JP2864866B2 - Method for producing organosilicon compound - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an organosilicon compound such as an alkylalkoxysilane useful as a surface modifier.
The present invention relates to a method for producing an organosilicon compound which can be efficiently synthesized in a high yield in a step.

[0002]

2. Description of the Related Art A reaction for adding a ≡SiH group to an organic compound having an unsaturated double bond is known as a hydrosilylation reaction, and is used for synthesizing a new organosilicon compound. Have been. In such a hydrosilylation reaction, various platinum-based catalysts are generally used. For example, platinum catalysts supported on activated carbon (U.S. Pat. No. 2,970,150) and chloroplatinic acid (Second Patent Publication No. , 823,218), platinum-organic compound complexes (3,159,601) and platinum-organofunctional siloxane complexes (JP-B-63-19218) are known.

[0003] On the other hand, organosilicon compounds such as alkylalkoxysilanes are produced by utilizing the above reaction. For example, after a hydrosilylation reaction between a terminal olefin compound and hydrochlorosilane, a chloro group is converted into an alkoxy group with an alcohol. It is synthesized in a two-step reaction. In the hydrosilylation at this time, the terminal double bond of the terminal olefin compound undergoes internal rearrangement, but finally a silyl group is added to the terminal.

[0004] However, the above reaction is a two-step reaction, so that there are problems such as inefficiency and treatment of by-product hydrochloride.

[0005] As a measure for solving such a problem, a method is considered in which the terminal olefin compound and the hydroalkoxysilane are directly hydrosilylated to omit the alkoxylation in the second step reaction. However, when this direct hydrosilylation reaction is carried out using the above-mentioned platinum catalyst, internal rearrangement of the terminal unsaturated double bond of the terminal olefin compound occurs, and a large amount of its isomer remains as a terminal reactant. However, the yield of the organosilicon compound was greatly reduced. Further, when the above reaction is carried out using a terminal olefin compound and a hydrogen-containing siloxane compound, the yield similarly becomes low.

[0006] Under such circumstances, it has been difficult to produce an organosilicon compound industrially advantageously using a hydrosilylation reaction using a terminal olefin compound as a raw material.

[0007] The present invention has been made in view of the above circumstances,
An object of the present invention is to provide a method for producing an organosilicon compound that can efficiently synthesize an organosilicon compound such as an alkylalkoxysilane in one step with a high yield using a terminal olefin compound.

[0008]

The present inventors have made intensive studies to achieve the above object, and as a result, have found that the terminal olefin compound represented by the following general formula (I) and the following general formulas (II) and (III) ) Or (IV) a hydrosilylation reaction with a silicon-bonded hydrogen-containing organosilicon compound to add a silicon-bonded hydrogen atom of the organosilicon compound to the —CH ＝ CH ₂ group of the olefin compound;
When a tertiary amine other than a tertiary amine in the form of an anion exchange resin is used in combination with platinum metal or a platinum compound as a catalyst, internal rearrangement of the terminal unsaturated double bond of the terminal olefin compound is suppressed as much as possible. An organic compound represented by the following general formula (V), (VI) or (VII) such as an alkylalkoxysilane or an alkylpolysiloxane is efficiently produced in a one-step reaction with little residual unreacted material and in high yield. The inventors have found that a silicon compound can be synthesized, and have accomplished the present invention.

[0009]

Embedded image R ¹ —CH ＝ CH ₂ (I) (wherein, R ¹ is a substituted or unsubstituted alkyl group having 2 to 30 carbon atoms) (However, in the formula, R ² and R ³ are the same or different and are each a substituted or unsubstituted alkyl group or aryl group having 1 to 10 carbon atoms, and k is an integer of 1 to ^3. ) (Wherein, R ^{4 to} R ¹⁰ are the same or different, respectively, substituted or unsubstituted alkyl groups, cycloalkyl groups or aryl groups, and X is a hydrogen atom, a substituted or unsubstituted alkyl group, a cycloalkyl group or An aryl group, m is an integer of m ≧ 0 when X is a hydrogen atom, m is an integer of m ≧ 1 when X is not a hydrogen atom, and n is an integer of n ≧ 0.) (Wherein, R ^{11 to} R ¹³ are the same or different substituted or unsubstituted alkyl, cycloalkyl or aryl groups, respectively, and p ≧ 0, q ≧ 1, p + q ≧ 3
It is. )

[0010]

Embedded image (However, in the formula, R ^{1 to} R ¹³ , k, m, n, p, q, and X are the same as described above.)

Accordingly, the present invention relates to the present invention, wherein the terminal olefin compound of the above formula (I) and the above formula (II), (III) or (I
V) reacting the silicon-bonded hydrogen-containing organosilicon compound of the present invention with a platinum metal or a catalyst comprising a platinum compound and a tertiary amine other than a tertiary amine in the form of an anion exchange resin; silicon-bonded hydrogen atoms was added the above formula of the compound above-mentioned organic silicon compound in -CH = CH ₂ group of (V), (VI), organosilicon, characterized in that to obtain a reaction product represented by (VII) A method for producing a compound is provided.

Hereinafter, the present invention will be described in more detail. The terminal olefin compound as a starting material of the organosilicon compound of the present invention is represented by the following general formula (I).

[0013]

Embedded image R ¹ —CH ＝ CH ₂ (I) (wherein R ¹ has 2 to 30 carbon atoms, preferably 2 to ¹ carbon atoms)
0 is a substituted or unsubstituted alkyl group, and the alkyl group may be linear or branched, and examples thereof include an ethyl group, a propyl group, a butyl group, and a pentyl group. )

Specific examples of the terminal olefin compound of the above formula (I) include propene, 1-butene, 1-pentene,
Examples include 1-hexene, 1-heptene, 1-octene, 1-decene and the like.

Next, another starting material, a silicon-bonded hydrogen-containing organosilicon compound, is represented by the following general formula (I)
(I), (III) or (IV).

[0016]

Embedded image (However, in the formula, R ² and R ³ are the same or different and are each a substituted or unsubstituted alkyl group or aryl group having 1 to 10 carbon atoms, and k is an integer of 1 to ^3. ) (Wherein, R ^{4 to} R ¹⁰ are the same or different, respectively, substituted or unsubstituted alkyl groups, cycloalkyl groups or aryl groups, and X is a hydrogen atom, a substituted or unsubstituted alkyl group, a cycloalkyl group or An aryl group, m is an integer of m ≧ 0 when X is a hydrogen atom, m is an integer of m ≧ 1 when X is not a hydrogen atom, and n is an integer of n ≧ 0.) (Wherein, R ^{11 to} R ¹³ are the same or different substituted or unsubstituted alkyl, cycloalkyl or aryl groups, respectively, and p ≧ 0, q ≧ 1, p + q ≧ 3
It is. )

In the above formula, examples of R ² and R ³ include a methyl group, an ethyl group, a butyl group and a propyl group.
Further, it may be an alkoxyalkyl group. In addition, R ⁴
Specific examples of R ¹³ to R ¹³ include a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms such as a methyl group, an ethyl group, a propyl group, a butyl group, a cyclopentyl group, a cyclohexyl group, and a phenyl group, and a cycloalkyl group and an aryl group. Is exemplified. Further, X is a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms and a cycloalkyl group, an aryl group, and the like, as in R ^{4 to} R ¹⁰ .

The formulas (II), (III) and (I)
Specific examples of the silicon-bonded hydrogen-containing organosilicon compound of V) include triethoxysilane, trimethoxysilane, tripropoxysilane, tributoxysilane, methyldimethoxysilane, ethyldimethoxysilane, methyldiethoxysilane, and dimethylmethoxysilane. , Ethyldiethoxysilane, dimethylethoxysilane, 1,1,
Examples thereof include 3,3-tetramethyldisiloxane and the following compounds.

[0019]

Embedded image

Among these silicon-bonded hydrogen-containing organosilicon compounds, trimethoxysilane, triethoxysilane, methyldimethoxysilane and methyldiethoxysilane are preferably used.

The organosilicon compound obtained by subjecting the terminal olefin compound of the formula (I) to a silicon-bonded hydrogen-containing organosilicon compound of the formula (II), (III) or (IV) to undergo a hydrosilylation reaction includes: For example, propyltrimethoxysilane, butyltrimethoxysilane, hexyltrimethoxysilane, octyltrimethoxysilane, decyltrimethoxysilane, hexyltriethoxysilane, octyltriethoxysilane, decyltriethoxysilane, hexylmethyldimethoxysilane,
Hexylmethyldiethoxysilane, octylmethyldimethoxysilane, octylmethyldiethoxysilane, decylmethyldimethoxysilane, decylmethyldiethoxysilane, dimethylhexylmethoxysilane, dimethyldecylmethoxysilane, 1,3-dihexyl-1,1,3,3
3-tetramethyldisiloxane, 1,3-didecyl-
Examples thereof include 1,1,3,3-tetramethyldisiloxane.

The amount of the terminal olefin compound of the above formula (I) and the silicon-bonded hydrogen-containing organosilicon compound of the formula (II), (III) or (IV) is not particularly limited. It is preferable to set the range of 3: 1 to 1: 1.3. If the molar ratio is outside the above range due to excessive use of the terminal olefin compound, the unreacted terminal olefin compound may increase, and if the molar ratio falls outside the above range by excessively using the silicon-bonded hydrogen-containing organosilicon compound. Side reactions other than hydrosilylation may increase,
Both tend to cause a decrease in yield.

In the method of the present invention, platinum metal or a platinum compound and tertiary amines other than tertiary amines in the form of an anion exchange resin are used as the catalyst.

Here, general platinum metals and platinum compounds can be used, and examples of the platinum compound include chloroplatinic acid. These platinum compounds are previously aliphatic alcohols having 1 to 10 carbon atoms, specifically, ethyl alcohol, propyl alcohol, isopropyl alcohol,
It is desirable to use it after dissolving in butyl alcohol, 2-ethylhexyl alcohol or the like, and further performing one or both of heat treatment and neutralization treatment as necessary.

As the platinum compound, a platinum complex can be used. This platinum complex may be zero-valent or divalent, and an olefin or a derivative thereof can be used as a ligand thereof. Specifically, ethylene, octene, cyclooctadiene, styrene, 1,3-divinyl-1,1,3,3
Examples include 3-tetramethyldisiloxane, 1,3,5,7-tetravinyl-1,3,5,7-tetramethyl-cyclotetrasiloxane, and the like.

In the present invention, the amount of platinum metal or platinum compound used is 10-
⁵ mol 10- ³ mol or less. When used in an amount smaller than the above range, the reactivity of hydrosilylation may decrease, and even when used in an amount larger than the above range, not only is it economically disadvantageous, but also the The internal rearrangement of the terminal double bond may increase, and the yield may decrease.

Next, as the tertiary amines, for example, compounds represented by the following general formula are preferably used.

[0028]

Embedded image (In the formula, R ¹⁴ , R ¹⁵ , and R ¹⁶ are the same or different and each is a substituted or unsubstituted monovalent hydrocarbon group, preferably a substituted or unsubstituted alkyl group or aryl group having 1 to 10 carbon atoms.) For example, an ethyl group, a propyl group,
Examples thereof include an isopropyl group, a butyl group, and a phenyl group. )

Specific examples of the tertiary amine represented by the above formula include triethylamine, tributylamine and diisopropylethylamine.

Further, tertiary amines containing a nitrogen atom in an aromatic ring such as pyridine, quinoline and 2,6-lutidine, and 1,8-diazabicyclo [5.4.
0] -7-undecene, 1,4-diazabicyclo [2.
2.2] Special cyclic amines such as octane and hexamethylenetetramine are also suitably used.

The tertiary amine is used in an amount of 1 to 1000 mol, especially 10 mol, per mol of platinum metal or platinum compound.
It is preferred to use it in an amount of about 100 mol. When the tertiary amine is used in an amount smaller than the above range, the effect of suppressing the internal rearrangement of the terminal double bond of the terminal olefin compound is reduced, and the yield may be reduced, and the yield may be reduced. When used in a large amount, the reactivity of hydrosilylation may decrease.

In the present invention, the above-mentioned terminal olefin compound of the formula (I) and a compound of the formula (II), (III) or (IV)
The hydrosilylation reaction with a silicon-bonded hydrogen-containing organosilicon compound is usually carried out without a solvent. In some cases, a solvent inert to the reaction raw materials, the target substance, and the catalyst may be used. The reaction may be carried out under normal pressure or under pressure, but it is usually preferable to carry out the reaction under normal pressure. Further, the reaction temperature is desirably 20 ° C or higher, preferably 40 to 100 ° C, and more preferably 40 to 60 ° C. If the reaction temperature is lower than 20 ° C., the progress of the hydrosilylation reaction may be slow, and the reaction temperature may be lower than 1 ° C.
When the temperature exceeds 00 ° C., internal rearrangement of the terminal double bond of the terminal olefin compound increases, and the yield of the target organosilicon compound may decrease. The reaction time depends on conditions such as the reaction temperature, the combination of the reaction raw materials, and the amount of the catalyst used, but usually about 5 to 10 hours is sufficient.

By the above method, the product of the formula (V) is converted from the terminal olefin compound of the formula (I) and the silicon compound of the formula (II), similarly to the compound of the formula (I) The product of formula (VI) is obtained from the compound of formula (I) and the compound of formula (VI).

[0034]

Embedded image (However, in the formula, R ^{1 to} R ¹³ , k, m, n, p, q, and X are the same as described above.)

[0035]

According to the method for producing an organosilicon compound of the present invention, an organosilicon compound represented by the above formula (V), (VI) or (VII), such as an alkylalkoxysilane or an alkylpolysiloxane, is reacted with a terminal olefin compound. Can be efficiently synthesized in one step at a high yield. Furthermore, the obtained alkoxysilanes and alkylpolysiloxanes are suitable for imparting excellent water repellency by being applied or internally added to the surface of, for example, concrete or building materials, mainly as a surface modifier for inorganic substances. Can be used.
Therefore, the method of the present invention is industrially very advantageous.

[0036]

EXAMPLES The present invention will be specifically described below with reference to examples and comparative examples, but the present invention is not limited to the following examples.

Example 1 20 equipped with a reflux condenser, a thermometer, a dropping funnel and a stirrer
In a 0 ml reactor, 1-decene 84 g (0.6 mol),
Hexamethylenetetramine 0.84 g (0.006 mol), 0.012 g of platinum catalyst _{(H 2 PtCl 6 · 6H 2} O) of those prepared from 2-ethylhexyl alcohol solution) as a platinum atom (0.00006 mol) was added Then, the mixture was heated to 50 ° C. while stirring. next,
73.2 g (0.6 mol) of trimethoxysilane was gradually dropped by a dropping funnel over 3.25 hours. afterwards,
After aging at the same temperature for 3.75 hours, the composition of the reaction solution was analyzed by gas chromatography at that time.
-Decene and trimethoxysilane are almost completely consumed, n-decyltrimethoxysilane 85.3%, 1-
The composition was as high as 3.9% of the two internal isomers of decene.

Comparative Example 1 28 g of 1-decene was placed in the same reactor as used in Example 1.
(0.2 mol), the same platinum catalyst as in Example 1 was added to 0.004 g (0.00002 mol) of platinum atoms, and heated to 50 ° C. while stirring. Next, 18.3 g (0.15 mol) of trimethoxysilane was gradually dropped from the dropping funnel over 1 hour. Thereafter, the mixture was aged at the same temperature for 9 hours. At that time, the composition of the reaction solution was analyzed by gas chromatography. As a result, 1-decene and trimethoxysilane were almost completely consumed. The composition was such as 1% and 26.5% of two 1-decene internal isomers.

Example 2 A reaction was carried out in the same manner as in Example 1 except that 1,8-diazabicyclo [5,4,0] -7-undecene was used instead of hexamethylenetetramine, and the reaction solution was subjected to gas chromatography. Analysis by chromatography revealed that n-decyltrimethoxysilane was 75.3% and two internal isomers of 1-decene were 4.1%.

Example 3 A reaction was carried out in the same manner as in Example 1 except that triethylamine was used instead of hexamethylenetetramine. The reaction solution was analyzed by gas chromatography to find that n-
It was 78% of decyltrimethoxysilane and 7.3% of an internal isomer of 1-decene.

Example 4 The reaction was carried out in the same manner as in Example 1 except that the used platinum catalyst and the used tertiary amine were not changed and the amount used was halved, and the reaction solution was analyzed by gas chromatography.
87.5% of n-decyltrimethoxysilane and 2.5% of two internal isomers of 1-decene.

Comparative Example 2 The reaction was carried out in the same manner as in Comparative Example 1 except that the amount of the platinum catalyst used was reduced to 1/20, and the reaction solution was analyzed by gas chromatography to find that n-decyltrimethoxysilane 7
2.6% and 15.8% of two 1-decene internal isomers.

Example 5 84 g of 1-decene was placed in the same reactor as used in Example 1.
(0.6 mol), hexamethylenetetramine 0.84 g
(0.006 mol), 0.012 g (0.00006 mol) of the same platinum catalyst as in Example 1 as platinum atoms was added, and the mixture was heated to 50 ° C. with stirring. Next, when 52 g (0.1 mol) of the raw material represented by the following formula (1) was added dropwise, and when half of the material was added dropwise, the ratio between 1-decene and internal rearranged product was determined by gas chromatography. -Decene: internal rearrangement = 3.93: 1. Thereafter, the remaining half amount was added dropwise (dropping time: 1.25 hours). After aging for 3.75 hours, IR of the reaction solution was measured.
The Si-H absorption near ^-1 had disappeared.

[0044]

Embedded image

Comparative Example 3 A reaction was carried out in the same manner as in Example 5, except that hexamethylenetetramine was not used and only a platinum catalyst was used. Equation (1) above
Was added dropwise, and the ratio of internal rearrangement at the same reaction rate as in Example 1 was confirmed by gas chromatography. As a result, 1-decene: internal rearrangement = 1.89:
It was one.

Continuing from the front page (72) Inventor Katsuhiro Uehara 28-1 Nishifukushima, Nishi-Jukumura, Nakakushiro-gun, Niigata Prefecture Shin-Etsu Chemical Co., Ltd., Synthetic Technology Research Laboratory (72) Inventor Toru Kubota Nishi-Fukushima, Niigata Prefecture 28-1 Shin-Etsu Chemical Co., Ltd., Synthetic Technology Research Institute (72) Inventor Mikio Endo 28-1 Nishifukushima, Oku-ku, Nishigata-gun, Niigata Prefecture Shin-Etsu Chemical Co., Ltd. -17488 (JP, A) (58) Fields investigated (Int. Cl. ⁶ , DB name) C07F 7/08 C07F 7/18 CA (STN) REGISTRY (STN) WPI (DIALOG)

Claims (1)

(57) [Claims] 1. An olefin compound having a terminal olefin represented by the following general formula (I) and the following general formula (II), (III) or (I)
Reacting the silicon-bonded hydrogen-containing organosilicon compound represented by V) with a platinum metal or a platinum compound and a tertiary amine other than a tertiary amine in the form of an anion exchange resin, -CH = CH of an olefin compound
_{The following} general formula (V), (VI) or (VII) wherein a silicon-bonded hydrogen atom of the above-mentioned organosilicon compound is added to _two groups.
A method for producing an organosilicon compound, characterized by obtaining a reaction product represented by the formula: Embedded image R ¹ —CH ＝ CH ₂ (I) (wherein, R ¹ is a substituted or unsubstituted alkyl group having 2 to 30 carbon atoms) (However, in the formula, R ² and R ³ are the same or different and are each a substituted or unsubstituted alkyl group or aryl group having 1 to 10 carbon atoms, and k is an integer of 1 to ^3. ) (Wherein, R ^{4 to} R ¹⁰ are the same or different, respectively, substituted or unsubstituted alkyl groups, cycloalkyl groups or aryl groups, and X is a hydrogen atom, a substituted or unsubstituted alkyl group, a cycloalkyl group or An aryl group, m is an integer of m ≧ 0 when X is a hydrogen atom, m is an integer of m ≧ 1 when X is not a hydrogen atom, and n is an integer of n ≧ 0.) (Wherein, R ^{11 to} R ¹³ are the same or different substituted or unsubstituted alkyl, cycloalkyl or aryl groups, respectively, and p ≧ 0, q ≧ 1, p + q ≧ 3
It is. ) (However, in the formula, R ^{1 to} R ¹³ , k, m, n, p, q, and X are the same as described above.)