JP2011046642A - Method for producing silane coupling agent - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing a silane coupling agent, by which the silane coupling agent lowering the hysteresis loss of a rubber composition and improving the abrasion resistance of the rubber composition can be obtained in a high yield, while preventing the production of byproducts. <P>SOLUTION: The method for producing the silane coupling agent is characterized by including a process for converting the halogen element of a haloalkyl group of a silane compound having the haloalkyl group and an aminoalkoxy group into a group to obtain a silane compound having a protected mercapto group and an aminoalkoxy group. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a method for producing a silane coupling agent, and obtains a silane coupling agent that reduces the hysteresis loss of the rubber composition and improves the wear resistance while suppressing the formation of by-products in a high yield. It is related with the manufacturing method which can be performed.

  Recently, from the viewpoint of vehicle safety, it is required to improve the safety of tires on wet road surfaces. In addition, from the viewpoint of reducing carbon dioxide emissions associated with increasing interest in environmental problems, it is also required to further reduce fuel consumption of vehicles.

  In response to these demands, conventionally, as a technique for achieving both improvement in performance on a wet road surface of a tire and reduction in rolling resistance, a technique of using an inorganic filler such as silica as a filler of a rubber composition used for a tire tread is known. It is known to be effective. However, rubber compositions containing inorganic fillers such as silica reduce tire rolling resistance, improve braking performance on wet road surfaces, and improve steering stability, but have high unvulcanized viscosity and multi-stage kneading. Therefore, there is a problem in workability. Therefore, in a rubber composition containing an inorganic filler such as silica, the breaking strength and wear resistance are greatly reduced, and problems such as vulcanization delay and poor filler dispersion occur. Therefore, when an inorganic filler such as silica is blended with the rubber composition for tread, the unvulcanized viscosity of the rubber composition is reduced, the modulus and wear resistance are ensured, and the hysteresis loss is further reduced. It is essential to add a silane coupling agent.

US Pat. No. 3,842,111 US Pat. No. 3,873,489

  However, since the silane coupling agent is expensive, the blending cost increases due to the blending of the silane coupling agent. Also, the addition of a dispersion improver decreases the unvulcanized viscosity of the rubber composition and improves workability, but also reduces the wear resistance.

  Therefore, the present inventors have examined, an organosilicon compound having one or more silicon-oxygen bonds (Si-O) and 1 to 10 sulfur atoms (S) in the molecule, Since the organosilicon compound introduced with a nitrogen-containing functional group has a high reaction rate with an inorganic filler such as silica, the efficiency of the coupling reaction can be improved by blending the organosilicon compound with the inorganic filler in the rubber component. It has been found that the wear resistance is greatly improved while greatly reducing the hysteresis loss of the rubber composition.

［式中、Ｒ'¹、Ｒ'²及びＲ'³が−Ｍ−Ｃ_lＨ_2l+1で表され、Ｒ⁴、Ｒ⁵、ｚ、Ｍ及びｌは、下記に定義されるとおりであり、但し、Ｒ'¹、Ｒ'²及びＲ'³中のＭの一つ以上が−Ｏ−である］で表されるシラン化合物に対し、アミノアルコール類を加え、必要に応じて、触媒としてｐ-トルエンスルホン酸、塩酸等の酸や、チタンテトラｎ-ブトキシド等のチタンアルコキシドを添加し、加熱して、アルコール交換反応によって合成できる。 The organosilicon compound is, for example, the following formula (A):

[Wherein R ′ ¹ , R ′ ² and R ′ ³ are represented by —M—C ₁ H _{2 1 + 1} , and R ⁴ , R ⁵ , z, M and l are as defined below. However, one or more of M in R ′ ¹ , R ′ ² and R ′ ³ is —O—], an amino alcohol is added to the silane compound represented by An acid such as p-toluenesulfonic acid or hydrochloric acid, or a titanium alkoxide such as titanium tetra n-butoxide is added, heated, and synthesized by an alcohol exchange reaction.

However, by an alcohol exchange reaction between a silane compound (a) having a trialkoxysilyl group together with a protected mercapto group, such as the silane compound represented by the above formula (A), and an amino alcohol (b), In the case of synthesizing the organosilicon compound (c), amino alcohols (b), alcohol desorbed from the silane compound (a), etc. cause a transesterification reaction, and various by-products (for example, d, e , F, g, etc.) (see the scheme shown below). And separation of these by-products (impurities) was usually difficult.

  Accordingly, an object of the present invention is to reduce the hysteresis loss of the rubber composition and improve the wear resistance while suppressing the generation of by-products through a route different from the above reaction route, and improving the wear resistance. It is in providing the manufacturing method which can obtain an agent.

As a result of intensive studies to achieve the above object, the present inventors have found that an organosilicon compound (a ′) having one or more silicon-oxygen bonds (Si—O) and a haloalkyl group in the molecule, A compound (h) having an aminoalkoxyl group introduced therein is synthesized by an alcohol exchange reaction with aminoalcohols (b), and then the halogen element of the compound (h) is converted into an alkanoylthio group, thereby reducing impurities. The inventors have found that an organosilicon compound (j) can be obtained, and have completed the present invention (see the scheme shown below).

  That is, the method for producing a silane coupling agent of the present invention converts a halogen element of a haloalkyl group of a silane compound having a haloalkyl group and an aminoalkoxyl group into an alkanoylthio group, thereby converting a protected mercapto group and an aminoalkoxyl group. The method includes a step of obtaining a silane compound.

  In the present invention, the haloalkyl group is an alkyl group substituted with one or more halogen elements such as fluorine, chlorine, bromine and iodine, and the aminoalkoxyl group is an amino group, an imino group, a substituted amino group. Group, an alkoxyl group containing a nitrogen-containing functional group such as a substituted imino group, and the alkanoylthio group is an alkanoyl group in which the oxygen of the carboxyl group is substituted with sulfur, and has the general formula R—C (═O) — S— (wherein R is a hydrogen atom or an alkyl group).

［式（I）中のＲ¹、Ｒ²及びＲ³は、少なくとも一つが下記一般式（II）又は式（III）：

（式中、Ｍは−Ｏ−又は−ＣＨ₂−で、Ｘ及びＹはそれぞれ独立して−Ｏ−、−ＮＲ⁸−又は−ＣＨ₂−で、Ｒ⁶は−ＯＲ⁸、−ＮＲ⁸Ｒ⁹又は−Ｒ⁸で、Ｒ⁷は−ＮＲ⁸Ｒ⁹、−ＮＲ⁸−ＮＲ⁸Ｒ⁹又は−Ｎ＝ＮＲ⁸で、但し、Ｒ⁸は−Ｃ_nＨ_2n+1であり、Ｒ⁹は−Ｃ_qＨ_2q+1であり、ｌ、ｍ、ｎ及びｑはそれぞれ独立して０〜２０である）で表され、その他が−Ｍ−Ｃ_rＨ_2r+1（ここで、Ｍは上記と同義であり、ｒは０〜２０である）又は−(Ｍ−Ｃ_lＨ_2l)_yＣ_sＨ_2s+1（ここで、Ｍ及びｌは上記と同義であり、ｙ及びｓはそれぞれ独立して１〜２０である）で表され、但し、Ｒ¹、Ｒ²及びＲ³の一つ以上はＭが−Ｏ−であり、
Ｒ⁴は下記一般式（IV）、式（V）又は式（i）：

（式中、Ｍ、Ｘ、Ｙ、Ｒ⁶、ｌ及びｍは上記と同義であり、Ｒ¹⁰は−ＮＲ⁸−、−ＮＲ⁸−ＮＲ⁸−又は−Ｎ＝Ｎ−で、但し、Ｒ⁸は上記と同義である）で表され、
Ｒ⁵は上記一般式（II）又は式（III）或いは−Ｃ_lＨ_2l−Ｒ¹¹（ここで、Ｒ¹¹は−ＮＲ⁸Ｒ⁹、−ＮＲ⁸−ＮＲ⁸Ｒ⁹、−Ｎ＝ＮＲ⁸又は−Ｍ−Ｃ_mＨ_2m+1であり、但し、Ｒ⁸、Ｒ⁹、Ｍ、ｌ及びｍは上記と同義である）で表され、
ｚは１〜１０である］で表されることが好ましい。 In the method for producing a silane coupling agent of the present invention, the protected silane compound having a mercapto group and an aminoalkoxyl group has the following general formula (I):

[At least one of R ¹ , R ² and R ³ in the formula (I) is represented by the following general formula (II) or formula (III):

(In the formula, M is —O— or —CH ₂ —, X and Y are independently —O—, —NR ⁸ — or —CH ₂ —, and R ⁶ is —OR ⁸ , —NR ⁸ R. ⁹ or -R ⁸ , R ⁷ is -NR ⁸ R ⁹ , -NR ⁸ -NR ⁸ R ⁹ or -N = NR ⁸ , provided that R ⁸ is -C _n H _{2n + 1} , R ⁹ is a _{-C q H 2q + 1, l} , m, n and q are represented by independently 0 to 20), others _{-M-C r H 2r + 1} ( wherein, M is the It has the same meaning as, r is 0 to 20) or _{- (M-C l H 2l} ) y C s H 2s + 1 ( where, M and l are as defined above, y and s are each independently Wherein one or more of R ¹ , R ² and R ³ is M is —O—,
R ⁴ represents the following general formula (IV), formula (V) or formula (i):

(In the formula, M, X, Y, R ⁶ , l and m are as defined above, and R ¹⁰ is —NR ⁸ —, —NR ⁸ —NR ⁸ — or —N═N—, wherein R ⁸ Is synonymous with the above),
R ⁵ represents the above general formula (II), formula (III), or —C ₁ H _2l —R ¹¹ (where R ¹¹ represents —NR ⁸ R ⁹ , —NR ⁸ —NR ⁸ R ⁹ , —N═NR ^8). or a _{-M-C m H 2m + 1} , ^{where, R 8, R 9, M} , l and m are represented by a is) defined above,
z is preferably 1 to 10.]

［式（VI）中のＷは−ＮＲ⁸−、−Ｏ−又は−ＣＲ⁸Ｒ¹⁵−（ここで、Ｒ¹⁵は−Ｒ⁹又は−Ｃ_mＨ_2m−Ｒ⁷であり、但し、Ｒ⁷は−ＮＲ⁸Ｒ⁹、−ＮＲ⁸−ＮＲ⁸Ｒ⁹又は−Ｎ＝ＮＲ⁸であり、Ｒ⁸は−Ｃ_nＨ_2n+1で、Ｒ⁹は−Ｃ_qＨ_2q+1で、ｍ、ｎ及びｑはそれぞれ独立して０〜２０である）で表され、
Ｒ¹²及びＲ¹³はそれぞれ独立して−Ｍ−Ｃ_lＨ_2l−（ここで、Ｍは−Ｏ−又は−ＣＨ₂−で、ｌは０〜２０である）で表され、
Ｒ¹⁴は−Ｍ−Ｃ_rＨ_2r+1又は−Ｍ−Ｃ_rＨ_2r−Ｒ⁷（ここで、Ｍ及びＲ⁷は上記と同義であり、ｒは０〜２０である）或いは−(Ｍ−Ｃ_lＨ_2l)_yＣ_sＨ_2s+1（ここで、Ｍ及びｌは上記と同義であり、ｙ及びｓはそれぞれ独立して１〜２０である）で表され、但し、Ｒ¹²、Ｒ¹³及びＲ¹⁴の一つ以上はＭが−Ｏ−であり、
Ｒ⁴は下記一般式（VII）、式（VIII）又は式（ii）：

（式中、Ｍ、ｌ及びｍは上記と同義であり、Ｘ及びＹはそれぞれ独立して−Ｏ−、−ＮＲ⁸−又は−ＣＨ₂−で、Ｒ⁶は−ＯＲ⁸、−ＮＲ⁸Ｒ⁹又は−Ｒ⁸で、Ｒ¹⁰は−ＮＲ⁸−、−ＮＲ⁸−ＮＲ⁸−又は−Ｎ＝Ｎ−であり、但し、Ｒ⁸及びＲ⁹は上記と同義である）で表され、
Ｒ⁵は下記一般式（IX）、式（X）又は式（iii）：

（式中、Ｍ、Ｘ、Ｙ、Ｒ⁶、Ｒ⁷、ｌ及びｍは上記と同義であり、Ｒ¹¹は−ＮＲ⁸Ｒ⁹、−ＮＲ⁸−ＮＲ⁸Ｒ⁹、−Ｎ＝ＮＲ⁸又は−Ｍ−Ｃ_mＨ_2m+1であり、但し、Ｒ⁸、Ｒ⁹、Ｍ及びｍは上記と同義である）で表され、
ｚは１〜１０である］で表されることが好ましい。 In the method for producing a silane coupling agent of the present invention, the protected silane compound having a mercapto group and an aminoalkoxyl group has the following general formula (VI):

[W in Formula (VI) is —NR ⁸ —, —O—, or —CR ⁸ R ¹⁵ — (wherein R ¹⁵ is —R ⁹ or —C _m H _2m —R ⁷ , where R ⁷ Is —NR ⁸ R ⁹ , —NR ⁸ —NR ⁸ R ⁹ or —N═NR ⁸ , R ⁸ is —C _n H _{2n + 1} , R ⁹ is —C _q H _{2q + 1} , m, n and q are each independently 0 to 20),
R ¹² and R ¹³ are each independently represented by —M—C ₁ H _{2 1} — (wherein M is —O— or —CH ₂ —, and 1 is 0 to 20),
R ¹⁴ represents —M—C _r H _{2r + 1} or —M—C _r H _2r —R ⁷ (wherein M and R ⁷ are as defined above, and r is 0 to 20) or — (M _{-C l H 2l) y C s} H 2s + 1 ( where, M and l are as defined above, y and s are expressed in each independently 1 to 20), where, R ^12, One or more of R ¹³ and R ¹⁴ is M is —O—;
R ⁴ represents the following general formula (VII), formula (VIII) or formula (ii):

Wherein M, l and m are as defined above, X and Y are each independently —O—, —NR ⁸ — or —CH ₂ —, and R ⁶ is —OR ⁸ , —NR ⁸ R ⁹ or -R ^8, R ¹⁰ is ^{-NR 8 -, - NR 8 -NR} 8 - or -N = a N-, provided that, R ⁸ and R ⁹ are represented by the same meaning as above),
R ⁵ represents the following general formula (IX), formula (X) or formula (iii):

(In the formula, M, X, Y, R ⁶ , R ⁷ , l and m are as defined above, and R ¹¹ is —NR ⁸ R ⁹ , —NR ⁸ —NR ⁸ R ⁹ , —N═NR ⁸ or a _{-M-C m H 2m + 1} , where, R ^8, R ^9, M and m are represented by the same meaning as above),
z is preferably 1 to 10.]

［式（XI）中のＷは−ＮＲ⁸−、−Ｏ−又は−ＣＲ⁸Ｒ¹⁵−（ここで、Ｒ¹⁵は−Ｒ⁹又は−Ｃ_mＨ_2m−Ｒ⁷であり、但し、Ｒ⁷は−ＮＲ⁸Ｒ⁹、−ＮＲ⁸−ＮＲ⁸Ｒ⁹又は−Ｎ＝ＮＲ⁸であり、Ｒ⁸は−Ｃ_nＨ_2n+1で、Ｒ⁹は−Ｃ_qＨ_2q+1で、ｍ、ｎ及びｑはそれぞれ独立して０〜２０である）で表され、
Ｒ¹²及びＲ¹³はそれぞれ独立して−Ｍ−Ｃ_lＨ_2l−（ここで、Ｍは−Ｏ−又は−ＣＨ₂−で、ｌは０〜２０である）で表され、
Ｒ¹⁴は−Ｍ−Ｃ_rＨ_2r+1又は−Ｍ−Ｃ_rＨ_2r−Ｒ⁷（ここで、Ｍ及びＲ⁷は上記と同義であり、ｒは０〜２０である）或いは−(Ｍ−Ｃ_lＨ_2l)_yＣ_sＨ_2s+1（ここで、Ｍ及びｌは上記と同義であり、ｙ及びｓはそれぞれ独立して１〜２０である）で表され、但し、Ｒ¹²、Ｒ¹³及びＲ¹⁴の一つ以上はＭが−Ｏ−であり、
Ｒ⁴は下記一般式（XII）、式（XIII）又は式（iv）：

(式中、Ｍ、ｌ及びｍは上記と同義であり、Ｘ及びＹはそれぞれ独立して−Ｏ−、−ＮＲ⁸−又は−ＣＨ₂−で、Ｒ⁶は−ＯＲ⁸、−ＮＲ⁸Ｒ⁹又は−Ｒ⁸で、Ｒ¹⁰は−ＮＲ⁸−、−ＮＲ⁸−ＮＲ⁸−又は−Ｎ＝Ｎ−であり、但し、Ｒ⁸及びＲ⁹は上記と同義である）で表され、
Ｒ⁵は下記一般式（XIV）、式（XV）又は式（v）：

（式中、Ｍ、Ｘ、Ｙ、Ｒ⁶、Ｒ⁷、ｌ及びｍは上記と同義であり、Ｒ¹¹は−ＮＲ⁸Ｒ⁹、−ＮＲ⁸−ＮＲ⁸Ｒ⁹、−Ｎ＝ＮＲ⁸又は−Ｍ−Ｃ_mＨ_2m+1であり、但し、Ｒ⁸、Ｒ⁹、Ｍ及びｍは上記と同義である）で表され、
ｘ及びｚはそれぞれ独立して１〜１０である］で表される構造を含むことが好ましい。 In the method for producing a silane coupling agent of the present invention, the protected silane compound having a mercapto group and an aminoalkoxyl group is represented by the following general formula (XI):

[W in Formula (XI) is —NR ⁸ —, —O—, or —CR ⁸ R ¹⁵ — (where R ¹⁵ is —R ⁹ or —C _m H _2m —R ⁷ , provided that R ⁷ Is —NR ⁸ R ⁹ , —NR ⁸ —NR ⁸ R ⁹ or —N═NR ⁸ , R ⁸ is —C _n H _{2n + 1} , R ⁹ is —C _q H _{2q + 1} , m, n and q are each independently 0 to 20),
R ¹² and R ¹³ are each independently represented by —M—C ₁ H _{2 1} — (wherein M is —O— or —CH ₂ —, and 1 is 0 to 20),
R ¹⁴ represents —M—C _r H _{2r + 1} or —M—C _r H _2r —R ⁷ (wherein M and R ⁷ are as defined above, and r is 0 to 20) or — (M _{-C l H 2l) y C s} H 2s + 1 ( where, M and l are as defined above, y and s are expressed in each independently 1 to 20), where, R ^12, One or more of R ¹³ and R ¹⁴ is M is —O—;
R ⁴ represents the following general formula (XII), formula (XIII) or formula (iv):

(Wherein M, l and m are as defined above, X and Y are each independently —O—, —NR ⁸ — or —CH ₂ —, R ⁶ is —OR ⁸ , —NR ⁸ R; ⁹ or -R ^8, R ¹⁰ is ^{-NR 8 -, - NR 8 -NR} 8 - or -N = a N-, provided that, R ⁸ and R ⁹ are represented by the same meaning as above),
R ⁵ is the following general formula (XIV), formula (XV) or formula (v):

(In the formula, M, X, Y, R ⁶ , R ⁷ , l and m are as defined above, and R ¹¹ is —NR ⁸ R ⁹ , —NR ⁸ —NR ⁸ R ⁹ , —N═NR ⁸ or a _{-M-C m H 2m + 1} , where, R ^8, R ^9, M and m are represented by the same meaning as above),
x and z are each independently 1 to 10].

  In the method for producing a silane coupling agent of the present invention, the protected silane compound having a mercapto group and an aminoalkoxyl group is represented by the compound represented by the above formula (VI) and the above formula (XI). A mixture with a compound containing a structure is also preferred.

  In the method for producing a silane coupling agent of the present invention, as the silane compound having a protected mercapto group and aminoalkoxyl group, 3-octanoylthio-propyl (monodimethylaminoethoxy) diethoxysilane, 3-octanoylthio-propyl ( Didimethylaminoethoxy) monoethoxysilane, 3-octanoylthio-propyltridimethylaminoethoxysilane, 3-octanoylthio-propyl (monodiethylaminoethoxy) diethoxysilane, 3-octanoylthio-propyl (didiethylaminoethoxy) monoethoxysilane, 3- Octanoylthio-propyltridiethylaminoethoxysilane, 3-octanoylthio-propyl (dimethylaminoethoxy) ethoxymethylsilane, 3-octanoylthio-propyl (dimethylaminoethoxy) di Methylsilane, 3-octanoylthio-propyl (didimethylaminoethoxy) monomethylsilane, 3-octanoylthio-propyl (diethylaminoethoxy) ethoxymethylsilane, 3-octanoylthio-propyl (diethylaminoethoxy) dimethylsilane, 3-octanoylthio-propyl (didiethylaminoethoxy) ) Monomethylsilane, 3-lauroylthio-propyl (monodimethylaminoethoxy) diethoxysilane, 3-lauroylthio-propyl (didimethylaminoethoxy) monoethoxysilane, 3-lauroylthio-propyltridimethylaminoethoxysilane, 3- Lauroylthio-propyl (monodiethylaminoethoxy) diethoxysilane, 3-lauroylthio-propyl (didiethylaminoethoxy) monoethoxysilane, 3-lauroylthio-propyltri Ethylaminoethoxysilane, 3-lauroylthio-propyl (dimethylaminoethoxy) ethoxymethylsilane, 3-lauroylthio-propyl (dimethylaminoethoxy) dimethylsilane, 3-lauroylthio-propyl (didimethylaminoethoxy) monomethylsilane, 3 -Lauroylthio-propyl (diethylaminoethoxy) ethoxymethylsilane, 3-lauroylthio-propyl (diethylaminoethoxy) dimethylsilane, 3-lauroylthio-propyl (didiethylaminoethoxy) monomethylsilane, 3-octanoylthio-propyl (ethoxy) 1, 3-Dioxa-6-methylaza-2-silacyclooctane, 3-octanoylthio-propyl (ethoxy) 1,3-dioxa-6-ethylaza-2-silacyclooctane, 3-octanoylthio-propyl (ethoxy) 1,3- Dioxa-6-propyl Pyraza-2-silacyclooctane, 3-octanoylthio-propyl (ethoxy) 1,3-dioxa-6-butylaza-2-silacyclooctane, 3-octanoylthio-propyl (methyl) 1,3-dioxa-6-methylaza- 2-Silacyclooctane, 3-octanoylthio-propyl (methyl) 1,3-dioxa-6-ethylaza-2-silacyclooctane, 3-octanoylthio-propyl (methyl) 1,3-dioxa-6-propylaza-2- Silacyclooctane, 3-octanoylthio-propyl (methyl) 1,3-dioxa-6-butylaza-2-silacyclooctane, 3-lauroylthio-propyl (ethoxy) 1,3-dioxa-6-methylaza-2-sila Cyclooctane, 3-lauroylthio-propyl (ethoxy) 1,3-dioxa-6-ethylaza-2-silacyclooctane, 3-lauroylthio-propyl (ethoxy) 1, 3-dioxa-6-propylaza-2-silacyclooctane, 3-lauroylthio-propyl (ethoxy) 1,3-dioxa-6-butylaza-2-silacyclooctane, 3-lauroylthio-propyl (methyl) 1, 3-Dioxa-6-methylaza-2-silacyclooctane, 3-lauroylthio-propyl (methyl) 1,3-dioxa-6-ethylaza-2-silacyclooctane, 3-lauroylthio-propyl (methyl) 1, 3-Dioxa-6-propylaza-2-silacyclooctane and 3-lauroylthio-propyl (methyl) 1,3-dioxa-6-butylaza-2-silacyclooctane are preferred.

  According to the present invention, by converting the halogen element of the haloalkyl group of the silane compound having a haloalkyl group and an aminoalkoxyl group into an alkanoylthio group, the rubber composition is produced in a high yield while suppressing the formation of by-products. It is possible to provide a silane coupling agent capable of reducing the hysteresis loss and improving the wear resistance.

  The present invention is described in detail below. The method for producing a silane coupling agent according to the present invention includes a silane having a protected mercapto group and an aminoalkoxyl group by converting a halogen element of the haloalkyl group of the silane compound having a haloalkyl group and an aminoalkoxyl group into an alkanoylthio group. It includes a step of obtaining a compound. In the method for producing a silane coupling agent of the present invention, an aminoalkoxyl group is introduced into a silane compound having a haloalkyl group, instead of introducing an aminoalkoxyl group after protecting the mercapto group of the silane compound having a mercapto group. Since a reaction route for converting the halogen element portion of the haloalkyl group into an alkanoylthio group is employed, the production of by-products can be greatly suppressed. In addition, the silane coupling agent obtained by the production method of the present invention, when blended with a rubber component together with an inorganic filler such as silica, greatly reduces the hysteresis loss of the rubber composition and greatly improves the wear resistance. Can be improved. In the present invention, the silane compound having a haloalkyl group and an aminoalkoxyl group preferably has one or more silicon-oxygen bonds (Si—O).

［式（XVI）中のＲ¹、Ｒ²及びＲ³は、少なくとも一つが上記一般式（II）又は式（III）で表され、その他が−Ｍ−Ｃ_rＨ_2r+1（ここで、Ｍは−Ｏ−又は−ＣＨ₂−で、ｒは０〜２０である）又は−(Ｍ−Ｃ_lＨ_2l)_yＣ_sＨ_2s+1（ここで、Ｍは上記と同義であり、ｌは０〜２０であり、ｙ及びｓはそれぞれ独立して１〜２０である）で表され、但し、Ｒ¹、Ｒ²及びＲ³の一つ以上はＭが−Ｏ−であり、Ｒ⁴は上記一般式（IV）、式（V）又は式（i）で表され、Ｔは、フルオロ基、クロロ基、ブロモ基又はヨード基である］で表される化合物、下記式（XVII）：

［式（XVII）中のＷは−ＮＲ⁸−、−Ｏ−又は−ＣＲ⁸Ｒ¹⁵−（ここで、Ｒ¹⁵は−Ｒ⁹又は−Ｃ_mＨ_2m−Ｒ⁷であり、但し、Ｒ⁷は−ＮＲ⁸Ｒ⁹、−ＮＲ⁸−ＮＲ⁸Ｒ⁹又は−Ｎ＝ＮＲ⁸であり、Ｒ⁸は−Ｃ_nＨ_2n+1で、Ｒ⁹は−Ｃ_qＨ_2q+1で、ｍ、ｎ及びｑはそれぞれ独立して０〜２０である）で表され、Ｒ¹²及びＲ¹³はそれぞれ独立して−Ｍ−Ｃ_lＨ_2l−（ここで、Ｍは−Ｏ−又は−ＣＨ₂−で、ｌは０〜２０である）で表され、Ｒ¹⁴は−Ｍ−Ｃ_rＨ_2r+1又は−Ｍ−Ｃ_rＨ_2r−Ｒ⁷（ここで、Ｍ及びＲ⁷は上記と同義であり、ｒは０〜２０である）或いは−(Ｍ−Ｃ_lＨ_2l)_yＣ_sＨ_2s+1（ここで、Ｍ及びｌは上記と同義であり、ｙ及びｓはそれぞれ独立して１〜２０である）で表され、但し、Ｒ¹²、Ｒ¹³及びＲ¹⁴の一つ以上はＭが−Ｏ−であり、Ｒ⁴は上記一般式（VII）、式（VIII）又は式（ii）で表され、Ｔは、フルオロ基、クロロ基、ブロモ基又はヨード基である］で表される化合物、及び下記式（XVIII）：

［式中（XVIII）のＷは−ＮＲ⁸−、−Ｏ−又は−ＣＲ⁸Ｒ¹⁵−（ここで、Ｒ¹⁵は−Ｒ⁹又は−Ｃ_mＨ_2m−Ｒ⁷であり、但し、Ｒ⁷は−ＮＲ⁸Ｒ⁹、−ＮＲ⁸−ＮＲ⁸Ｒ⁹又は−Ｎ＝ＮＲ⁸であり、Ｒ⁸は−Ｃ_nＨ_2n+1で、Ｒ⁹は−Ｃ_qＨ_2q+1で、ｍ、ｎ及びｑはそれぞれ独立して０〜２０である）で表され、Ｒ¹²及びＲ¹³はそれぞれ独立して−Ｍ−Ｃ_lＨ_2l−（ここで、Ｍは−Ｏ−又は−ＣＨ₂−で、ｌは０〜２０である）で表され、Ｒ¹⁴は−Ｍ−Ｃ_rＨ_2r+1又は−Ｍ−Ｃ_rＨ_2r−Ｒ⁷（ここで、Ｍ及びＲ⁷は上記と同義であり、ｒは０〜２０である）或いは−(Ｍ−Ｃ_lＨ_2l)_yＣ_sＨ_2s+1（ここで、Ｍ及びｌは上記と同義であり、ｙ及びｓはそれぞれ独立して１〜２０である）で表され、但し、Ｒ¹²、Ｒ¹³及びＲ¹⁴の一つ以上はＭが−Ｏ−であり、Ｒ⁴は上記一般式（XII）、式（XIII）又は式（iv）で表され、ｘは１〜１０であり、Ｔは、フルオロ基、クロロ基、ブロモ基又はヨード基である］で表される構造を含む化合物が好ましい。これら原料シラン化合物は、一種単独で用いてもよいし、二種以上を組み合わせて用いてもよい。 A silane compound (hereinafter also referred to as a raw material silane compound) used in the method for producing a silane coupling agent of the present invention is a silane compound having a haloalkyl group and an aminoalkoxyl group, and more specifically, the following formula (XVI) :

[At least one of R ¹ , R ² and R ³ in the formula (XVI) is represented by the above general formula (II) or (III), and the other is -M-C _r H _{2r + 1} (wherein M is —O— or —CH ₂ —, and r is 0 to 20) or — (M—C ₁ H _2l ) _y C _s H _{2s + 1} (where M is as defined above, l Is 0 to 20, y and s are each independently 1 to 20), provided that one or more of R ¹ , R ² and R ³ is M is —O—, and R ⁴ Is represented by the above general formula (IV), formula (V) or formula (i), and T is a fluoro group, chloro group, bromo group or iodo group], a compound represented by the following formula (XVII):

[W in Formula (XVII) is —NR ⁸ —, —O—, or —CR ⁸ R ¹⁵ — (wherein R ¹⁵ is —R ⁹ or —C _m H _2m —R ⁷ , where R ⁷ Is —NR ⁸ R ⁹ , —NR ⁸ —NR ⁸ R ⁹ or —N═NR ⁸ , R ⁸ is —C _n H _{2n + 1} , R ⁹ is —C _q H _{2q + 1} , m, n and q are each independently 0 to 20), and R ¹² and R ¹³ are each independently —M—C ₁ H _2l — (where M is —O— or —CH ₂ —. Wherein R is 0 to 20, and R ¹⁴ is —M—C _r H _{2r + 1} or —M—C _r H _2r —R ⁷ (wherein M and R ⁷ are as defined above). There, r is a is) or _{0~20 - (M-C l H} 2l) y C s H 2s + 1 ( where, M and l are as defined above, y and s are each independently 1 In which at least one of R ¹² , R ¹³ and R ¹⁴ is M is —O—. , R ⁴ is represented by the above general formula (VII), formula (VIII) or formula (ii), and T is a fluoro group, chloro group, bromo group or iodo group], and the following formula (XVIII):

[W in the formula (XVIII) is —NR ⁸ —, —O— or —CR ⁸ R ¹⁵ — (wherein R ¹⁵ is —R ⁹ or —C _m H _2m —R ⁷ , where R ⁷ Is —NR ⁸ R ⁹ , —NR ⁸ —NR ⁸ R ⁹ or —N═NR ⁸ , R ⁸ is —C _n H _{2n + 1} , R ⁹ is —C _q H _{2q + 1} , m, n and q are each independently 0 to 20), and R ¹² and R ¹³ are each independently —M—C ₁ H _2l — (where M is —O— or —CH ₂ —. Wherein R is 0 to 20, and R ¹⁴ is —M—C _r H _{2r + 1} or —M—C _r H _2r —R ⁷ (wherein M and R ⁷ are as defined above). There, r is a is) or _{0~20 - (M-C l H} 2l) y C s H 2s + 1 ( where, M and l are as defined above, y and s are each independently 1 expressed in a 20), provided that one or more M of R ^12, R ¹³ and R ¹⁴ is -O- der , R ⁴ is the general formula (XII), is represented by the formula (XIII) or formula (iv), x is 1 to 10, T is fluoro, chloro group, a bromo group or an iodo group] Compounds containing the structure represented are preferred. These raw material silane compounds may be used individually by 1 type, and may be used in combination of 2 or more types.

<< Compound of Formula (XVI) >>
In the above formula (XVI), T is a fluoro group, a chloro group, a bromo group or an iodo group, and preferably a chloro group, a bromo group or an iodo group. In addition, at least one of R ¹ , R ² and R ³ is represented by the above general formula (II) or formula (III), and the other is —M—C _r H _{2r + 1} (where M is —O— Or —CH ₂ —, r is 0 to 20, preferably 0 to 10) or — (M—C ₁ H _{2 l} ) _y C _s H _{2s + 1} (where M is as defined above). Wherein l is 0-20, preferably in the range 0-10, and y and s are each independently 1-20. Provided that M is —O— in one or more of R ¹ , R ² and R ³ . Incidentally, -C _r H _{2r + 1,} since r is 0 to 20, hydrogen or an alkyl group having 1 to 20 carbon atoms. Further, -C _s H _{2s + 1,} since s is 1 to 20, an alkyl group having 1 to 20 carbon atoms. Here, as the alkyl group having 1 to 20 carbon atoms, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, decyl group, dodecyl group, tridecyl group, tetradecyl group, Examples include a pentadecyl group, a hexadecyl group, a heptadecyl group, a stearyl group, and the like. The alkyl group may be linear or branched. In addition, since l is 0 to 20, —C ₁ H _2l — is a single bond or an alkylene group having 1 to 20 carbon atoms. Here, as a C1-C20 alkylene group, a methylene group, ethylene group, trimethylene group, a propylene group, etc. are mentioned, This alkylene group may be linear or branched.

In the above formulas (II) and (III), M is —O— or —CH ₂ —, and l is 0 to 20, preferably 0 to 10. Moreover, in said formula (II), m is 0-20, and the range of 0-10 is preferable. Incidentally, -C _m H _{2m + 1,} since m is 0 to 20, hydrogen or an alkyl group having 1 to 20 carbon atoms. Here, the alkyl group having 1 to 20 carbon atoms is as described above. Further, -C _l H _2l- is as described above.

In the above formula (II), X and Y are each independently —O—, —NR ⁸ — or —CH ₂ —. Wherein, R ⁸ is -C _n H _{2n + 1, n} is 0 to 20, preferably in the range of 0. Note that -C _n H _{2n + 1} is hydrogen or an alkyl group having 1 to 20 carbon atoms because n is 0 to 20. R ⁶ is —OR ⁸ , —NR ⁸ R ⁹ or —R ⁸ . Wherein, R ⁸ is _{-C n H 2n + 1, R} 9 is -C _q H _{2q + 1,} n and q are 0 to 20 independently, preferably in the range of 0 . Note that the -C _n H _{2n + 1,} are as described above, -C _q H _{2q + 1,} since q is 0 to 20, hydrogen or an alkyl group having 1 to 20 carbon atoms. The alkyl group having 1 to 20 carbon atoms is as described above.

In the above formula (III), R ⁷ is —NR ⁸ R ⁹ , —NR ⁸ —NR ⁸ R ^9, or —N═NR ⁸ . Wherein, R ⁸ is _{-C n H 2n + 1, R} 9 is -C _q H _{2q + 1,} n and q are 0 to 20 independently, preferably in the range of 0 . Note that the -C _n H _{2n + 1} and -C _q H _{2q + 1,} is as described above.

In the above formula (XVI), R ⁴ is represented by the above general formula (IV), formula (V) or formula (i), and particularly preferably represented by —C ₁ H _2l —. And l is 0 to 20, preferably in the range of 0 to 10. In addition, since l is 0 to 20, —C ₁ H _2l — is a single bond or an alkylene group having 1 to 20 carbon atoms. Here, the alkylene group having 1 to 20 carbon atoms is as described above.

In the above formula (IV), formula (V) and formula (i), M is —O— or —CH ₂ —, l and m are each independently 0 to 20, and a range of 0 to 10 is preferable. Note that -C _l H _2l -and -C _m H _2m -are a single bond or an alkylene group having 1 to 20 carbon atoms because l and m are 0 to 20. Here, the alkylene group having 1 to 20 carbon atoms is as described above. In the formula (IV), X and Y are each independently —O—, —NR ⁸ — or —CH ₂ —, and R ⁶ is —OR ⁸ , —NR ⁸ R ⁹ or —R ⁸ . is there. R ⁸ and R ⁹ are as described above. Further, in the above formula (V), R ¹⁰ is —NR ⁸ —, —NR ⁸ —NR ⁸ — or —N═N—, wherein R ⁸ is —C _n H _{2n + 1} , the -C _n H _{2n + 1,} as described above.

<< Compound of Formula (XVII) >>
In the above formula (XVII), T is a fluoro group, a chloro group, a bromo group or an iodo group, and preferably a chloro group, a bromo group or an iodo group. Further, W is, -NR ⁸ -, - O-or -CR ⁸ R ¹⁵ - is represented by, wherein, R ¹⁵ is -R ⁹ or -C _m H _2m -R ^7, provided that, R ⁷ is -NR ⁸ R ^9, a -NR ⁸ -NR ⁸ R ⁹ or -N = NR ^8, R ⁸ is _{-C n H 2n + 1, R} 9 is _{-C q H 2q + 1, m} , n And q are each independently 0 to 20, preferably in the range of 0 to 10. Incidentally, -C _m H _2m -, since m is 0-20, a single bond or an alkylene group with 1 to 20 carbon atoms. Here, as a C1-C20 alkylene group, a methylene group, ethylene group, trimethylene group, a propylene group, etc. are mentioned, This alkylene group may be linear or branched. Moreover, -C _n H _{2n + 1} and -C _q H _{2q + 1,} since n and q are 0 to 20, hydrogen or an alkyl group having 1 to 20 carbon atoms. Here, as the alkyl group having 1 to 20 carbon atoms, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, decyl group, dodecyl group, tridecyl group, tetradecyl group, Examples include a pentadecyl group, a hexadecyl group, a heptadecyl group, a stearyl group, and the like. The alkyl group may be linear or branched.

In the formula (XVII), R ¹² and R ¹³ are each independently represented by —M—C ₁ H _{2 l} —, and R ¹⁴ is —M—C _r H _{2r + 1} or —M—C _r H _2r —. R ⁷ or — (M—C ₁ H _{2 1} ) _y C _s H _{2s + 1} , where M is —O— or —CH ₂ —, and R ⁷ is —NR ⁸ R ⁹ , —NR ⁸ is a -NR ⁸ R ⁹ or -N = NR ^8, R ⁸ is _{-C n H 2n + 1, R} 9 is _{-C q H 2q + 1, l} , n, q and r are each independently 0 to 20 and a range of 0 to 10 is preferable, and y and s are each independently 1 to 20. However, in one or more of R ¹² , R ¹³ and R ¹⁴ , M is —O—. In addition, since l is 0 to 20, —C ₁ H _2l — is a single bond or an alkylene group having 1 to 20 carbon atoms. Here, the alkylene group having 1 to 20 carbon atoms is as described above. It is. Further, -C _r H _{2r + 1,} since r is 0 to 20, hydrogen or an alkyl group having 1 to 20 carbon atoms. Further, -C _s H _{2s + 1,} since s is 1 to 20, an alkyl group having 1 to 20 carbon atoms. Here, the alkyl group having 1 to 20 carbon atoms is as described above. Note that the -C _n H _{2n + 1} and -C _q H _{2q + 1,} is as described above.

In the above formula (XVII), R ⁴ is represented by the above general formula (VII), formula (VIII) or formula (ii), and particularly preferably represented by —C ₁ H _2l —. , L is 0-20, with a range of 0-10 being preferred. In addition, -C _l H _2l- is as described above.

In the above formula (VII), formula (VIII), and formula (ii), M is —O— or —CH ₂ —, l and m are each independently 0-20, and the range of 0-10 is preferable. In the above formula (VII), X and Y are each independently —O—, —NR ⁸ — or —CH ₂ —, and R ⁶ is —OR ⁸ , —NR ⁸ R ⁹ or —R ⁸ . Yes, where R ⁸ is —C _n H _{2n + 1} and R ⁹ is —C _q H _{2q + 1} . Further, in the above formula (VIII), R ¹⁰ is —NR ⁸ —, —NR ⁸ —NR ⁸ —, or —N═N—, where R ⁸ is —C _n H _{2n + 1} . Note that the -C _n H _{2n + 1} and -C _q H _{2q + 1,} is as described above.

<< Compound containing structure of formula (XVIII) >>
In said formula (XVIII), x is 1-10, the range of 1-5 is preferable, and the range of 1-2 is still more preferable. If x exceeds 10, it becomes difficult to synthesize. T is a fluoro group, a chloro group, a bromo group or an iodo group, and is preferably a chloro group, a bromo group or an iodo group. Further, W is represented by —NR ⁸ —, —O— or —CR ⁸ R ¹⁵ —, wherein R ¹⁵ is —R ⁹ or —C _m H _2m —R ⁷ , where R ⁷ is -NR ⁸ R ^9, a -NR ⁸ -NR ⁸ R ⁹ or -N = NR ^8, R ⁸ is _{-C n H 2n + 1, R} 9 is _{-C q H 2q + 1, m} , n And q are each independently 0 to 20, preferably in the range of 0 to 10. Incidentally, -C _m H _2m -, since m is 0-20, a single bond or an alkylene group with 1 to 20 carbon atoms. Here, as a C1-C20 alkylene group, a methylene group, ethylene group, trimethylene group, a propylene group, etc. are mentioned, This alkylene group may be linear or branched. Moreover, -C _n H _{2n + 1} and -C _q H _{2q + 1,} since n and q are 0 to 20, hydrogen or an alkyl group having 1 to 20 carbon atoms. Here, as the alkyl group having 1 to 20 carbon atoms, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, decyl group, dodecyl group, tridecyl group, tetradecyl group, Examples include a pentadecyl group, a hexadecyl group, a heptadecyl group, a stearyl group, and the like. The alkyl group may be linear or branched.

In the above formula (XVIII), R ¹² and R ¹³ are each independently represented by —M—C ₁ H _{2 l} —, and R ¹⁴ is —M—C _r H _{2r + 1} or —M—C _r H _2r —. R ⁷ or — (M—C ₁ H _{2 1} ) _y C _s H _{2s + 1} , where M is —O— or —CH ₂ —, and R ⁷ is —NR ⁸ R ⁹ , —NR ⁸ is a -NR ⁸ R ⁹ or -N = NR ^8, R ⁸ is _{-C n H 2n + 1, R} 9 is _{-C q H 2q + 1, l} , n, q and r are each independently 0 to 20 and a range of 0 to 10 is preferable, and y and s are each independently 1 to 20. However, in one or more of R ¹² , R ¹³ and R ¹⁴ , M is —O—. In addition, since l is 0 to 20, —C ₁ H _2l — is a single bond or an alkylene group having 1 to 20 carbon atoms. Here, the alkylene group having 1 to 20 carbon atoms is as described above. It is. Further, -C _r H _{2r + 1,} since r is 0 to 20, hydrogen or an alkyl group having 1 to 20 carbon atoms. Further, -C _s H _{2s + 1,} since s is 1 to 20, an alkyl group having 1 to 20 carbon atoms. Here, the alkyl group having 1 to 20 carbon atoms is as described above. Note that the -C _n H _{2n + 1} and -C _q H _{2q + 1,} is as described above.

In the formula (XVIII), R ⁴ is represented by the general formula (XII), formula (XIII) or formula (iv), and is particularly preferably represented by —C ₁ H _2l —. , L is 0-20, with a range of 0-10 being preferred. In addition, -C _l H _2l- is as described above.

In the above formula (XII), formula (XIII) and formula (iv), M is —O— or —CH ₂ —, and l and m are 0 to 20, preferably 0 to 10. In the above formula (XII), X and Y are each independently —O—, —NR ⁸ — or —CH ₂ —, and R ⁶ is —OR ⁸ , —NR ⁸ R ⁹ or —R ⁸ . Yes, where R ⁸ is —C _n H _{2n + 1} and R ⁹ is —C _q H _{2q + 1} . Further, in the above formula (XIII), R ¹⁰ is —NR ⁸ —, —NR ⁸ —NR ⁸ —, or —N═N—, wherein R ⁸ is —C _n H _{2n + 1} . Note that the -C _n H _{2n + 1} and -C _q H _{2q + 1,} is as described above.

Incidentally, the raw material silane compound, for example, represented by the general formula ^{(XVI), R 1, R} 2 and R ³ is -M-C _l H _{2l + 1} or or _{- (M-C l H 2l} ) y 2- (dimethylamino) ethanol, 2- (diethylamino) ethanol, a compound represented by C _s H _{2s + 1} , wherein one or more of M in R ¹ , R ² and R ³ is —O—; Add amine compounds such as 2- (dimethylamino) propanol, 2- (diethylamino) propanol, and N-methyldiethanolamine, and then use p-toluenesulfonic acid, hydrochloric acid and other acids as catalysts, and titanium alkoxides such as titanium tetra-n-butoxide. And heating to replace one or more of R ¹ , R ² and R ³ with a nitrogen-containing group represented by formula (II) or (III), or replacing R ¹ and R ² with —R ¹² — It can be synthesized by substituting with a nitrogen-containing group represented by W—R ¹³ —. Here, when an amine compound having two hydroxy groups such as N-methyldiethanolamine is used as the amine compound, a silane compound represented by the above general formula (XVII) is obtained. The silane compound is condensed between molecules. In the condensate of the silane compound, for example, a silane compound having a structure represented by the general formula (XVIII) is included. In addition, when the said raw material silane compound is a mixture of the silane compound (monomer or monomer) which has a haloalkyl group and an amino alkoxyl group, and its condensate, the kind of silane compound, an amine compound, and a catalyst, reaction temperature The proportion of the raw material silane compound produced can be adjusted by appropriately selecting the reaction time and the like.

  Here, when the raw material silane compound is a mixture of a silane compound (monomer or monomer) having a haloalkyl group and an aminoalkoxyl group and a condensate thereof, the raw material silane compound contains a monomer. The rate is 30 to 99% by mass, the content of the dimer is 1 to 60% by mass, the content of the trimer is 50% by mass or less, and the multimer of the tetramer or more is 40% by mass or less. It is preferable. Specifically, when the raw material silane compound is a mixture of a compound represented by the general formula (XVII) and a compound containing a structure represented by the general formula (XVIII), the general formula ( The content of the compound represented by XVII) is preferably 70 to 99% by mass, and the content of the compound containing the structure represented by the general formula (XVIII) is preferably 1 to 30% by mass. Moreover, the compound containing the structure represented by the general formula (XVIII) is 50 to 80% by mass of a compound in which x is 1 in the formula, 1 to 50% by mass of a compound in which x is 2, and x is 3 or more. It is preferable to contain the compound which is 10 mass% or less.

  Specific examples of the raw material silane compound include, for example, 3-chloropropyl (monodimethylaminoethoxy) diethoxysilane, 3-chloropropyl (didimethylaminoethoxy) monoethoxysilane, 3-chloropropyltridimethylaminoethoxysilane, 3-chloropropyl (monodiethylaminoethoxy) diethoxysilane, 3-chloropropyl (didiethylaminoethoxy) monoethoxysilane, 3-chloropropyltridiethylaminoethoxysilane, 3-chloropropyl (dimethylaminoethoxy) ethoxymethylsilane, 3- Chloropropyl (dimethylaminoethoxy) dimethylsilane, 3-chloropropyl (didimethylaminoethoxy) monomethylsilane, 3-chloropropyl (diethylaminoethoxy) ethoxymethylsilane, 3-chloropropyl (diethylamino) Ethoxy) dimethylsilane, 3-chloropropyl (didiethylaminoethoxy) monomethylsilane, 3-chloropropyl (ethoxy) 1,3-dioxa-6-methylaza-2-silacyclooctane, 3-chloropropyl (ethoxy) 1,3 -Dioxa-6-ethylaza-2-silacyclooctane, 3-chloropropyl (ethoxy) 1,3-dioxa-6-propylaza-2-silacyclooctane, 3-chloropropyl (ethoxy) 1,3-dioxa-6 -Butylaza-2-silacyclooctane, 3-chloropropyl (methyl) 1,3-dioxa-6-methylaza-2-silacyclooctane, 3-chloropropyl (methyl) 1,3-dioxa-6-ethylaza-2 -Silacyclooctane, 3-chloropropyl (methyl) 1,3-dioxa-6-propylaza-2-silacyclooctane, 3-chloropropyl (methyl) 1,3-dioxa-6-butylaza- -Silacyclooctane, 3-bromopropyl (monodimethylaminoethoxy) diethoxysilane, 3-bromopropyl (didimethylaminoethoxy) monoethoxysilane, 3-bromopropyltridimethylaminoethoxysilane, 3-bromopropyl (monodiethylamino) Ethoxy) diethoxysilane, 3-bromopropyl (didiethylaminoethoxy) monoethoxysilane, 3-bromopropyltridiethylaminoethoxysilane, 3-bromopropyl (dimethylaminoethoxy) ethoxymethylsilane, 3-bromopropyl (dimethylaminoethoxy) Dimethylsilane, 3-bromopropyl (didimethylaminoethoxy) monomethylsilane, 3-bromopropyl (diethylaminoethoxy) ethoxymethylsilane, 3-bromopropyl (diethylaminoethoxy) dimethylsilane 3-bromopropyl (didiethylaminoethoxy) monomethylsilane, 3-bromopropyl (ethoxy) 1,3-dioxa-6-methylaza-2-silacyclooctane, 3-bromopropyl (ethoxy) 1,3-dioxa-6- Ethylaza-2-silacyclooctane, 3-bromopropyl (ethoxy) 1,3-dioxa-6-propylaza-2-silacyclooctane, 3-bromopropyl (ethoxy) 1,3-dioxa-6-butylaza-2- Silacyclooctane, 3-bromopropyl (methyl) 1,3-dioxa-6-methylaza-2-silacyclooctane, 3-bromopropyl (methyl) 1,3-dioxa-6-ethylaza-2-silacyclooctane, 3-bromopropyl (methyl) 1,3-dioxa-6-propylaza-2-silacyclooctane, 3-bromopropyl (methyl) 1,3-dioxa-6-butylaza-2-silacyclooctane, 3 -Iodopropyl (monodimethylaminoethoxy) diethoxysilane, 3-iodopropyl (didimethylaminoethoxy) monoethoxysilane, 3-iodopropyltridimethylaminoethoxysilane, 3-iodopropyl (monodiethylaminoethoxy) diethoxysilane, 3-iodopropyl (didiethylaminoethoxy) monoethoxysilane, 3-iodopropyltridiethylaminoethoxysilane, 3-iodopropyl (dimethylaminoethoxy) ethoxymethylsilane, 3-iodopropyl (dimethylaminoethoxy) dimethylsilane, 3-iodo Propyl (didimethylaminoethoxy) monomethylsilane, 3-iodopropyl (diethylaminoethoxy) ethoxymethylsilane, 3-iodopropyl (diethylaminoethoxy) dimethylsilane, 3-iodopropyl (didie Tilaminoethoxy) monomethylsilane, 3-iodopropyl (ethoxy) 1,3-dioxa-6-methylaza-2-silacyclooctane, 3-iodopropyl (ethoxy) 1,3-dioxa-6-ethylaza-2-sila Cyclooctane, 3-iodopropyl (ethoxy) 1,3-dioxa-6-propylaza-2-silacyclooctane, 3-iodopropyl (ethoxy) 1,3-dioxa-6-butylaza-2-silacyclooctane, 3, -Iodopropyl (methyl) 1,3-dioxa-6-methylaza-2-silacyclooctane, 3-iodopropyl (methyl) 1,3-dioxa-6-ethylaza-2-silacyclooctane, 3-iodopropyl ( Methyl) 1,3-dioxa-6-propylaza-2-silacyclooctane, 3-iodopropyl (methyl) 1,3-dioxa-6-butylaza-2-silacyclooctane, and the like.

式（XIX）において、ｚは１〜１０であり、１〜４の範囲が好ましく、１であるこが特に好ましい。また、Ｒ⁵は、上記一般式（II）、式（III）、式（IX）、式（X）、式（iii）、式（XIV）、式（XV）又は式（v）或いは−Ｃ_lＨ_2l−Ｒ¹¹であり、ここで、Ｒ¹¹は−ＮＲ⁸Ｒ⁹、−ＮＲ⁸−ＮＲ⁸Ｒ⁹、−Ｎ＝ＮＲ⁸又は−Ｍ−Ｃ_mＨ_2m+1であり、但し、Ｍは−Ｏ−又は−ＣＨ₂−で、Ｒ⁸は−Ｃ_nＨ_2n+1で、Ｒ⁹は−Ｃ_qＨ_2q+1であり、ｌ、ｍ、ｎ及びｑはそれぞれ独立して０〜２０であり、０〜１０の範囲が好ましい。なお、−Ｃ_lＨ_2l−は、ｌが０〜２０であるため、単結合又は炭素数１〜２０のアルキレン基である。ここで、炭素数１〜２０のアルキレン基としては、メチレン基、エチレン基、トリメチレン基、プロピレン基等が挙げられ、該アルキレン基は、直鎖状でも分岐状でもよい。また、−Ｃ_mＨ_2m+1、−Ｃ_nＨ_2n+1及び−Ｃ_qＨ_2q+1は、ｍ、ｎ及びｑが０〜２０であるため、水素又は炭素数１〜２０のアルキル基である。ここで、炭素数１〜２０のアルキル基としては、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基、デシル基、ドデシル基、トリデシル基、テトラデシル基、ペンタデシル基、ヘキサデシル基、ヘプタデシル基、ステアリル基等が挙げられ、該アルキル基は、直鎖状でも、分岐状でもよい。そして、上記一般式（II）及び式（III）については、上記式（XVI）の化合物にて説明したとおりであり、上記式（IX）及び式（XIV）については、上記式（II）と同様に定義され、上記式（X）及び式（XV）については、上記式（III）と同様に定義される。また、上記式（iii）及び式（v）は、−Ｃ_lＨ_2l−Ｒ¹¹であり、上述の通りである。更に、Ｑは、アルカリ金属であり、ナトリウム（Ｎａ）又はカリウム（Ｋ）が好ましい。 Moreover, the manufacturing method of the silane coupling agent of this invention makes the thiocarboxylate represented by the following general formula (XIX) react with the said raw material silane compound (The silane compound which has a haloalkyl group and an amino alkoxyl group). By converting the halogen element of the haloalkyl group of the raw material silane compound into an alkanoylthio group, a silane compound having a protected mercapto group and aminoalkoxyl group can be obtained. In the present invention, the silane compound having a protected mercapto group and aminoalkoxyl group preferably has one or more silicon-oxygen bonds (Si-O).

In the formula (XIX), z is 1 to 10, preferably in the range of 1 to 4, and particularly preferably 1. R ⁵ represents the general formula (II), formula (III), formula (IX), formula (X), formula (iii), formula (XIV), formula (XV), formula (v), or —C. _l H _2l -R ¹¹ , wherein R ¹¹ is -NR ⁸ R ⁹ , -NR ⁸ -NR ⁸ R ⁹ , -N = NR ⁸ or -M-C _m H _{2m + 1} , M is —O— or —CH ₂ —, R ⁸ is —C _n H _{2n + 1} , R ⁹ is —C _q H _{2q + 1} , and l, m, n and q are each independently 0 It is -20, and the range of 0-10 is preferable. In addition, since l is 0 to 20, —C ₁ H _2l — is a single bond or an alkylene group having 1 to 20 carbon atoms. Here, as a C1-C20 alkylene group, a methylene group, ethylene group, trimethylene group, a propylene group, etc. are mentioned, This alkylene group may be linear or branched. _{Further, -C m H 2m + 1,} -C n H 2n + 1 and -C _q H _{2q + 1} is, m, for n and q are 0 to 20, hydrogen or an alkyl group having 1 to 20 carbon atoms It is. Here, as the alkyl group having 1 to 20 carbon atoms, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, decyl group, dodecyl group, tridecyl group, tetradecyl group, Examples include a pentadecyl group, a hexadecyl group, a heptadecyl group, a stearyl group, and the like. The alkyl group may be linear or branched. The general formula (II) and the formula (III) are as described in the compound of the formula (XVI), and the formula (IX) and the formula (XIV) are the same as those of the formula (II) and The same definition is applied, and the formula (X) and the formula (XV) are defined in the same manner as the formula (III). Further, the formula (iii) and formula (v) is -C _l H _2l -R ^11, are as described above. Furthermore, Q is an alkali metal, preferably sodium (Na) or potassium (K).

  In addition, as said thiocarboxylate, a commercial item can be used conveniently, Specifically, sodium thioacetate, potassium thioacetate, sodium thiooctanoate, potassium thiooctanoate, sodium thiolaurate, potassium thiolaurate, etc. Can be mentioned. In addition, when thiocarboxylate cannot be obtained, it can be easily produced by neutralization of thiocarboxylic acid with a more appropriate base. If neither the desired thiocarboxylic acid nor its salt is available, an appropriate acid halide or acid anhydride and sulfide, hydrosulfide, or a mixture thereof (eg, aqueous sodium hydrosulfide NaSH) and An aqueous solution of a thiocarboxylate can be produced by synthesizing a thiocarbonyl group by the above reaction.

  The conversion reaction from the halogen element of the haloalkyl group of the raw material silane compound to the alkanoylthio group can be carried out under known reaction conditions, for example, in Japanese translations of PCT publication No. 2007-521305, JP-T 2008-536845, etc. As described, methyltrioctylammonium chloride, tetramethylammonium chloride, tetramethylammonium bromide, tetramethylammonium iodide, tetramethylammonium hydroxide, tetraethylammonium chloride, tetraethylammonium bromide, tetraethylammonium iodide, water In the presence or absence of a phase transfer catalyst such as tetraethylammonium oxide, tetrabutylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium iodide, tetrabutylammonium hydroxide, etc. The aqueous solution of the thiocarboxylate represented by the formula (XIX) and the above raw material silane compound are mixed, the solution is stirred until the desired degree of reaction is reached, the organic phase is separated from the aqueous phase, filtered, heated or It consists of removing residual volatile components using vacuum.

  In the method for producing a silane coupling agent of the present invention, the amount of the thiocarboxylate used is from 0.75 to 1.5 mol per mol of the haloalkyl group of the raw material silane compound from the viewpoint of suppressing the production of by-products and improving the yield. An equivalent range is preferred, with 1.0 molar equivalent being particularly preferred. If the amount of thiocarboxylate used per mole of haloalkyl group is less than 0.75 molar equivalent, the yield of the silane coupling agent decreases, while if it exceeds 1.5 molar equivalent, impurities may be generated.

  In the method for producing a silane coupling agent of the present invention, when the conversion reaction to an alkanoylthio group is performed in the presence of the phase transfer catalyst, the concentration of the phase transfer catalyst in the reaction solution is not particularly limited. However, it is preferable that it is 1 ppm-3 mass%. As the solvent, for example, hexane, octane, decane, benzene, toluene, xylene, tetrahydrofuran (THF), chloroform, ethyl acetate, 1,2-dichloroethane, dibutyl ether, mesitylene, dioxane and the like are used as the solvent. be able to.

  In addition, in the manufacturing method of the silane coupling agent of this invention, the temperature of the conversion reaction to an alkanoylthio group has the preferable range of 30-80 degreeC, and the reaction time has the preferable range of 1-20 hours.

  The silane compound obtained by the method for producing a silane coupling agent of the present invention (hereinafter referred to as a generated silane compound) is a silane compound having a protected mercapto group and an aminoalkoxyl group, a condensate thereof, or a mixture thereof. Specifically, the compound represented by the above formula (I), the compound represented by the above formula (VI), the compound containing the structure represented by the above formula (XI), and the above formula (VI). And a mixture of the compound having the structure represented by the above formula (XI). The compound represented by the formula (I) is obtained by reacting the compound of the formula (XVI) with the compound of the formula (XIX), and the compound represented by the formula (VI) is The compound of the above formula (XVII) is obtained by reacting the compound of the above formula (XIX), and the compound represented by the above formula (XI) is a compound containing the structure of the above formula (XVIII). It can be obtained by reacting with the compound of the above formula (XIX).

  Here, when the generated silane compound is a mixture of a silane compound (monomer or monomer) having a protected mercapto group and an aminoalkoxyl group and a condensate thereof, The content of the trimer is 30 to 99% by mass, the content of the dimer is 1 to 60% by mass, the content of the trimer is 50% by mass or less, and the mass of the tetramer or higher is 40% by mass. % Or less is preferable. Specifically, when the generated silane compound is a mixture of a compound represented by the general formula (VI) and a compound including a structure represented by the general formula (XI), the general formula ( It is preferable that the content rate of the compound represented by VI) is 70-99 mass%, and the content rate of the compound containing the structure represented by general formula (XI) is 1-30 mass%. Moreover, the compound containing the structure represented by general formula (XI) is 50-80 mass% of the compound in which x is 1 in the formula, 1-50 mass% of the compound in which x is 2, and x is 3 or more. It is preferable to contain the compound which is 10 mass% or less.

<< Compound of Formula (I) >>
In the above formula (I), z is 1 to 10, preferably in the range of 1 to 4, and particularly preferably 1. R ¹ , R ² , R ³ and R ⁴ are as defined in the above formula (XVI), while R ⁵ is as defined in the above formula (XIX).

<< Compound of Formula (VI) >>
In the above formula (VI), z is 1 to 10, preferably in the range of 1 to 4, and particularly preferably 1. W, R ¹² , R ¹³ , R ¹⁴ and R ⁴ are as defined in the above formula (XVII), while R ⁵ is as defined in the above formula (XIX).

<< Compound containing structure of formula (XI) >>
In the above formula (XI), z is 1 to 10, preferably 1 to 4, and particularly preferably 1. W, R ¹² , R ¹³ , R ¹⁴ , R ⁴ and x are as defined in the above formula (XVIII), while R ⁵ is as defined in the above formula (XIX). .

  Specific examples of the generated silane compound include, for example, 3-octanoylthio-propyl (monodimethylaminoethoxy) diethoxysilane, 3-octanoylthio-propyl (didimethylaminoethoxy) monoethoxysilane, and 3-octanoylthio-propyltridimethylamino. Ethoxysilane, 3-octanoylthio-propyl (monodiethylaminoethoxy) diethoxysilane, 3-octanoylthio-propyl (didiethylaminoethoxy) monoethoxysilane, 3-octanoylthio-propyltridiethylaminoethoxysilane, 3-octanoylthio-propyl (dimethylaminoethoxy) ) Ethoxymethylsilane, 3-octanoylthio-propyl (dimethylaminoethoxy) dimethylsilane, 3-octanoylthio-propyl (didimethylaminoethoxy) monomethylsila 3-octanoylthio-propyl (diethylaminoethoxy) ethoxymethylsilane, 3-octanoylthio-propyl (diethylaminoethoxy) dimethylsilane, 3-octanoylthio-propyl (didiethylaminoethoxy) monomethylsilane, 3-lauroylthio-propyl (monodimethylaminoethoxy) ) Diethoxysilane, 3-lauroylthio-propyl (didimethylaminoethoxy) monoethoxysilane, 3-lauroylthio-propyltridimethylaminoethoxysilane, 3-lauroylthio-propyl (monodiethylaminoethoxy) diethoxysilane, 3- Lauroylthio-propyl (didiethylaminoethoxy) monoethoxysilane, 3-lauroylthio-propyltridiethylaminoethoxysilane, 3-lauroylthio-propyl (dimethylaminoethoxy) eth Xymethylsilane, 3-lauroylthio-propyl (dimethylaminoethoxy) dimethylsilane, 3-lauroylthio-propyl (didimethylaminoethoxy) monomethylsilane, 3-lauroylthio-propyl (diethylaminoethoxy) ethoxymethylsilane, 3-lauroyl Thio-propyl (diethylaminoethoxy) dimethylsilane, 3-lauroylthio-propyl (didiethylaminoethoxy) monomethylsilane, 3-octanoylthio-propyl (ethoxy) 1,3-dioxa-6-methylaza-2-silacyclooctane, 3- Octanoylthio-propyl (ethoxy) 1,3-dioxa-6-ethylaza-2-silacyclooctane, 3-octanoylthio-propyl (ethoxy) 1,3-dioxa-6-propylaza-2-silacyclooctane, 3-octanoylthio- Propyl (ethoxy) 1,3-dioxy -6-Butylaza-2-silacyclooctane, 3-octanoylthio-propyl (methyl) 1,3-dioxa-6-methylaza-2-silacyclooctane, 3-octanoylthio-propyl (methyl) 1,3-dioxa-6 -Ethylaza-2-silacyclooctane, 3-octanoylthio-propyl (methyl) 1,3-dioxa-6-propylaza-2-silacyclooctane, 3-octanoylthio-propyl (methyl) 1,3-dioxa-6-butylaza -2-Silacyclooctane, 3-lauroylthio-propyl (ethoxy) 1,3-dioxa-6-methylaza-2-silacyclooctane, 3-lauroylthio-propyl (ethoxy) 1,3-dioxa-6-ethylaza -2-Silacyclooctane, 3-lauroylthio-propyl (ethoxy) 1,3-dioxa-6-propylaza-2-silacyclooctane, 3-lauroylthio-propyl (ethoxy) ) 1,3-Dioxa-6-butylaza-2-silacyclooctane, 3-lauroylthio-propyl (methyl) 1,3-dioxa-6-methylaza-2-silacyclooctane, 3-lauroylthio-propyl (methyl) ) 1,3-Dioxa-6-ethylaza-2-silacyclooctane, 3-lauroylthio-propyl (methyl) 1,3-dioxa-6-propylaza-2-silacyclooctane and 3-lauroylthio-propyl (methyl) ) 1,3-dioxa-6-butylaza-2-silacyclooctane and the like.

  Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to the following examples.

(Comparative Example 1)
<Production of 3-octanoylthio-propyl (ethoxy) 1,3-dioxa-6-methylaza-2-silacyclooctane>
At room temperature, 20 g of 3-octanoylthio-propyltriethoxysilane, 6.7 g of N-methyldiethanolamine, 0.1 g of titanium tetra-n-butoxide, and 70 mL of xylene were charged into a 200 mL eggplant flask. While flowing dry nitrogen and stirring with a magnetic stirrer, the mixture was heated in an oil bath at 170 to 180 ° C for 8 hours. Thereafter, the solvent was removed by a rotary evaporator, and the remaining volatile components were removed by a rotary pump and a cold trap to obtain 23 g of a yellow transparent liquid. The purity of the obtained liquid was measured by gas chromatography (GC) and found to be 85%. Moreover, when the obtained liquid was analyzed by ¹ H-NMR, 0.7 (t; 2H), 0.9 (t; 3H), 1.2 (t; 3H), 1.4 (m; 8H), 1.7 (m; 4H) , 2.4, 2.3 (s × 2; total 3H), 2.5 (m; 6H), 2.9 (t; 2H), 3.8 (m; 6H), 3-octanoylthio-propyl (ethoxy) 1,3-dioxa- It was found to be 6-methylaza-2-silacyclooctane.

Example 1
<Production of 3-octanoylthio-propyl (ethoxy) 1,3-dioxa-6-methylaza-2-silacyclooctane>
At room temperature, 12 g of 3-chloropropyltriethoxysilane, 6 g of N-methyldiethanolamine, 0.1 g of titanium tetra-n-butoxide, and 100 mL of xylene were charged into a 200 mL eggplant flask. The mixture (hereinafter referred to as a xylene solution) was cooled to room temperature after heating for 10 hours at 170 to 180 ° C. in an oil bath while flowing dry nitrogen and stirring with a magnetic stirrer.
Next, an aqueous solution (30 ml) of sodium thiooctanoate (9.1 g) was heated to 50 ° C., and the xylene solution was added all at once to this aqueous solution. Subsequently, 0.005 grams of concentrated methyltrioctylammonium chloride aqueous solution was added and stirred continuously at 70 ° C. for 10 hours, then the solution was allowed to cool to ambient temperature, the organic phase was separated by a separatory funnel, and an evaporator was used. After concentration, 10 g of a yellow transparent liquid was obtained.
When the purity of the obtained liquid was measured by gas chromatography (GC), it was found that the purity was 90%, which was significantly improved as compared with Comparative Example 1. Moreover, when the obtained liquid was analyzed by ¹ H-NMR, 0.7 (t; 2H), 0.9 (t; 3H), 1.2 (t; 3H), 1.4 (m; 8H), 1.7 (m; 4H) , 2.4, 2.3 (s × 2; total 3H), 2.5 (m; 6H), 2.9 (t; 2H), 3.8 (m; 6H), 3-octanoylthio-propyl (ethoxy) 1,3-dioxa- It was found to be 6-methylaza-2-silacyclooctane.

(Example 2)
<Production of 3-octanoylthio-propyl (methyl) 1,3-dioxa-6-methylaza-2-silacyclooctane>
At room temperature, a 200 mL eggplant flask was charged with 9.1 g of 3-chloropropylmethyldimethoxysilane, 6 g of N-methyldiethanolamine, 0.1 g of titanium tetra-n-butoxide, and 100 mL of xylene. The mixture (hereinafter referred to as a xylene solution) was cooled to room temperature after heating for 10 hours at 170 to 180 ° C. in an oil bath while flowing dry nitrogen and stirring with a magnetic stirrer.
Next, an aqueous solution (30 ml) of sodium thiooctanoate (9.1 g) was heated to 50 ° C., and the xylene solution was added all at once to this solution. Subsequently, 0.005 grams of concentrated methyltrioctylammonium chloride aqueous solution was added and stirred continuously at 70 ° C. for 10 hours, then the solution was allowed to cool to ambient temperature, the organic phase was separated by a separatory funnel, and an evaporator was used. After concentration, 12 g of a yellow transparent liquid was obtained.
When the purity of the obtained liquid was measured by gas chromatography (GC), the purity was 88%. Moreover, when the obtained liquid was analyzed by ¹ H-NMR, 0.1 (s; 3H), 0.7 (t; 2H), 0.9 (t; 3H), 1.4 (m; 8H), 1.7 (m; 4H) , 2.4, 2.3 (s × 2; total 3H), 2.5 (m; 6H), 2.9 (t; 2H), 3.8 (m; 4H), 3-octanoylthio-propyl (methyl) 1,3-dioxa- It was found to be 6-methylaza-2-silacyclooctane.

(Example 3)
<Production of 3-lauroylthio-propyl (methyl) 1,3-dioxa-6-butylaza-2-silacyclooctane>
At room temperature, a 200 mL eggplant flask was charged with 9.1 g of 3-chloropropylmethyldimethoxysilane, 8.1 g of N-butyldiethanolamine, 0.1 g of titanium tetra-n-butoxide, and 100 mL of xylene. The mixture (hereinafter referred to as a xylene solution) was cooled to room temperature after heating for 10 hours at 170 to 180 ° C. in an oil bath while flowing dry nitrogen and stirring with a magnetic stirrer.
Next, an aqueous solution (30 ml) of sodium thiolaurate (11.9 g) was heated to 50 ° C., and the xylene solution was added all at once to this solution. Subsequently, 0.005 grams of concentrated methyltrioctylammonium chloride aqueous solution was added and stirred continuously at 70 ° C. for 10 hours, then the solution was allowed to cool to ambient temperature, the organic phase was separated by a separatory funnel, and an evaporator was used. After concentration, 13 g of a yellow transparent liquid was obtained.
When the purity of the obtained liquid was measured by gas chromatography (GC), the purity was 93%. Further, when the obtained liquid was analyzed by ¹ H-NMR, 0.1 (s; 3H), 0.7 (t; 2H), 0.9 (t; 3H), 1.4 (m; 16H), 1.7 (m; 4H) , 2.4, 2.3 (s × 2; total 3H), 2.5 (m; 6H),
2.9 (t; 2H) and 3.8 (m; 4H), which were found to be 3-lauroylthio-propyl (methyl) 1,3-dioxa-6-butylaza-2-silacyclooctane.

(Example 4)
<Production of 3-octanoylthio-propyl (didiethylaminoethoxy) methylsilane>
At room temperature, 18.2 g of 3-chloropropylmethyldimethoxysilane and 23.5 g of diethylaminoethanol were charged into a 200 mL eggplant flask. While stirring with a magnetic stirrer while flowing dry nitrogen, the mixture (hereinafter referred to as a xylene solution) was cooled to room temperature after heating at 150 to 160 ° C. for 6 hours in an oil bath.
Next, an aqueous solution (60 ml) of sodium thiooctanoate (18.2 g) was heated to 50 ° C., and the xylene solution was added all at once to this solution. Subsequently, 0.01 gram of concentrated methyltrioctylammonium chloride aqueous solution was added and stirred continuously for 10 hours at 70 ° C., then the solution was allowed to cool to ambient temperature, the organic phase was separated by a separatory funnel, and 40 g of A yellow transparent liquid was obtained.
When the purity of the obtained liquid was measured by gas chromatography (GC), the purity was 95%. Moreover, when the obtained liquid was analyzed by ¹ H-NMR, 0.11 (s; 3H), 0.68 (t; 2H), 0.88 (t; 3H), 1.02 (t; 12H), 1.2-1.4 (m; 8H), 1.64 (m; 4H), 2.51-2.62 (m; 14H), 2.88 (t; 2H), 3.74 (t; 4H), and 3-octanoylthio-propyl (didiethylaminoethoxy) methylsilane I understood.

(Example 5)
<Production of 3-octanoylthio-propyl (decanoxy) 1,3-dioxa-6-methylaza-2-silacyclooctane>
At room temperature, 12.0 g of 3-chloropropyltriethoxysilane, 6 g of N-methyldiethanolamine, 0.1 g of titanium tetra-n-butoxide and 100 mL of xylene were charged into a 200 mL eggplant flask. While stirring with a magnetic stirrer while flowing dry nitrogen, the mixture (hereinafter referred to as a xylene solution) was cooled to room temperature after heating at 170 to 180 ° C. for 10 hours in an oil bath.
Next, an aqueous solution (30 ml) of sodium thiooctanoate (9.1 g) was heated to 50 ° C., and the xylene solution was added all at once to this solution. Subsequently, 0.005 grams of concentrated methyltrioctylammonium chloride aqueous solution was added and stirred continuously at 70 ° C. for 10 hours, then the solution was allowed to cool to ambient temperature, the organic phase was separated by a separatory funnel, and an evaporator was used. After concentration, 14.5 g of a yellow transparent liquid was obtained.
When the purity of the obtained liquid was measured by gas chromatography (GC), the purity was 91%. Moreover, when the obtained liquid was analyzed by ¹ H-NMR, 0.7 (t; 2H), 0.9 (t; 6H), 1.3 (m; 22H), 1.6 (m; 2H), 1.7 (m; 4H) , 2.4, 2.3 (s × 2; total 3H), 2.5 (m; 6H), 2.9 (t; 2H), 3.7-3.8 (m; 6H), 3-octanoylthio-propyl (decanoxy) 1,3- It was found to be dioxa-6-methylaza-2-silacyclooctane.

Claims (6)

  A silane comprising a step of obtaining a silane compound having a protected mercapto group and an aminoalkoxyl group by converting a halogen element of the haloalkyl group of the silane compound having a haloalkyl group and an aminoalkoxyl group into an alkanoylthio group A method for producing a coupling agent. The silane compound having a protected mercapto group and aminoalkoxyl group is represented by the following general formula (I):

[At least one of R ¹ , R ² and R ³ in the formula (I) is represented by the following general formula (II) or formula (III):

(In the formula, M is —O— or —CH ₂ —, X and Y are independently —O—, —NR ⁸ — or —CH ₂ —, and R ⁶ is —OR ⁸ , —NR ⁸ R. ⁹ or -R ⁸ , R ⁷ is -NR ⁸ R ⁹ , -NR ⁸ -NR ⁸ R ⁹ or -N = NR ⁸ , provided that R ⁸ is -C _n H _{2n + 1} , R ⁹ is a _{-C q H 2q + 1, l} , m, n and q are represented by independently 0 to 20), others _{-M-C r H 2r + 1} ( wherein, M is the It has the same meaning as, r is 0 to 20) or _{- (M-C l H 2l} ) y C s H 2s + 1 ( where, M and l are as defined above, y and s are each independently Wherein one or more of R ¹ , R ² and R ³ is M is —O—,
R ⁴ represents the following general formula (IV), formula (V) or formula (i):

(In the formula, M, X, Y, R ⁶ , l and m are as defined above, and R ¹⁰ is —NR ⁸ —, —NR ⁸ —NR ⁸ — or —N═N—, wherein R ⁸ Is synonymous with the above),
R ⁵ represents the above general formula (II), formula (III), or —C ₁ H _2l —R ¹¹ (where R ¹¹ represents —NR ⁸ R ⁹ , —NR ⁸ —NR ⁸ R ⁹ , —N═NR ^8). or a _{-M-C m H 2m + 1} , ^{where, R 8, R 9, M} , l and m are represented by a is) defined above,
z is 1-10]. The manufacturing method of the silane coupling agent of Claim 1 characterized by the above-mentioned. The silane compound having a protected mercapto group and aminoalkoxyl group is represented by the following general formula (VI):

[W in Formula (VI) is —NR ⁸ —, —O—, or —CR ⁸ R ¹⁵ — (wherein R ¹⁵ is —R ⁹ or —C _m H _2m —R ⁷ , where R ⁷ Is —NR ⁸ R ⁹ , —NR ⁸ —NR ⁸ R ⁹ or —N═NR ⁸ , R ⁸ is —C _n H _{2n + 1} , R ⁹ is —C _q H _{2q + 1} , m, n and q are each independently 0 to 20),
R ¹² and R ¹³ are each independently represented by —M—C ₁ H _{2 1} — (wherein M is —O— or —CH ₂ —, and 1 is 0 to 20),
R ¹⁴ represents —M—C _r H _{2r + 1} or —M—C _r H _2r —R ⁷ (wherein M and R ⁷ are as defined above, and r is 0 to 20) or — (M _{-C l H 2l) y C s} H 2s + 1 ( where, M and l are as defined above, y and s are expressed in each independently 1 to 20), where, R ^12, One or more of R ¹³ and R ¹⁴ is M is —O—;
R ⁴ represents the following general formula (VII), formula (VIII) or formula (ii):

Wherein M, l and m are as defined above, X and Y are each independently —O—, —NR ⁸ — or —CH ₂ —, and R ⁶ is —OR ⁸ , —NR ⁸ R ⁹ or -R ^8, R ¹⁰ is ^{-NR 8 -, - NR 8 -NR} 8 - or -N = a N-, provided that, R ⁸ and R ⁹ are represented by the same meaning as above),
R ⁵ represents the following general formula (IX), formula (X) or formula (iii):

(In the formula, M, X, Y, R ⁶ , R ⁷ , l and m are as defined above, and R ¹¹ is —NR ⁸ R ⁹ , —NR ⁸ —NR ⁸ R ⁹ , —N═NR ⁸ or a _{-M-C m H 2m + 1} , where, R ^8, R ^9, M and m are represented by the same meaning as above),
z is 1-10]. The manufacturing method of the silane coupling agent of Claim 1 characterized by the above-mentioned. The silane compound having a protected mercapto group and aminoalkoxyl group is represented by the following general formula (XI):

[W in Formula (XI) is —NR ⁸ —, —O—, or —CR ⁸ R ¹⁵ — (where R ¹⁵ is —R ⁹ or —C _m H _2m —R ⁷ , provided that R ⁷ Is —NR ⁸ R ⁹ , —NR ⁸ —NR ⁸ R ⁹ or —N═NR ⁸ , R ⁸ is —C _n H _{2n + 1} , R ⁹ is —C _q H _{2q + 1} , m, n and q are each independently 0 to 20),
R ¹² and R ¹³ are each independently represented by —M—C ₁ H _{2 1} — (wherein M is —O— or —CH ₂ —, and 1 is 0 to 20),
R ¹⁴ represents —M—C _r H _{2r + 1} or —M—C _r H _2r —R ⁷ (wherein M and R ⁷ are as defined above, and r is 0 to 20) or — (M _{-C l H 2l) y C s} H 2s + 1 ( where, M and l are as defined above, y and s are expressed in each independently 1 to 20), where, R ^12, One or more of R ¹³ and R ¹⁴ is M is —O—;
R ⁴ represents the following general formula (XII), formula (XIII) or formula (iv):

(Wherein M, l and m are as defined above, X and Y are each independently —O—, —NR ⁸ — or —CH ₂ —, R ⁶ is —OR ⁸ , —NR ⁸ R; ⁹ or -R ^8, R ¹⁰ is ^{-NR 8 -, - NR 8 -NR} 8 - or -N = a N-, provided that, R ⁸ and R ⁹ are represented by the same meaning as above),
R ⁵ is the following general formula (XIV), formula (XV) or formula (v):

(In the formula, M, X, Y, R ⁶ , R ⁷ , l and m are as defined above, and R ¹¹ is —NR ⁸ R ⁹ , —NR ⁸ —NR ⁸ R ⁹ , —N═NR ⁸ or a _{-M-C m H 2m + 1} , where, R ^8, R ^9, M and m are represented by the same meaning as above),
The method for producing a silane coupling agent according to claim 1, wherein x and z are each independently 1 to 10].   The silane compound having a protected mercapto group and aminoalkoxyl group is a mixture of a compound represented by the above formula (VI) and a compound containing a structure represented by the above formula (XI). The manufacturing method of the silane coupling agent of Claim 1.   The protected silane compound having a mercapto group and an aminoalkoxyl group is 3-octanoylthio-propyl (monodimethylaminoethoxy) diethoxysilane, 3-octanoylthio-propyl (didimethylaminoethoxy) monoethoxysilane, 3-octanoylthio- Propyltridimethylaminoethoxysilane, 3-octanoylthio-propyl (monodiethylaminoethoxy) diethoxysilane, 3-octanoylthio-propyl (didiethylaminoethoxy) monoethoxysilane, 3-octanoylthio-propyltridiethylaminoethoxysilane, 3-octanoylthio-propyl (Dimethylaminoethoxy) ethoxymethylsilane, 3-octanoylthio-propyl (dimethylaminoethoxy) dimethylsilane, 3-octanoylthio-propyl (didimethyla Minoethoxy) monomethylsilane, 3-octanoylthio-propyl (diethylaminoethoxy) ethoxymethylsilane, 3-octanoylthio-propyl (diethylaminoethoxy) dimethylsilane, 3-octanoylthio-propyl (didiethylaminoethoxy) monomethylsilane, 3-lauroylthio-propyl ( Monodimethylaminoethoxy) diethoxysilane, 3-lauroylthio-propyl (didimethylaminoethoxy) monoethoxysilane, 3-lauroylthio-propyltridimethylaminoethoxysilane, 3-lauroylthio-propyl (monodiethylaminoethoxy) diethoxy Silane, 3-lauroylthio-propyl (didiethylaminoethoxy) monoethoxysilane, 3-lauroylthio-propyltridiethylaminoethoxysilane, 3-lauroylthio-propiyl (Dimethylaminoethoxy) ethoxymethylsilane, 3-lauroylthio-propyl (dimethylaminoethoxy) dimethylsilane, 3-lauroylthio-propyl (didimethylaminoethoxy) monomethylsilane, 3-lauroylthio-propyl (diethylaminoethoxy) ethoxymethyl Silane, 3-lauroylthio-propyl (diethylaminoethoxy) dimethylsilane, 3-lauroylthio-propyl (didiethylaminoethoxy) monomethylsilane, 3-octanoylthio-propyl (ethoxy) 1,3-dioxa-6-methylaza-2-sila Cyclooctane, 3-octanoylthio-propyl (ethoxy) 1,3-dioxa-6-ethylaza-2-silacyclooctane, 3-octanoylthio-propyl (ethoxy) 1,3-dioxa-6-propylaza-2-silacyclooctane 3-octanoylthiope Lopyl (ethoxy) 1,3-dioxa-6-butylaza-2-silacyclooctane, 3-octanoylthio-propyl (methyl) 1,3-dioxa-6-methylaza-2-silacyclooctane, 3-octanoylthio-propyl ( Methyl) 1,3-dioxa-6-ethylaza-2-silacyclooctane, 3-octanoylthio-propyl (methyl) 1,3-dioxa-6-propylaza-2-silacyclooctane, 3-octanoylthio-propyl (methyl) 1,3-dioxa-6-butylaza-2-silacyclooctane, 3-lauroylthio-propyl (ethoxy) 1,3-dioxa-6-methylaza-2-silacyclooctane, 3-lauroylthio-propyl (ethoxy) 1,3-dioxa-6-ethylaza-2-silacyclooctane, 3-lauroylthio-propyl (ethoxy) 1,3-dioxa-6-propylaza-2-silacyclooctane, 3-ra Uroylthio-propyl (ethoxy) 1,3-dioxa-6-butylaza-2-silacyclooctane, 3-lauroylthio-propyl (methyl) 1,3-dioxa-6-methylaza-2-silacyclooctane, 3-lauroyl Thio-propyl (methyl) 1,3-dioxa-6-ethylaza-2-silacyclooctane, 3-lauroylthio-propyl (methyl) 1,3-dioxa-6-propylaza-2-silacyclooctane and 3-lauroyl The method for producing a silane coupling agent according to claim 1, wherein the silane coupling agent is selected from the group consisting of thio-propyl (methyl) 1,3-dioxa-6-butylaza-2-silacyclooctane.