two alkoxy groups at both ends (i.e., -OR ¹ and -X) so will have a binding property between the resulting silane coupling agent and the inorganic compound becomes good . Further, an alkoxy group having 1 to 3 carbon atoms has high hydrolyzability, so that the bondability with an inorganic compound is further improved.

When R ² and R ³ are a methyl group or an ethyl group, the silane coupling agent can be produced from inexpensive raw materials and the “characteristics of silicone”
Is preferable because R ² and R ³ are all methyl groups. Further, when two R ¹ and two Xs present in one molecule are the same group, it is preferable because the synthesis of the silane coupling agent is easy, and -OR ¹ and -X are the same group. Is more preferred. Further, when -OR ¹ and -X are ethoxy groups, there is an advantage that the obtained silane coupling agent has low toxicity.

As the carbon functional group R ⁰ in the above formula (II), one having an appropriate structure and an organic bonding group may be selected according to the type and use of the organic compound to be coupled. However, those having an acryloyl group as the organic bonding group as in the fourth invention are preferable. This is because the acryloyl group among the functional groups described in the third invention has a particularly high reactivity to an organic compound, and therefore, the silane coupling agent in which the carbon functional group R ⁰ has an acryloyl group is suitable for both organic compounds and inorganic compounds. And good coupling properties, and thus excellent coupling performance.

In the above formula (II), n is 0 to 1
It is a positive number of 0000. This is because if n exceeds 10,000, problems occur such as the viscosity being too high and handling difficult. From the viewpoint of preventing this problem, n is preferably 1,000 or less, and more preferably 200 or less. Further, in order to more favorably exhibit the properties of silicone, n is preferably 1 or more, and more preferably 3 or more.

[0040]

The present invention will now be described more specifically with reference to examples and comparative examples.

(Synthesis Example 1) This is an example of synthesizing α, ω-dihydrosiloxane represented by the above formula (I), which is used as a raw material in the method for producing a silane coupling agent of the present invention. According to the reaction formula shown in the following formula (5), R ¹ in the above formula (I) is an ethyl group, X is an ethoxy group, both R ² and R ³ are methyl groups, and n
Α, ω-type polydimethylsiloxane (hereinafter referred to as “silicone A”) having a value of about 20 was synthesized.

[0042]

Embedded image

The raw materials used are as follows. [Raw materials] (1) Polydimethylsiloxane-α, ω-diol (manufactured by Dow Corning Toray Silicone Co., Ltd., number average molecular weight 1,272 (in terms of polystyrene)) (2) Triethoxysilane (manufactured by Toagosei Co., Ltd. Product name "Tries")

Hereinafter, the reaction operation will be described. A 100 ml four-necked flask equipped with a stirrer, a thermometer, and a cooler was charged with 10.0 g (7.9 mmol) of polydimethylsiloxane-α, ω-diol, and after degassing under vacuum, the system was purged with nitrogen. The reactor was heated to 60 ° C and triethoxysilane 1
5.0 g (92 mmol) was added, and the reaction was allowed to proceed with stirring while maintaining the inside of the system at 60 ° C. The progress of the reaction was followed by gas chromatography. After 6 hours, it was confirmed that the composition ratio of the raw material triethoxysilane and the by-produced ethanol had not changed, and the reaction was terminated. Excess triethoxysilane and by-produced ethanol were removed from the obtained reaction solution under reduced pressure. Further, under a heated vacuum atmosphere (60 to 70 ° C., 0.01 torr), volatile impurities are removed, and a colorless and transparent viscous liquid is obtained.
8 g were obtained.

The obtained substance was identified as 2 in the IR chart.
A peak indicating the presence of a hydrogen atom bonded to a terminal silicon atom was observed at around 200 cm ^-1 . Also, the N
In the MR chart, a peak at 3.8 ppm (corresponding to a hydrogen atom (Si—OCH ₂ —) bonded to a carbon atom adjacent to oxygen in an ethoxy group bonded to a terminal silicon atom) and a peak at 4.7 ppm (terminal The ratio of the number of ethoxy groups bonded to the terminal silicon atoms to the number of hydrogen atoms is 2: 1 based on the ratio of the peak area to the hydrogen atom (corresponding to the hydrogen atom (Si-H) bonded to the silicon atom). understood.
From the above, it was confirmed that silicone A in which R ¹ in the above formula (I) was an ethyl group, X was an ethoxy group, and both R ² and R ³ were methyl groups was synthesized.

(Example 1) Silicone A obtained in Synthesis Example 1
Was added with a terminal unsaturated compound to produce a polysiloxane-type silane coupling agent in which the organic compound bonding group was an acryloyl group. Hereinafter, the reaction operation will be described. 30.0 g (21 mmol) of silicone A and 60.0 g (47 mmol) of allyl acrylate were put into a 100 ml reactor equipped with a stirrer, a thermometer and a cooler, and the temperature of the system was raised to 70 to 80 ° C. PtCl ₂ (C ₆ H ₅
100 μl of a 0.05M benzonitrile solution of CN) ₂ was charged. Then, while maintaining the inside of the system at 70 to 80 ° C,
Allowed to react for hours. After completion of the reaction, excess volatile substances such as allyl acrylate and benzonitrile were distilled off to obtain a target substance, silane coupling agent B-1.

(Example 2) Silicone A obtained in Synthesis Example 1
Was added with a terminal unsaturated compound to produce a polysiloxane-type silane coupling agent in which the organic compound bonding group was an epoxy group. Hereinafter, the reaction operation will be described. In a 100 ml reactor equipped with a stirrer, thermometer and cooler,
After adding 30.0 g (21 mmol) of silicone A and 5 g (44 mmol) of allyl glycidyl ether, the temperature of the system was raised to 70 to 80 ° C., and then PtCl ₂ (C ₆ H ₅ C)
100 μl of a 0.05 M benzonitrile solution of N) ₂ was charged. Thereafter, the reaction was carried out for 4 hours while maintaining the inside of the system at 70 to 80 ° C. After completion of the reaction, volatile substances such as excess allyl glycidyl ether and benzonitrile are distilled off,
The target substance, the silane coupling agent B-2, was obtained.

The present invention is not limited to the specific embodiments described above, but may be variously modified within the scope of the present invention in accordance with the purpose and application.

[0049]

According to the method for producing an organosilicon compound of the present invention, a silane coupling agent and another organosilicon compound can be produced in a simple process. In addition, the silane coupling agent obtained by the production method of the present invention has a main chain of a siloxane bond, and in addition to the function as a normal silane coupling agent for bonding an organic compound and an inorganic compound, is obtained. It has a function of imparting so-called "silicone properties" such as releasability, surface lubricity and water / oil repellency to the resulting composite material. Therefore, it is useful as a special purpose silicone modifier capable of exhibiting advanced functions. Also, unlike conventional silane coupling agents that have only a single silicon atom, they show good coupling performance to calcium carbonate and the like.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Takehisa Yamamura 1-1, Funamicho, Minato-ku, Nagoya-shi, Aichi Prefecture Inside Nagoya Research Institute, Toagosei Co., Ltd. (72) Inventor Kaoru Kimura Funamicho, Minato-ku, Nagoya-shi, Aichi No. 1, No. 1 Toagosei Co., Ltd. Nagoya Research Laboratory

Claims (4)

[Claims] An organosilicon compound characterized by adding an unsaturated compound having at least one terminal unsaturated group to α, ω-dihydrosiloxane represented by the structural formula shown in the following formula (I). Production method. Embedded image (Provided that R ¹ , R ² , and R ³ are each an alkyl group, a cycloalkyl group, or an aryl group, X is an alkoxy group, an aryloxy group, an alkyl group, a cycloalkyl group, or an aryl group; It is a positive number of 10,000.) 2. The method according to claim 1, wherein an unsaturated compound having at least one terminal unsaturated group is added to the α, ω-dihydrosiloxane represented by the structural formula represented by the formula (I). And a method for producing a silane coupling agent represented by the following structural formula (II). Embedded image (Where R ⁰ is a residue formed as a result of an addition reaction of an unsaturated compound and is a carbon functional group capable of bonding to an organic compound, and the meanings of R ¹ , R ² , R ³ , X and n are as defined above. Formula (I)
Is the same as that shown in FIG. ) 3. The method for producing a silane coupling agent according to claim 2, wherein the carbon functional group has a (meth) acryloyl group, a vinyl group, an epoxy group, an amino group, a mercapto group, or a halogen atom. 4. R ¹ in the formula (II) according to claim 2,
R ² and R ³ are each an alkyl group having 1 to 3 carbon atoms, X in the formula (II) is an alkoxy group having 1 to 3 carbon atoms, and the carbon functional group has an acryloyl group. A method for producing the described silane coupling agent.