JPH08134219A - Organopolysiloxane containing both mercapto and hydrolyzable groups and production thereof - Google Patents

Abstract

PURPOSE: To obtain an organopolysiloxane which contains both mercapto and hydrolyzable groups and is suitable for, e.g. a coating material by the hydrolysis or co-condensation through hydrolysis of a specified mercapto-containing com pound in the presence of a fluorine compound. CONSTITUTION: A mercapto-containing compound of formula I (wherein R<1> is a mercapto-containing substituent; R<4> is a 1-18C hydrocarbon group; R<5> is a 1-4C hydrocarbon group; and e is 0, 1 or 2), a mixture of the compound of formula I and a silane containing hydrolyzable groups and represented by formula II (wherein R<6> is H or a 1-18C hydrocarbon group; R<7> is a 1-4C hydrocarbon group, etc.; and f is 0, or 1 to 3), or a mixture of the compound of formula I, that of formula II and that of formula III (wherein R<8> is H or a 1-18C hydrocarbon group; R<9> is a 1-4C hydrocarbon group, etc.; and 0.1<=g+h+i<=3) is subjected to hydrolysis or co-condensation through hydrolysis in the presence of a fluorine compound to give an organopolysiloxane containing both mercapto and hydrolyzable groups in the molecule and represented by formula IV (wherein R<2> is a 1-18C hydrocarbon group; R<3> is a group of formula V or a 1-4C hydrocarbon group; and 0.1<a+b+c+c+d<=3).

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel organopolysiloxane containing a mercapto group and a hydrolyzable group, and a method for producing the novel organopolysiloxane.

[0002]

Conventionally, silane coupling agents containing a mercapto group have been known, but no silicone oligomer or polymer containing both a mercapto group and a hydrolyzable group has been known.

[0003]

An object of the present invention is to provide a novel organopolysiloxane having both a mercapto group (--SH) and a hydrolyzable group. A further object of the present invention is to provide a method for producing the above novel organopolysiloxane.

[0004]

One of the above objects of the present invention is to provide an organopolysiloxane containing a mercapto group and a hydrolyzable group represented by the following average composition formula (1) in one molecule.

[0005]

Embedded image R ¹ _a R ² _b Si (OR ³ ) _c (OH) _d O _{(4- (a + b + c + d)) / 2} (1) (wherein R ¹ is a mercapto group Contains substituent, R ² has 1 carbon
To 18 substituted or unsubstituted one or more groups selected from hydrocarbon groups, R ³ is _{C 2 H 5 (CH 3)} C = N- group and a saturated or unsaturated having 1 to 4 carbon atoms One or more groups selected from the hydrocarbon groups, and a is 0 <a ≦
1, b is 0 ≦ b ≦ 2, c is 0.1 <c ≦ 2.25 and d
Is a number satisfying 0 ≦ d ≦ 2.25, and 0.1
<A + b + c + d ≦ 3 is satisfied. ) Is achieved.

Another object of the present invention is to provide a mercapto group-containing compound represented by the following general formula (2) R ¹ (R ⁴ ) _e Si (OR ⁵ ) _3-e (2) (wherein R ¹ is a mercapto group-containing substituent, R ⁴ is a carbon number 1
~ 18 substituted or unsubstituted hydrocarbon group, R ⁵ is a saturated or unsaturated hydrocarbon group having 1 to 4 carbon atoms, and e is 0,
Represents a numerical value of 1 or 2. Or a silane compound containing a mercapto group-containing compound represented by the general formula (2) and one or more hydrolyzable groups represented by the following general formula (3), the following general formula (4) A mixture of a partially or completely hydrolyzed product of a hydrolyzable group-containing organopolysiloxane represented by and / or a silane compound of the following general formula (3) and a hydrolyzable group-containing organosiloxane of the following general formula (4). (R ⁶ ) _f Si (OR ⁷ ) _4-f (3) (In the formula, R ⁶ is hydrogen or a substituted or unsubstituted hydrocarbon group having 1 to 18 carbon atoms which may be the same or different,
R ⁷ is a saturated or unsaturated hydrocarbon group having 1 to 4 carbon atoms or C ₂ H ₅ (CH ₃ ) C═N-group, and f is 0,
Represents the number 1, 2, or 3. ) R ⁸ _g SiO _{(4-ghi) / 2} (OR ⁹ ) _h (OH) _i (4) (In the formula, R ⁸ is hydrogen or a substituent having 1 to 18 carbon atoms which may be the same or different, or An unsubstituted hydrocarbon group,
R ⁹ is a saturated or unsaturated hydrocarbon group having 1 to 4 carbon atoms or C ₂ H ₅ (CH ₃ ) C═N-group, and g is 0 ≦ g ≦ 2.
Satisfying the condition, h is 0.01 ≦ h ≦ 3, i is a positive number satisfying 0 ≦ i ≦ 3, but 0.1 ≦ g + h + i ≦ 3. )
Is hydrolyzed / cohydrolyzed in the presence of a fluorine-containing compound.
The following average composition formula (5) R ¹ _a R ² _b Si (OR ³ ) _c (OH) _d O _{(4- (a + b + c + d)) / 2} ...... ( 5) (In the formula, R ¹ is a mercapto group-containing substituent, R ² is R ⁴ , R ⁶
And / or is derived from a group represented by R ⁸ and has 1 to 1 carbon atoms
1 or 2 or more groups selected from the substituted or unsubstituted hydrocarbon group of 8, R ³ is derived from the group represented by R ⁵ , R ⁷ and / or R ⁹ and has 1 to 4 carbon atoms. saturated or unsaturated hydrocarbon group and a _{C 2 H 5 (CH 3)} C = one or more groups selected from N- group and a is 0 <a ≦ 1, b is 0
≦ b ≦ 2, c is 0.1 <c ≦ 2.25, and d is 0 ≦ d ≦
It is a number that respectively satisfies 2.25, and 0.1 <a + b +
It satisfies c + d ≦ 3. ) Is achieved by a method for producing an organopolysiloxane containing a mercapto group and a hydrolyzable group represented by the formula (1) in one molecule.

The present invention will be described in more detail below. The present invention provides a novel mercapto group-containing organopolysiloxane represented by the following average composition formula (1).

[0008]

Embedded image R ¹ _a R ² _b Si (OR ³ ) _c (OH) _d O _{(4- (a + b + c + d)) / 2} (1)

Here, R ¹ is a mercapto group-containing substituent, specifically, -C ₃ H ₆ SH, -C ₂ H ₄ -C ₆ H ₄ -C.
H ₂ SH and the like.

R ² is a group R ^{4 of} a mercapto group-containing compound described below and / or a group R ^{6 of} a 1 to 4 functional hydrolyzable group-containing silane which is optionally added, a hydrolyzable group-containing organopolysiloxane, and / Or derived from a group R ⁸ of a partial or complete hydrolyzate of the above-mentioned silane compound and the above-mentioned hydrolyzable group-containing organopolysiloxane and having 1 to 1 carbon atoms
One or two or more groups selected from 18 substituted or unsubstituted hydrocarbon groups. That R ² represents one kind or two or more kinds of groups will be described later in relation to the production method.

Specific examples of the substituted or unsubstituted hydrocarbon represented by R ² include the following.

[0012]

Embedded image —CH ₃ , —CH ₂ CH ₃ , —CH ₂ CH ₂ CH ₃ ,
_{-CH- (CH 3) 2, -CH} 2 CH 2 CH 2 CH 3, -CH
_{(CH 3) CH 2 CH 3} , -CH 2 CH (CH 3) CH 3, -
_{C (CH 3) -A, -} (CH 2) 5 -CH 3, -CH 2 CH 2
_{CF 2 CF 2 CF 2 CF 3} , -CHCH 2 CF 3, -CH 2 C
_{H 2 -A, -A-CH 3} , -CH 3 (CH 2) 5, -A ( where, A represents a benzene ring.)

R ³ is derived from a C ₂ H ₅ (CH ₃ ) C═N-group and a group represented by R ⁵ , R ⁷ and / or R ⁹ and is a substituted or unsubstituted group having 1 to 4 carbon atoms. It represents a group selected from hydrocarbon groups. Examples of the substituted or unsubstituted hydrocarbon group having 1 to 4 carbon atoms include the groups below.

[0014]

Embedded image —CH ₃ , —CH ₂ CH ₃ , —CH ₂ CH ₂ CH ₃ ,
_{-CH- (CH 3) 2, -CH} 2 CH 2 CH 2 CH 3, -CH
_{(CH 3) CH 2 CH 3} , -CH 2 CH (CH 3) CH 3, -
_{C (CH 3) 3, -CH} 3 C = CH

Further, in the above formula, a, b and c are respectively 0 <a ≦ 1, b is 0 ≦ b ≦ 2 and c is 0 <c ≦ 2.25.
And d are numerical values that satisfy 0 ≦ d ≦ 2.25. However,
0.1 <a + b + c + d ≦ 3. Also, c is 0.5
It is preferably a positive number that satisfies ≦ c ≦ 2.25, and more preferably 0.8 ≦ c ≦ 2.

The organopolysiloxane containing a mercapto group and an alkoxy group of the present invention is represented by the above compositional formula (1), and it is sufficient that a to d are numbers satisfying the above ranges, linear, branched, You may have a cyclic | annular thing and the structure which these combined. Further, the degree of polymerization of the organopolysiloxane of the present invention may be any dimer having two Si atoms to a polymer having about 10,000 Si atoms. Particularly, a polymer having about 3 to 50 Si atoms is preferable. More preferably, it is a simple substance or a mixture of oligomers having 10 or less Si atoms. The organopolysiloxane of the present invention may not contain a silanol group, that is, d = 0 in the general formula (1). Also in this case, the preferable range of c is 0.5 ≦ c ≦ 2.25, and more preferably 0.8 ≦ c ≦ 2.

Next, a method for producing the mercapto group- and alkoxy group-containing organopolysiloxane of the present invention will be described. In the method of the present invention, a mercapto group-containing alkoxysilane is used alone or in combination and subjected to a hydrolysis / condensation reaction, or the alkoxysilane and a 1 to 4 functional hydrolyzable group-containing silane, a hydrolyzable group-containing organopolysiloxane and When a mixture of the above-mentioned hydrolyzable silane compound and a hydrolyzable group-containing organopolysiloxane with a partial or complete hydrolyzate polymer is subjected to a cohydrolysis / condensation reaction, the reaction is carried out with fluorine-containing fluorine as a hydrolysis catalyst. It is carried out in the presence of a silicon compound.

The mercapto group-containing alkoxysilane used as a raw material in this reaction is, for example, a compound represented by the following general formula (2).

[0019]

Embedded image R ¹ (R ⁴ ) _e Si (OR ⁵ ) _3-e (2) (wherein R ¹ , R ⁴ R ⁵ have the same meanings as described above, and e is 0, It is a number of 1 or 2.)

These compounds can be used alone or in combination as a mixture of two or more kinds. In the above formula, the mercapto group-containing substituent of R ¹ is the one exemplified in the above formula (1), that is, —C ₃ H ₆ SH, —C ₂ H ₄ —C ₆ H ₄ —CH.
₂ SH, etc.

Examples of the substituted or unsubstituted hydrocarbon group for R ⁴ include the following.

[0022]

Embedded image —CH ₃ , —CH ₂ CH ₃ , —CH ₂ CH ₂ CH ₃ ,
_{-CH- (CH 3) 2, -CH} 2 CH 2 CH 2 CH 3, -CH
_{(CH 3) CH 2 CH 3} , -CH 2 CH (CH 3) CH 3, -
_{C (CH 3) -A, -} (CH 2) 5 -CH 3, -CH 2 CH 2
_{CF 2 CF 2 CF 2 CF 3} , -CHCH 2 CF 3, -CH 2 C
_{H 2 -A, -A-CH 3} , -CH 3 (CH 2) 5, -A ( where, A represents a benzene ring.)

Further, examples of the saturated or unsaturated hydrocarbon group other than the C ₂ H ₅ (CH ₃ ) C═N-group of R ⁵ include the following.

[0024]

Embedded image —CH ₃ , —CH ₂ CH ₃ , —CH ₂ CH ₂ CH ₃ ,
_{-CH- (CH 3) 2, -CH} 2 CH 2 CH 2 CH 3, -CH
_{(CH 3) CH 2 CH 3} , -CH 2 CH (CH 3) CH 3, -
_{C (CH 3) 3, -CH} 3 C = CH 2

A particularly preferred mercapto group-containing compound is γ-mercaptotrimethoxysilane.

The above-mentioned mercapto group-containing alkoxysilanes can be used alone or as a mixture as described above to form the novel organopolysiloxane of the present invention. If necessary, 1 to 3 represented by the following general formula (3) can be used. A tetrafunctional hydrolyzable group-containing silane, a hydrolyzable group-containing polysiloxane represented by the following general formula (4), and / or a portion of the hydrolyzable group-containing silane and the hydrolyzable group-containing polysiloxane, or It can be used in combination with a silicone compound obtained by complete hydrolysis.

[0027]

(R ⁶ ) _f Si (OR ⁷ ) _4-f (3) (In the formula, R ⁶ , R ⁷ and f have the same meanings as described above.)

[0028]

_{Embedded image} R ⁸ _g SiO _{(4-ghi) / 2} (OR ⁹ ) _h (OH) _i (4) (wherein R ⁸ , R ⁹ , g, h and i have the same meanings as described above). Have.)

Examples of the hydrolyzable group-containing silane of the above formula (3) include the following.

[0030]

[Chemical 10]

[0031]

[Chemical 11]

[0032]

[Chemical 12]

[0033]

[Chemical 13]

[0034]

Embedded image

[0035]

[Chemical 15]

[0036]

Embedded image

[0037]

[Chemical 17]

[0038]

Embedded image

[0039]

[Chemical 19]

[0040]

Embedded image

[0041]

[Chemical 21]

On the other hand, examples of the hydrolyzable group-containing polysiloxane of the formula (4) include the following alkoxy group-containing disiloxanes.

[0043]

[Chemical formula 22]

[0044]

[Chemical formula 23]

[0045]

[Chemical formula 24]

[0046]

[Chemical 25]

[0047]

[Chemical formula 26]

Furthermore, a silicone compound which is (co) hydrolyzed with the silane compound of the general formula (3) and the above-mentioned alkoxy group-containing disiloxane to form a polymer can also be used.

The structure of the polymer of the silicone compound may be linear, branched, cyclic or a combination thereof. Other than the above, among the commercially available silicone resins, those containing an alkoxy group having 1 to 4 carbon atoms can be used. In this case, the above-mentioned commercially available silicone resin can be used as the hydrolyzable group-containing silicone of the present invention even if it partially contains silanol groups.

Further, in the present invention, a silicone resin having only a silanol group at the terminal can be used in combination if necessary.

These hydrolyzable group-containing silanes,
When the hydrolyzable group-containing disiloxane and / or the silicone resin are used, they can be used as one kind or as a mixture of two or more kinds.

As described above, the at least one mercapto group-containing alkoxysilane represented by the general formula (1) can be used alone, but the hydrolyzable group-containing silane, the hydrolyzable group-containing disiloxane and / or the silicone resin are used. When mixed with, the mixing ratio is not particularly limited. Preferably, the proportion of the mercapto group-containing alkoxysilane is 0.1 to 100% by weight, more preferably 1 to 100% by weight. That is, when the mixing ratio is less than 0.1% by weight, the mercapto group is not uniformly distributed in the final organopolysiloxane, and the compatibility and the reactivity are poor, which is not preferable. By appropriately adjusting the types and amounts of the hydrolyzable group-containing silane, the hydrolyzable group-containing siloxane and / or the silicone resin used in the above range, a mercapto group-containing organopolysiloxane having desired properties can be obtained.

In the composition formula (1), R ² is one or more selected from a substituted or unsubstituted hydrocarbon group having 1 to 18 carbon atoms, which means that a mercapto group-containing alkoxysilane is one. When used alone, R
^The group represented by 2 is composed of one kind of hydrocarbon derived from the group represented by R ⁴ in the formula (2), but two or more kinds of mercapto group-containing alkoxysilanes are used or the silane represented by the general formula (3). When the compound and the siloxane and / or silicone resin represented by the general formula (4) are used in combination, R ² is a different hydrocarbon group represented by R ⁴ or a silane compound, R ⁶ and R ⁸ of the siloxane and / or silicone resin. This is because it has a different hydrocarbon group derived from the group represented as R ² .

As the hydrolysis catalyst used in the present invention,
Although an acid or alkaline catalyst that is usually used can be used, a fluorine-containing compound is used in the production method of the present invention. When a fluorine-containing compound is used, the amount of silanol is smaller and the molecular weight distribution is narrower than when an acid or alkali catalyst is used. Of course, a fluorine-containing compound and an acid or alkali catalyst may be used in combination.

Examples of the acid catalysts include inorganic acids such as hydrochloric acid, nitric acid, phosphoric acid and sulfuric acid, and organic acids such as methanesulfonic acid, paratoluenesulfonic acid, oxalic acid, maleic acid and trifluoroacetic acid. Examples of the alkaline catalyst include inorganic bases such as sodium carbonate, sodium hydroxide, potassium hydroxide, ammonia and ammonium hydroxide, and organic bases such as amines.

The fluorine-containing compound used in the present invention may be any of a fluorine-containing inorganic salt compound, a fluorinated quaternary ammonium salt compound and a fluorine-containing organosilicon compound. These fluorine-containing compounds act as a catalyst for the hydrolysis reaction in the present invention.

As the above-mentioned fluorine-containing inorganic salt compound, Li
F, NaF, KF, CsF, MgF2, BaF 2, B
_{F 3, AlF 3, CuF 2} , ZnF 2, SbF 2, can be exemplified such as, but is not particularly limited to these.

Examples of the fluorinated quaternary ammonium salt compound include those represented by the following formula.

[0059]

[Chemical 27]

As the fluorine-containing organosilicon compound, Si
_{F 4, H 2 SiF 6,} Na 2 SiF 6, (NH 4) 2 SiF 6, F
_{-Si (OCH 3) 3, F} -Si (OCH 2 CH 3) 3, F-
Si (OCH ₂ CH ₂ CH ₂ CH ₃ ) ₃ , F ₂ Si (OC
_{H 3) 2, F 3 Si} (OCH 3) or the like can be mentioned.

Of these, considering the solubility in solvent, operability and stability, in the present invention, NaF,
[(CH ₃ ) ₄ N ⁺ ] F ⁻ and Na ₂ SiF ₆ are particularly preferable.
Most preferred is KF.

The amount of the fluorine-containing compound added in the present invention is 0.0 with respect to the number of moles of Si atoms present in the entire alkoxy group-containing organosilicon compound to be hydrolyzed.
It is preferably in the range of 0001 to 10 mol%, and particularly preferably 0.0001 to 1 mol%. When an acid or alkali catalyst is used in combination, the acid or alkali varies depending on the type with respect to the number of moles of the above Si atom, but it is 0.
It is preferably from 00001 to 1 mol%.

The fluorine-containing compound may be added directly to the hydrolysis raw material, or may be diluted with water or an organic solvent and added.

As described above, the degree of polymerization of the mercapto group- and hydrolyzable group-containing organopolysiloxane of the present invention is Si.
The dimer of 2 atoms to the polymer of about 10,000 Si atoms may be used, but the degree of polymerization of the silane compound is determined by the amount of water used for hydrolysis. For example, when the hydrolyzable silane raw material to be used is a monomer having one silicon atom, from 1 mol of the hydrolyzable silane raw material, a mercapto group containing Z silicon atoms and a hydrolyzable group-containing organopolysiloxane are prepared. To get, (Z
-1) / Z mol of water may be used during the hydrolysis reaction. When the amount of water used for the hydrolysis reaction is 1 mol or more, that is, the same mol or more as the hydrolyzable silane raw material is used, a resin body having many branched structures is obtained.

In the production method of the present invention, organic solvents such as alcohols, ethers, esters and ketones may be used if necessary. Specific examples of these organic solvents include methyl alcohol, ethyl alcohol, 1-
Alcohols such as propyl alcohol and 2-propyl alcohol, ethers such as diethyl ether and dipropyl ether, esters such as methyl acetate, ethyl acetate and ethyl acetoacetate, ketones such as acetone, diethyl ketone, methyl ethyl ketone and methyl isobutyl ketone. Can be mentioned. Further, a nonpolar solvent such as hexane, benzene, toluene, xylene may be used together with the above solvent. In the present invention, it is particularly preferable to use alcohols such as methyl alcohol and ethyl alcohol.

The amount of the solvent used is up to 1000 parts by weight based on 100 parts by weight of the raw material hydrolyzable group-containing silane.

The amount (mol) of water used for the hydrolysis needs to be 50 times or less mol of all the hydrolyzable groups (mol) in the raw material. Beyond that, the pot yield will decrease, which is economically disadvantageous. However, in the range of 1/2 to 50 times by mole, in the method of the present invention using a fluorine-containing compound as a catalyst, most of the remaining hydrolyzable groups and silanol groups disappear, so that in particular c of the composition formula (1) Value 0.5 ≤
In order to satisfy c ≦ 2.25, it is necessary that the amount is less than 1/2 mol of the hydrolyzable group in all the raw materials before hydrolysis. When it is used more than that, the hydrolyzable group does not remain.

Therefore, when the hydrolyzable group-containing organopolysiloxane is used in combination as a hydrolysis raw material, it is necessary to consider the amount of siloxane bonds already present in the hydrolyzable group-containing organopolysiloxane when designing the molecule. is there.

As an actual reaction operation for carrying out the present invention, a hydrolyzable silane as a raw material for the hydrolysis reaction, a fluorine-containing compound used as a catalyst, and a mixed system of an organic solvent are mixed with a predetermined amount of water. Alternatively, it is preferable to add an organic solvent diluent diluted with water dropwise.

The fluorine-containing compound as the catalyst may be added to the aqueous system. It is not preferable to reverse the order of addition such that the mixed system is added to water or a water-diluted organic solvent, because the reaction system easily gels.

The (co) hydrolysis / condensation reaction is carried out at 0 ° C to 100 ° C.
It may be carried out in the range of 20 ° C, and particularly preferably in the range of 20 ° C to 80 ° C.

Since the fluorine-containing compound catalyst used in the present invention remarkably promotes the (co) hydrolysis / condensation reaction, the added water is completely consumed, and silanol groups are hardly left. An organopolysiloxane compound having the following structure can be obtained. After the reaction, the catalyst used is removed, but the by-produced alcohol may be distilled off and then filtered, or the organic solvent system having a high hydrophobicity may be changed and then washed with water.

[0073]

EXAMPLES The present invention will now be described in more detail by way of examples, which should not be construed as limiting the invention. Example 1 [(HSC ₃ H ₆ ) _0.168 (CH ₃ ) _0.833 SiO _0.833 (O
CH ₃ ) _1.334 ] ₆ production

196.8 g (1.0 mol) of γ-mercaptopropyltrimethoxysilane was placed in a flask equipped with a stirrer, a Liebig condenser, a dropping funnel, and a thermometer.
679.7 g (5 mol) of methyltrimethoxysilane,
300 g of methanol was charged, and 89.9 g of 0.1N hydrochloric acid aqueous solution (water; 5.0 mol, HCl; 9 × 10 ⁻³⁾ under stirring.
Mol) and 90 g of methanol were added dropwise over 30 minutes, and the mixture was aged at 25 ° C. for 2.5 hours. Then, 3.49 g of a 1% potassium fluoride methanol solution (KF; 6 ×
(10 ⁻⁴ mol) was added, and the mixture was held at 25 ° C. for 3 hours for hydrolysis and condensation. Further, the alcohol produced under the condition of 100 ° C./30 mmHg was distilled off and then filtered. As a result, a mercapto group- and alkoxy group-containing silicone resin (1) was obtained (amount 585 g, yield 90.5%). This resin has a nonvolatile content of 75.6%, a viscosity of 9.2 centistokes (cs, 25 ° C.), a specific gravity of 1.130 (25 ° C.), a refractive index of 1.4146 (25 ° C.), and an SH amount of 5.2 wt% ( The theoretical value was 5.1% by weight), and the amount of S was 5.5% by weight. The ¹ H-NMR analysis result revealed that the obtained substance had the following average composition formula.

[0075]

_{Embedded image} (HSC ₃ H ₆ ) _0.2 (CH ₃ ) _0.8 SiO _0.833
(OCH ₃ ) _1.2

The above structural formula was also supported by the analysis results of ²⁹ Si-NMR and infrared absorption spectrum. Also, GPC
As a result of analysis, the weight average molecular weight is 808 (dispersion degree 1.7).
Met. Since the low-molecular-weight substance was slightly distilled off, it was slightly out of the theoretical value, but it was almost as set. ²⁹ S
Table 1 shows the analysis results of the i-NMR spectrum.

[0077]

[Table 1]

The analysis results of ¹ H-NMR spectrum are shown in Table 2.
As shown in.

[0079]

[Table 2]

Further, the infrared absorption spectrum of this resin is shown in FIG. Absorption of Si-O-Si group; 1104 cm ^-1 Si-OC
Absorption of H ³ ; 2481 cm ^-1 , 1198 cm ^-1 , 110
4 cm ^-1

Example 2 [(HSC ₃ H ₆ ) _0.167 SiO _0.833 (OCH ₃ ).
_0.167 (OCH ₂ CH ₃ ) _2.000 ] ₆ 262.4 g (1.34 mol) of γ-mercaptopropyltrimethoxysilane and tetraethoxy in a flask equipped with a stirrer, a Liebig condenser, a dropping funnel, and a thermometer. 1386.1 g (6.67 mol) of silane and 368.0 g of methanol were charged, and 120.0 g of 0.05N hydrochloric acid aqueous solution (water; 6.67 mol, HCl; 6 × 10 6) under stirring.
^-3 mol) and 92 g of methanol were added dropwise over 30 minutes, and the mixture was aged at 25 ° C for 2.5 hours. Then 1%
23.3 g of a solution of potassium fluoride in methanol (KF;
(4 × 10 ⁻³ mol), and kept at 25 ° C. for 3 hours for hydrolysis / condensation. Further, the alcohol produced under the condition of 100 ° C./30 mmHg was distilled off and then filtered.
As a result, a mercapto group- and alkoxy group-containing silicone resin (2) was obtained (yield 1072 g, yield 89.9).
%). This resin has a nonvolatile content of 62.7%, a viscosity of 7.5 centistokes (cs, 25 ° C.), and a specific gravity of 1.093 (25
C.), the refractive index was 1.4134 (25.degree. C.), the SH amount was 3.9% by weight (theoretical value was 3.6% by weight), and the S amount was 3.9% by weight. The ¹ H-NMR analysis result revealed that the obtained substance had the following average composition formula.

[0082]

_{Embedded image} (HSC ₃ H ₆ ) _0.167 SiO _0.833 (OCH ₃ )
_0.167 (OCH ₂ CH ₃ ) _2.000

The above structural formula was also supported from the results of analysis of ²⁹ Si-NMR and infrared absorption spectrum. ²⁹ Si-NMR
Table 3 shows the spectrum analysis results.

[0084]

[Table 3]

The results of analysis of ¹ H-NMR spectrum are shown in Table 4.
As shown in.

[0086]

[Table 4]

Further, the infrared absorption spectrum of this resin is shown in FIG. Absorption of Si-O-Si group; 1104 cm ^-1 Si-OC
Absorption of H ³ ; 2481 cm ^-1 , 1198 cm ^-1 , 110
4 cm ^-1

Example 3 [(HSC ₃ H ₆ ) _0.1 (C ₆ H ₅ ) _0.3 (CH ₃ ) _0.6 SiO
Production of _0.9 (OCH ₃ ) _0.4 (OC ₃ H ₇ ) _0.8 ] ₁₀ 196.4 g (1.0) of γ-mercaptopropyltrimethoxysilane in a flask equipped with a stirrer, a Liebig condenser, a dropping funnel, and a thermometer. Mole), the following chemical formula 30
525 g (1.5 mol) of the above disiloxane and 994.2 g (3.0 mol) of the disiloxane of the following chemical formula 31 were charged, and 77.2 g (water;
A mixed solution of 4.29 mol, HCl; 4 × 10 ⁻³ mol) and 77.2 g of methanol was added dropwise over 30 minutes, and the mixture was aged at 25 ° C. for 2.5 hours. Next, 2.9 g (KF; 5 × 10 ⁻⁴ mol) of a methanol solution of 1% potassium fluoride was added,
The mixture was aged at 25 ° C. for 3 hours to carry out a hydrolysis / condensation reaction. Further, the alcohol produced under the condition of 100 ° C./10 mmHg was distilled off and then filtered. As a result, a mercapto group-containing silicone resin (3) was obtained (yield 1120).
g, yield 79.1%). This resin has a nonvolatile content of 69.5.
%, Viscosity 14.5 centistokes (cs, 25 ° C.),
The specific gravity was 1.089, the refractive index was 1.4530, the SH amount was 2.5% by weight (theoretical value: 2.3% by weight), and the S amount was 2.2% by weight.

[0089]

Embedded image

[0090]

[Chemical 31]

From the ¹ H-NMR analysis results, the obtained substance was found to have the following average composition formula.

[0092]

Embedded image (HSC ₃ H ₆ ) _0.1 (C ₆ H ₅ ) _0.3 (CH ₃ )
_0.6 SiO _0.9 (OCH ₃ ) _0.4 (OC ₃ H ₇ ) _0.65 (OH)
_0.15

It was confirmed that the above structural formula was supported by ²⁹ Si-NMR and infrared absorption spectrum, and that it was as set. The infrared absorption spectrum of this resin is shown in FIG.

Example 4 [(HSC ₃ H ₆ ) _0.167 (CH ₃ ) _0.833 SiO _0.833 (O
CH ₃ ) _1.334 ] ₆ production stirrer, Liebig cooler,
In a flask equipped with a dropping funnel and a thermometer, 196.8 g (1.0%) of γ-mercaptopropyltrimethoxysilane was added.
Mol) and 679.7 g of methyltrimethoxysilane
(5.0 mol) and 300 g of methanol were charged, and 89.9 g of 0.1N hydrochloric acid aqueous solution (water; 5.0 mol, H
Cl; 9 × 10 ⁻³ mol) and 90 g of methanol were added dropwise over 30 minutes, and the mixture was aged at 25 ° C. for 2.5 hours.
Next, the alcohol produced under the conditions of 100 ° C./30 mmHg was distilled off and then filtered. As a result, a mercapto group-containing silicone resin (4) was obtained (yield 529 g,
Yield 89.8%). This resin has a nonvolatile content of 47.2%, a viscosity of 4.9 centistokes (cs, 25 ° C.), and a specific gravity of 1.
The refractive index was 113, the refractive index was 1.4150, the SH amount was 5.7% by weight (theoretical value: 5.1% by weight), and the S amount was 5.5% by weight. The obtained substance was found to have the following average composition formula from the ¹ H-NMR analysis result.

[0095]

Embedded image (HSC ₃ H ₆ ) _0.1 (C ₆ H ₅ ) _0.3 (CH ₃ )
_0.6 SiO _0.9 (OCH ₃ ) _0.4 (OC ₃ H ₇ ) _0.65 (OH)
_0.15

From the ²⁹ Si-NMR and infrared absorption spectra, it was confirmed that the above structural formula was supported and that it was as set. The infrared absorption spectrum of this resin is shown in FIG.

Example 5 [(HSC ₃ H ₆ ) _0.167 (CH ₃ ) _0.833 SiO _0.967 (O
CH ₃ ) _1.067 ] ₃₀ 104.4 g of 0.1N hydrochloric acid aqueous solution (water; 5.8 mol,
HCl; 10.4 × 10 ⁻³ mol)
In the same manner as described above, a silicone resin having a degree of polymerization of 30 was obtained (yield 505.7 g, yield 83.0%). This resin has a nonvolatile content of 85.2% and a viscosity of 215 centistokes (cs, 2
5 ° C.), specific gravity 1.141 (25 ° C.), SH amount of 5.5 wt% (theoretical value 5.4 wt%), and S amount of 5.4 wt%.

Example 6 The same procedure as in Example 1 was carried out except that 0.1N hydrochloric acid aqueous solution was used, and the yield was 520.2, the yield was 80.5%, the non-volatile content was 76.2%, the viscosity was 12.1 cs. Specific gravity 1.132, S
The H amount was 5.4% (theoretical value 5.1%), and the S amount was 5.6%.

[0099]

As described above, since the novel silicone compound of the present invention has a mercapto group and a hydrolyzable silyl group in the molecule, it can be cured by reacting with the mercapto group. It can be applied as a material, an adhesive, a cross-linking agent such as a sealing material, or a reactive diluent. Further, due to its structure, it can be used as an oligomeric silane coupling agent as a reinforcing agent for a composite material composed of an organic resin and an inorganic material. Alternatively, it can be used as a chain transfer agent during the polymerization of the acrylic compound. Compared with the silane coupling agent, the content of Si can be increased by using the compound of the present invention. Further, compared with the mercapto-modified silicone oil, the crosslinkability is improved because it has an alkoxy group. According to the production method of the present invention, it is possible to easily obtain a fluorine-containing compound, which is neutral, and is excellent in operability and safety, as a catalyst by using a raw material that is industrially easily available.

[Brief description of drawings]

1 is an infrared absorption spectrum of a mercapto group- and alkoxy group-containing organopolysiloxane obtained in Example 1. FIG.

2 is an infrared absorption spectrum of the organopolysiloxane containing a mercapto group and an alkoxy group obtained in Example 2. FIG.

3 is an infrared absorption spectrum of a mercapto group- and alkoxy group-containing organopolysiloxane obtained in Example 3. FIG.

4 is an infrared absorption spectrum of a mercapto group- and alkoxy group-containing organopolysiloxane obtained in Example 4. FIG.

Claims (5)

[Claims] 1. An organopolysiloxane having a mercapto group and a hydrolyzable group represented by the following average composition formula (1) in one molecule, R ¹ _a R ² _b Si (OR ³ ) _c (OH) _d. O _{(4- (a + b + c + d)) / 2} (1) (In the formula, R ¹ is a mercapto group-containing substituent, and R ² is 1 carbon atom.
To 18 substituted or unsubstituted one or more groups selected from hydrocarbon groups, R ³ is _{C 2 H 5 (CH 3)} C = N- group and a saturated or unsaturated having 1 to 4 carbon atoms One or more groups selected from the hydrocarbon groups, and a is 0 <a ≦
1, b is 0 ≦ b ≦ 2, c is 0.1 <c ≦ 2.25 and d
Is a number satisfying 0 ≦ d ≦ 2.25, and 0.1
<A + b + c + d ≦ 3 is satisfied. ). 2. In the general formula (1), d = 0 and c is 0.5.
The organopolysiloxane according to claim 1, wherein the organopolysiloxane is a positive number satisfying ≤c≤2.25. 3. A mercapto group-containing compound represented by the following general formula (2) R ¹ (R ⁴ ) _e Si (OR ⁵ ) _3-e (2) (In the formula, R ¹ is a mercapto group-containing substituent. Group, R ⁴ has 1 carbon atom
~ 18 substituted or unsubstituted hydrocarbon group, R ⁵ is a saturated or unsaturated hydrocarbon group having 1 to 4 carbon atoms, e is 0,
Represents the number 1 or 2. Or a silane compound containing a mercapto group-containing compound represented by the general formula (2) and one or more hydrolyzable groups represented by the following general formula (3), the following general formula (4) A partially or completely hydrolyzed product of the hydrolyzable group-containing organopolysiloxane represented by and / or the silane compound of the following general formula (3) and the hydrolyzable group-containing organopolysiloxane of the following general formula (4) Mixture (R ⁶ ) _f Si (OR ⁷ ) _4-f (3) (wherein R ⁶ is hydrogen or a substituted or unsubstituted hydrocarbon group having 1 to 18 carbon atoms which may be the same or different,
R ⁷ is a saturated or unsaturated hydrocarbon group having 1 to 4 carbon atoms or C ₂ H ₅ (CH ₃ ) C═N-group, and f is 0,
Represents the number 1, 2, or 3. ) R ⁸ _g SiO _{(4-ghi) / 2} (OR ⁹ ) _h (OH) _i (4) (In the formula, R ⁸ is hydrogen or a substituent having 1 to 18 carbon atoms which may be the same or different, or An unsubstituted hydrocarbon group,
R ⁹ is a saturated or unsaturated hydrocarbon group having 1 to 4 carbon atoms or C ₂ H ₅ (CH ₃ ) C═N-group, and g is 0 ≦ g ≦ 2.
Satisfying the condition, h is 0.01 ≦ h ≦ 3, i is a positive number satisfying 0 ≦ i ≦ 3, but 0.1 ≦ g + h + i ≦ 3. )
Is hydrolyzed / cohydrolyzed in the presence of a fluorine-containing compound.
The following average composition formula (5) R ¹ _a R ² _b Si (OR ³ ) _c (OH) _d O _{(4- (a + b + c + d)) / 2} ...... ( 5) (In the formula, R ¹ is a mercapto group-containing substituent, R ² is R ⁴ , R ⁶
And / or is derived from a group represented by R ⁸ and has 1 to 1 carbon atoms
1 or 2 or more groups selected from the substituted or unsubstituted hydrocarbon group of 8, R ³ is derived from the group represented by R ⁵ , R ⁷ and / or R ⁹ and has 1 to 4 carbon atoms. saturated or unsaturated hydrocarbon group and a _{C 2 H 5 (CH 3)} C = one or more groups selected from N- group and a is 0 <a ≦ 1, b is 0
≦ b ≦ 2, c is 0.1 <c ≦ 2.25, d is 0 ≦ d ≦
It is a number that respectively satisfies 2.25, and 0.1 <a + b +
It satisfies c + d ≦ 3. ) A method for producing an organopolysiloxane containing a mercapto group and a hydrolyzable group represented by the formula (1) in one molecule. 4. The d in the general formula (5) according to claim 3, wherein the number of moles of water used for hydrolysis is less than 1/2 of the total number of moles of alkoxy groups in the raw material before hydrolysis. =
The method for producing an organopolysiloxane according to claim 3, wherein the organopolysiloxane has a mercapto group and a hydrolyzable group of 0, 0.5 ≦ c ≦ 2.25. 5. The method for producing an organopolysiloxane according to claim 3, wherein the fluorine-containing compound has a mercapto group and a hydrolyzable group, which is KF.