JP2013216612A - Sulfur-containing organosilicon compound having new structure, and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a sulfur-containing organosilicon compound giving rubber characteristics with a low loss tangent contributing to a low fuel consumption by a tire, while maintaining its tensile characteristics, etc., and a method for producing the same.SOLUTION: A sulfur-containing organosilicon compound having ≥2 thioether groups is found to be a sulfur-containing organosilicon compound giving rubber characteristics with a low loss tangent. Also, methods for producing the sulfur-containing organosilicon compound having ≥2 thioether groups includes a method of reacting a halogen-containing organosilicon compound with a polythiol and/or an alkali metal salt of the polythiol, and a method for reacting a mercaptosilane compound having ≥2 thioether groups with an acid halide.

Description

  The present invention relates to a sulfur-containing organosilicon compound having a novel structure and its production. The sulfur-containing organosilicon compound of the present invention reacts with a synthetic rubber or natural rubber having an unsaturated bond, a filler such as silica, clay or talc, or a filler such as surface-modified carbon black blended in the rubber. And a sulfur-containing organosilicon compound that provides rubber properties that reduce the viscosity and loss tangent of the rubber compound.

  Sulfur-containing organosilicon compounds are industrially useful compounds that have been known for a long time, and are used in silica-containing rubbers as fuel-saving tires.

  Silica-containing rubber has a remarkable increase in compound viscosity and loss tangent / dynamic elastic modulus due to the interaction of silanol groups on the silica surface. Therefore, the reaction of the organosilicon compound, so-called silane coupling agent, with the silanol group on the silica surface reduces the interaction of the silanol group, and the sulfur-containing organosilicon compound also reacts with the diene rubber, thereby producing a silica-containing rubber. Reduces loss tangent and dynamic elastic modulus.

  Since the sulfur-containing organosilicon compound reacts with rubber and silica to reduce loss tangent, when used as a tire tread formulation, rolling resistance is reduced and a fuel-saving tire is obtained. However, conventional coupling agents such as those disclosed in JP-A-48-29726 and JP-A-51-125207 reduce the loss tangent as well as the dynamic elastic modulus. The running stability becomes worse. Moreover, the viscosity reduction as a composition of the silica-containing rubber was not sufficient, and in order to avoid the burning phenomenon at the time of kneading, the kneading was performed twice and three times, and workability was poor. In addition, an organic silicon compound containing a thioether group has been proposed in JP 2003-519237, but there are problems such as a complicated synthesis method and the use of an expensive catalyst.

JP 48-29726 A JP 51-125207 A Special table 2003-519237

  In view of the above-mentioned problems of the prior art, an object of the present invention is to provide a sulfur-containing organosilicon compound that provides rubber characteristics with a low loss tangent that contributes to fuel efficiency reduction of tires while maintaining characteristics such as tensile characteristics, and a method for producing the same. It is to provide.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that a sulfur-containing organosilicon compound having two or more thioether groups is a sulfur-containing organosilicon compound that provides rubber properties with low loss tangent. . In addition, as a method for producing a sulfur-containing organosilicon compound having two or more thioether groups, a method for reacting a halogen-containing organosilicon compound with polythiol and / or polythiol alkali metal salt, a mercaptosilane compound having two or more thioether groups and an acid halide A production method in which is reacted is disclosed.

（式（１）中、Ｒ^１は炭素数１〜１０の二価のアルキル基、又はフェニル基であり、Ｙが一般式（４）、一般式（５）、又は炭素数１〜８の一価のアルキル基で置換されていてもよいシラトラン基（Ｎ≡(ＣＨ_２ＣＨ_２Ｏ)_３Ｓｉ−）であり、ｐは２〜５の整数である。）

（式（２）中、Ｒ^１は炭素数１〜１０の二価のアルキル基、又はフェニル基であり、Ｙが一般式（４）、一般式（５）、又は炭素数１〜８の一価のアルキル基で置換されていてもよいシラトラン基（Ｎ≡(ＣＨ_２ＣＨ_２Ｏ)_３Ｓｉ−）であり、ｐは２〜５の整数であり、ｑは０〜８である。）

（式（３）中、Ｒ^１は炭素数１〜１０の二価のアルキル基、又はフェニル基であり、Ｙが一般式（４）、一般式（５）、又は炭素数１〜８の一価のアルキル基で置換されていてもよいシラトラン基（Ｎ≡(ＣＨ_２ＣＨ_２Ｏ)_３Ｓｉ−）であり、Ｒ^２は炭素数１〜１６の一価のアルキル基、フェニル基、炭素数１〜６の一価のアルキル基及び炭素数７〜１２のアラルキル基から選択される基が置換しているアリール基、ナフチル基のいずれかであり、ｐは２〜５の整数である。）

（式（４）中、Ｒ^３、Ｒ^４、Ｒ^５はそれぞれ同一であっても異なっていてもよく、炭素数１〜１８の一価のアルキル基、炭素数１〜１８の一価のアルコキシ基、ＯＨ基、又はＣ_ｎＨ_２ｎ−１Ｏ−（（ＣＨ_２)_ｍＯ）_ｒで表されｎは１〜１８、ｍは１〜６、ｒは１〜１８であるポリアルキレングリコールモノアルキルエーテル基であり、Ｒ^３、Ｒ^４、Ｒ^５の少なくとも１つはアルコキシ基、ＯＨ基、又はポリアルキレングリコールモノアルキルエーテル基である。）

（式（５）中、Ｒ^６は炭素数１〜１８の一価のアルコキシ基、ＯＨ基、又はＣ_ｎＨ_２ｎ−１Ｏ−（（ＣＨ_２）_ｍＯ）_ｒで表され、ｎは１〜１８、ｍは１〜６、ｒは１〜１８であるポリアルキレングリコールモノアルキルエーテル基であり、Ｒ^７、Ｒ^８は互いに同一でも異なっていてもよく、炭素数１〜８の二価のアルキル基であり、Ｗは−Ｃ(＝Ｏ)−、−Ｏ−、−ＮＲ^９−、−ＣＲ^１０Ｒ^１１−でありＲ^９、Ｒ^１０、Ｒ^１１は炭素数１〜１８のアルキル基又は水素である。） That is, the present invention is a sulfur-containing organosilicon compound having two or more thioether groups, and is preferably a sulfur-containing organosilicon compound selected from the group of sulfur-containing organosilicon compounds described in the general formulas (1) to (3). .

(In the formula (1), ^{R 1} is a divalent alkyl group, or a phenyl group having 1 to 10 carbon atoms, Y is the general formula (4), the general formula (5), or one having 1 to 8 carbon atoms A silatrane group (N≡ (CH ₂ CH ₂ O) ₃ Si—) optionally substituted with a valent alkyl group, and p is an integer of 2 to 5.

(In the formula (2), ^{R 1} is a divalent alkyl group, or a phenyl group having 1 to 10 carbon atoms, Y is the general formula (4), the general formula (5), or one having 1 to 8 carbon atoms A silatrane group (N≡ (CH ₂ CH ₂ O) ₃ Si—) optionally substituted with a valent alkyl group, p is an integer of 2 to 5, and q is 0 to 8.

(In the formula (3), ^{R 1} is a divalent alkyl group, or a phenyl group having 1 to 10 carbon atoms, Y is the general formula (4), the general formula (5), or one having 1 to 8 carbon atoms A silatrane group (N≡ (CH ₂ CH ₂ O) ₃ Si—) optionally substituted with a valent alkyl group, and R ² is a monovalent alkyl group having 1 to 16 carbon atoms, a phenyl group, a carbon number A group selected from a monovalent alkyl group of 1 to 6 and an aralkyl group having 7 to 12 carbon atoms is an aryl group or a naphthyl group substituted, and p is an integer of 2 to 5.)

(In Formula (4), R < ³ >, R < ⁴ >, R < ⁵ > may be same or different, respectively, a C1-C18 monovalent alkyl group, C1-C18 monovalent alkoxy group, OH group, or _{C n H 2n-1 O -} ((CH 2) m O) is represented n with _r 1-18, m is 1 to 6, r is 1 to 18 polyalkylene glycol monoalkyl An ether group, and at least one of R ³ , R ⁴ , and R ⁵ is an alkoxy group, an OH group, or a polyalkylene glycol monoalkyl ether group.)

(In the formula (5), ^{R 6} is an alkoxy group, OH group of monovalent to 18 carbon atoms, or _C n _H 2n-1 O - represented by _{((CH 2) m O)} r, n is 1 -18, m is a polyalkylene glycol monoalkyl ether group in which 1 to 6 and r is 1 to 18, R ⁷ and R ⁸ may be the same or different from each other, and are divalent having 1 to 8 carbon atoms. An alkyl group, W is —C (═O) —, —O—, —NR ⁹ —, —CR ¹⁰ R ¹¹ —, and R ⁹ , R ¹⁰ , R ¹¹ are each an alkyl group having 1 to 18 carbon atoms or Hydrogen.)

（式（６）中、Ｒ^１及びＹは一般式（１）と同じであり、Ｘはハロゲン原子である。）

（式（７）中、ｐは一般式（１）と同じである。）

（式（８）中、Ｍはアルカリ金属であり、ｐは一般式（１）と同じである。） As the method for producing the sulfur-containing organosilicon compound represented by the general formula (1) and the sulfur-containing organosilicon compound represented by the general formula (2), the halogen-containing organosilicon compound represented by the general formula (6) and the general formula ( The manufacturing method which makes the polythiol shown by 7) and / or the polythiol alkali metal salt shown by General formula (8) react is mentioned.

(In formula (6), R ¹ and Y are the same as in general formula (1), and X is a halogen atom.)

(In formula (7), p is the same as in general formula (1).)

(In formula (8), M is an alkali metal, and p is the same as in general formula (1).)

（式（１）中、Ｒ^１、Ｙ及びｐは式（３）と同じ。）

（式（９）中、Ｒ^２は式（３）と同じであり、Ｘはハロゲン原子である。） The method for producing the sulfur-containing organosilicon compound represented by the general formula (3) includes a method for reacting the sulfur-containing organosilicon compound represented by the general formula (1) with the acid halide represented by the general formula (9). It is done. This production method may be carried out in the state of a mixture in which the sulfur-containing organosilicon compound represented by the general formula (1) and the sulfur-containing organosilicon compound represented by the general formula (2) coexist.

(In formula (1), R ¹ , Y and p are the same as in formula (3).)

(In formula (9), R ² is the same as in formula (3), and X is a halogen atom.)

  By blending a silica-containing rubber composition with a sulfur-containing organosilicon compound having two or more thioether groups of the present invention, rubber characteristics with low loss tangent can be provided.

（式（１）中、Ｒ^１は炭素数１〜１０の二価のアルキル基、又はフェニル基であり、Ｙが一般式（４）、一般式（５）、又は炭素数１〜８の一価のアルキル基で置換されていてもよいシラトラン基（Ｎ≡(ＣＨ_２ＣＨ_２Ｏ)_３Ｓｉ−）であり、ｐは２〜５の整数である。）

（式（２）中、Ｒ^１は炭素数１〜１０の二価のアルキル基、又はフェニル基であり、Ｙが一般式（４）、一般式（５）、又は炭素数１〜８の一価のアルキル基で置換されていてもよいシラトラン基（Ｎ≡(ＣＨ_２ＣＨ_２Ｏ)_３Ｓｉ−）であり、ｐは２〜５の整数であり、ｑは０〜８である。）

（式（３）中、Ｒ^１は炭素数１〜１０の二価のアルキル基、又はフェニル基であり、Ｙが一般式（４）、一般式（５）、又は炭素数１〜８の一価のアルキル基で置換されていてもよいシラトラン基（Ｎ≡(ＣＨ_２ＣＨ_２Ｏ)_３Ｓｉ−）であり、Ｒ^２は炭素数１〜１６の一価のアルキル基、フェニル基、炭素数１〜６の一価のアルキル基及び炭素数７〜１２のアラルキル基から選択される置換基が置換しているアリール基、ナフチル基のいずれかであり、ｐは２〜５の整数である。）

（式（４）中、Ｒ^３、Ｒ^４、Ｒ^５はそれぞれ同一であっても異なっていてもよく、炭素数１〜１８の一価のアルキル基、炭素数１〜１８の一価のアルコキシ基、ＯＨ基、又はＣ_ｎＨ_２ｎ−１Ｏ−（（ＣＨ_２)_ｍＯ）_ｒで表されｎは１〜１８、ｍは１〜６、ｒは１〜１８であるポリアルキレングリコールモノアルキルエーテル基であり、Ｒ^３、Ｒ^４、Ｒ^５の少なくとも１つはアルコキシ基、ＯＨ基、又はポリアルキレングリコールモノアルキルエーテル基である。）

（式（５）中、Ｒ^６は炭素数１〜１８の一価のアルコキシ基、ＯＨ基、又はＣ_ｎＨ_２ｎ−１Ｏ−（（ＣＨ_２）_ｍＯ）_ｒで表され、ｎは１〜１８、ｍは１〜６、ｒは１〜１８であるポリアルキレングリコールモノアルキルエーテル基であり、Ｒ^７、Ｒ^８は互いに同一でも異なっていてもよく、炭素数１〜８の二価のアルキル基であり、Ｗは−Ｃ(＝Ｏ)−、−Ｏ−、−ＮＲ^９−、−ＣＲ^１０Ｒ^１１−でありＲ^９、Ｒ^１０、Ｒ^１１は炭素数１〜１８のアルキル基又は水素である。） The present invention is a sulfur-containing organosilicon compound having two or more thioether groups, and is preferably a sulfur-containing organosilicon compound selected from the group of sulfur-containing organosilicon compounds described in the general formulas (1) to (3).

(In the formula (1), ^{R 1} is a divalent alkyl group, or a phenyl group having 1 to 10 carbon atoms, Y is the general formula (4), the general formula (5), or one having 1 to 8 carbon atoms A silatrane group (N≡ (CH ₂ CH ₂ O) ₃ Si—) optionally substituted with a valent alkyl group, and p is an integer of 2 to 5.

(In the formula (2), ^{R 1} is a divalent alkyl group, or a phenyl group having 1 to 10 carbon atoms, Y is the general formula (4), the general formula (5), or one having 1 to 8 carbon atoms A silatrane group (N≡ (CH ₂ CH ₂ O) ₃ Si—) optionally substituted with a valent alkyl group, p is an integer of 2 to 5, and q is 0 to 8.

(In the formula (3), ^{R 1} is a divalent alkyl group, or a phenyl group having 1 to 10 carbon atoms, Y is the general formula (4), the general formula (5), or one having 1 to 8 carbon atoms A silatrane group (N≡ (CH ₂ CH ₂ O) ₃ Si—) optionally substituted with a valent alkyl group, and R ² is a monovalent alkyl group having 1 to 16 carbon atoms, a phenyl group, a carbon number It is either an aryl group or a naphthyl group substituted by a substituent selected from a monovalent alkyl group of 1 to 6 and an aralkyl group having 7 to 12 carbon atoms, and p is an integer of 2 to 5. )

(In Formula (4), R < ³ >, R < ⁴ >, R < ⁵ > may be same or different, respectively, a C1-C18 monovalent alkyl group, C1-C18 monovalent alkoxy group, OH group, or _{C n H 2n-1 O -} ((CH 2) m O) is represented n with _r 1-18, m is 1 to 6, r is 1 to 18 polyalkylene glycol monoalkyl An ether group, and at least one of R ³ , R ⁴ , and R ⁵ is an alkoxy group, an OH group, or a polyalkylene glycol monoalkyl ether group.)

(In the formula (5), ^{R 6} is an alkoxy group, OH group of monovalent to 18 carbon atoms, or _C n _H 2n-1 O - represented by _{((CH 2) m O)} r, n is 1 -18, m is a polyalkylene glycol monoalkyl ether group in which 1 to 6 and r is 1 to 18, R ⁷ and R ⁸ may be the same or different from each other, and are divalent having 1 to 8 carbon atoms. An alkyl group, W is —C (═O) —, —O—, —NR ⁹ —, —CR ¹⁰ R ¹¹ —, and R ⁹ , R ¹⁰ , R ¹¹ are each an alkyl group having 1 to 18 carbon atoms or Hydrogen.)

In formulas (1) to (3), R ¹ is more preferably a divalent alkyl group having 1 to 8 carbon atoms or a phenyl group, and a divalent alkyl group having 1 to 6 carbon atoms or a phenyl group. It is particularly preferred. These alkyl groups may be linear or branched.

  In the formulas (1) to (3), p is preferably an integer of 2 to 4.

  In Formula (2), q is preferably an integer of 0 to 6, and particularly preferably an integer of 0 to 3.

In the formula (3), R ² is a group selected from a monovalent alkyl group having 1 to 16 carbon atoms, a phenyl group, a monovalent alkyl group having 1 to 6 carbon atoms and an aralkyl group having 7 to 12 carbon atoms. Is preferably any of the substituted aryl groups, particularly preferably a monovalent alkyl group having 1 to 16 carbon atoms or a phenyl group.

In Formula (4), R ³ , R ⁴ , and R ⁵ are each a monovalent alkyl group having 1 to 8 carbon atoms, a monovalent alkoxy group having 1 to 8 carbon atoms, C _n H _2n-1 O — (( CH ₂ ) _m O) It is more preferably any one of polyalkylene glycol monoalkyl ether groups represented by _r , where n is 1 to 8, m is 1 to 4, and r is 1 to 8, and 4 monovalent alkyl group, an alkoxy group monovalent having 1 to 4 carbon _{atoms, C n H 2n-1 O} - represented by _{((CH 2) m O)} r n is 2 to 8, m is 2 4 and r are particularly preferably any one of 1 to 6 polyalkylene glycol monoalkyl ether groups.
R ³ , R ⁴ and R ⁵ may be linear or branched.

In the formula (5), R ⁶ is a monovalent alkoxy group having 1 to 8 carbon atoms, C _n H _2n-1 O — ((CH ₂ ) _m O) _r , where n is 1 to 8, and m is 1-4, r is more preferably either a polyalkylene glycol monoalkyl ether groups 1 to 8, or alkoxy group of monovalent to 4 carbon atoms _{C n H 2n-1 O -} (( CH ₂ ) _m O) It is particularly preferable that any one of polyalkylene glycol monoalkyl ether groups represented by _r , wherein n is 2 to 8, m is 2 to 4, and r is 1 to 6.
In Formula (5), it is preferable that R < ⁷ >, R < ⁸ > is a C1-C4 bivalent alkyl group.
In the formula (5), R ⁹ , R ¹⁰ and R ¹¹ are preferably either an alkyl group having 1 to 8 carbon atoms or hydrogen, and any one of an alkyl group having 1 to 4 carbon atoms or hydrogen. It is more preferable.
R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ may be linear or branched.

  In the present application, the sulfur-containing organosilicon compound represented by the general formula (2) is a compound in which the mercapto group of the sulfur-containing organosilicon compound represented by the general formula (1) is oxidized to form a sulfide, and the sulfide is condensed. Yes, it can also be described as a sulfide condensation compound of a sulfur-containing organosilicon compound represented by the general formula (1).

（式（６）中、Ｒ^１及びＹは一般式（１）と同じであり、Ｘはハロゲン原子であり、塩素原子、又は臭素原子であることが好ましく、塩素原子が特に好ましい。）

（式（７）中、ｐは一般式（１）と同じである。）

（式（８）中、Ｍはアルカリ金属であり、Ｎａ、又はＫであることが好ましい。ｐは一般式（１）と同じである。） In the method for producing a sulfur-containing organosilicon compound having two or more thioether groups of the present invention, a method for producing a sulfur-containing organosilicon compound represented by the general formula (1) and a sulfur-containing organosilicon compound represented by the general formula (2) And a production method of reacting the halogen-containing organosilicon compound represented by the general formula (6) with the polythiol represented by the general formula (7) and / or the polythiol alkali metal salt represented by the general formula (8).

(In Formula (6), R ¹ and Y are the same as those in General Formula (1), X is a halogen atom, preferably a chlorine atom or a bromine atom, and particularly preferably a chlorine atom.)

(In formula (7), p is the same as in general formula (1).)

(In formula (8), M is an alkali metal and is preferably Na or K. p is the same as in formula (1).)

  Specific examples of the halogen-containing organosilicon compound represented by the general formula (6) include 1-chloromethyldimethylmethoxysilane, 1-chloromethylmethyldiethoxysilane, 1-chloromethyldimethylethoxysilane, 3-chloropropyltrimethyl. Methoxysilane, 3-chloropropyltriethoxysilane, 3-chloropropyldimethoxymethylsilane, 3-chloropropylmethyldiethoxysilane, 3-chloropropyldimethylethoxysilane, 1-bromomethyltrimethoxysilane, 1-bromomethyltriethoxy Silane, 1-bromomethylmethyldimethoxysilane, 1-bromomethylmethyldiethoxysilane, 1-bromomethyldimethylmethoxysilane, 1-bromomethyldimethylethoxysilane, 3-bromopropyltrimethoxysilane, 3-butyl Mopropyltriethoxysilane, 3-bromopropylmethyldimethoxysilane, 3-bromopropylmethyldiethoxysilane, 3-bromopropyldimethylethoxysilane, 3-chloropropyltrioctoxysilane, 3-chloropropylmethyldioctoxysilane, 3-chloropropyltrihexoxysilane, 3-chloropropylmethyldihexoxysilane, 3-chloropropyltridecanoxysilane, 3-chloropropylmethyldecanoxysilane, 3-chloropropyltrioctadecanoxysilane, 3 -Chloropropylmethyldioctadecanoxysilane, 3-chloropropylethoxydiethyleneglycoxysilane, 3-chloropropylmethyldiethyleneglycoxysilane, 3-chloropropyltrimethoxysilane and polyethylene group Cole (repeating unit 1-8) monobutyl ether reaction product, 3-chloropropyltrimethoxysilane and polyethylene glycol (repeating unit 1-8) monoethyl ether reaction product, 3-chloropropyltrimethoxysilane and polyethylene glycol (repeat Unit 1-8) Reaction product of monomethyl ether, reaction product of 3-chloropropyltrimethoxysilane and 2-methyl-1,3-propanediol, 3-chloropropyltrimethoxysilane and 2,2-dimethyl-1,3- Propanediol reactant, 3-chloropropyltrimethoxysilane and N-methyldiethanolamine reactant, 3-chloropropyldimethoxymethylsilane and N-methyldiethanolamine reactant, 3-chloropropyltrimethoxysilane and N-butyldiethanolamine The opposite of Things, 3-chloropropyl reaction of dimethoxy methyl silane and N- butyl diethanolamine, 3-chloropropyl Sila Trang, and 3-chloromethyl-sila Trang like.

  Specific examples of the polythiol represented by the general formula (7) include 2,2′-thiodiethane-1-thiol, 3,6-dithiaoctane-1,8-dithiol, 3,6,9-trithiaundecane-1. , 11-dithiol, 3,6,9,12-tetrathiatetradecane-1,14-dithiol.

  Specific examples of the polythiol alkali metal salt represented by the general formula (8) include 2,2′-thiodiethane-1-thiol, 3,6-dithiaoctane-1,8-dithiol, 3,6,9-trithia. Examples thereof include a sodium salt or a potassium salt of a compound selected from undecane-1,11-dithiol, 3,6,9,12-tetrathiatetradecane-1,14-dithiol.

  Although the usage-amount of the polythiol shown by General formula (7) and / or the polythiol alkali metal salt shown by General formula (8) is not specifically limited, With respect to the halogen-containing organosilicon compound shown by General formula (6), It is preferable to make it react by 0.3-2 equivalent, It is more preferable to make it react by 0.4-1.5 equivalent, It is especially preferable to make it react by 0.45-1.2 equivalent.

  In the production method in which the halogen-containing organosilicon compound represented by the general formula (6) and the polythiol represented by the general formula (7) and / or the polythiol alkali metal salt represented by the general formula (8) are reacted, an inert gas atmosphere It is preferable to make it react below, and inert gas, such as nitrogen gas and argon gas, is used.

  In the production method in which the halogen-containing organosilicon compound represented by the general formula (6) and the polythiol represented by the general formula (7) and / or the polythiol alkali metal salt represented by the general formula (8) are reacted, It is preferable to make it react, and alcohols, ethers, ketones, amides, and these combinations can be illustrated. Examples of alcohols include methanol, ethanol, and propanol. Examples of ethers include tetrahydrofuran, 2-methyltetrahydrofuran, tetrahydropyran, crown ether, dimethoxyethane, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, diethylene glycol dibutyl ether, Examples include propylene glycol dimethyl ether. Examples of ketones include acetone and methyl ethyl ketone. Examples of amides include N, N-dimethylformamide (DMF) and N, N-dimethylacetamide. Can do. Among polar solvents, alcohols and amides are preferable, and methanol, ethanol, and N, N-dimethylformamide (DMF) are particularly preferable.

  Although the usage-amount of a polar solvent is not specifically limited, It is preferable to make it react 0.1 to 20 weight times with respect to the halogen-containing organosilicon compound shown by General formula (6), 0.1 to 10 weight times It is more preferable to react, and it is particularly preferable to react at 0.5 to 10 times by weight.

  In the production method of reacting the halogen-containing organosilicon compound represented by the general formula (6) with the polythiol represented by the general formula (7) and / or the polythiol alkali metal salt represented by the general formula (8), a basic substance is used. Alkylamine, sodium hydroxide, ammonia and the like can be exemplified, and triethylamine, sodium hydroxide and ammonia are preferable.

  Although the usage-amount of a basic substance is not specifically limited, It is preferable to make it react by 0.9-3 equivalent with respect to the halogen-containing organosilicon compound shown by General formula (6), and it reacts by 0.9-2 equivalent More preferably, the reaction is performed at 1.0 to 1.5 equivalents.

  As reaction conditions of this invention, it can be made to react on the conditions in the range of a normal pressure to 1 Mpa. The reaction temperature is preferably 30 to 150 ° C, more preferably 40 to 150 ° C, and particularly preferably 50 to 120 ° C. The reaction time is not particularly limited, but can be 30 minutes to 24 hours.

（式（１）中、Ｒ^１、Ｙ及びｐは式（３）と同じ。）

（式（９）中、Ｒ^２は式（３）と同じであり、Ｘはハロゲン原子であり、塩素原子、又は臭素原子が好ましい。） In the method for producing a sulfur-containing organosilicon compound having two or more thioether groups of the present invention, the sulfur-containing organosilicon compound represented by the general formula (1) is used as the method for producing the sulfur-containing organosilicon compound represented by the general formula (3). A production method of reacting a compound with an acid halide represented by the general formula (9) can be mentioned. This production method may be performed in the state of a mixture in which the sulfur-containing organosilicon compound represented by the general formula (1) and the sulfur-containing organosilicon compound represented by the general formula (2) coexist. It may be obtained by a production method in which the halogen-containing organosilicon compound shown is reacted with the polythiol shown by the general formula (7) and / or the polythiol alkali metal salt shown by the general formula (8). It may be purified.

(In formula (1), R ¹ , Y and p are the same as in formula (3).)

(In Formula (9), R ² is the same as Formula (3), X is a halogen atom, and a chlorine atom or a bromine atom is preferable.)

  Specific examples of the acid halide represented by the general formula (9) include acetic acid chloride, acetic acid bromide, propionic acid chloride, propionic acid bromide, octyl acid chloride, octylic acid bromide, benzoic acid chloride, benzoic acid bromide, para-t -Butylbenzoic acid chloride, para-t-butylbenzoic acid bromide, p-toluic acid chloride, p-toluic acid bromide, meta-toluic acid chloride, meta-toluic acid bromide, naphthoic acid chloride, naphthoic acid bromide, acetic acid phenyl chloride, acetic acid phenyl bromide , Diphenyl-4-carboxylic acid chloride, diphenyl-4-carboxylic acid bromide, diphenylacetic acid chloride, diphenylacetic acid bromide, butanoic acid chloride, butanoic acid bromide, pentanoic acid Roraido, pentanoic acid bromide, hexanoic acid chloride, hexanoic acid bromide, decanoic acid chloride, decanoic acid bromide, chloride dodecanoic acid, dodecanoic acid bromide, hexadecanoic acid chloride, hexadecanoic acid bromide include octadecanoic acid chloride and octadecanoic acid bromide.

  Although the usage-amount of the acid halide shown by General formula (9) is not specifically limited, It is preferable to make it react with 0.8-5 equivalent with respect to the sulfur-containing organosilicon compound shown by General formula (1), 0 It is more preferable to make it react by 0.9-3 equivalent, and it is especially preferable to make it react by 0.95-2.1 equivalent.

  In the production method in which the sulfur-containing organosilicon compound represented by the general formula (1) and the acid halide represented by the general formula (9) are reacted, the reaction is preferably performed in an inert gas atmosphere, such as nitrogen gas or argon gas. Inert gases are used.

  In the production method in which the sulfur-containing organosilicon compound represented by the general formula (1) and the acid halide represented by the general formula (9) are reacted, a basic substance may be used, and alkylamine, sodium hydroxide, ammonia Examples thereof include triethylamine, sodium hydroxide, and ammonia.

  Although the usage-amount of a basic substance is not specifically limited, It is preferable to make it react by 0.9-3 equivalent with respect to the sulfur-containing organosilicon compound shown by General formula (1), and it reacts by 0.9-2 equivalent More preferably, the reaction is performed at 1.0 to 1.5 equivalents.

  The production method in which the sulfur-containing organosilicon compound represented by the general formula (1) and the acid halide represented by the general formula (9) are reacted may be performed in an aprotic polar solvent. Examples of the aprotic polar solvent include ethers, ketones, amides and nitriles. Examples of ethers include tetrahydrofuran, 2-methyltetrahydrofuran, tetrahydropyran, crown ether, dimethoxyethane, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, diethylene glycol dibutyl ether, and propylene glycol dimethyl ether. Examples of ketones include acetone and methyl ethyl ketone. Examples of amides include N, N-dimethylformamide (DMF) and N, N-dimethylacetamide. Examples of nitriles include acetonitrile and propionitrile.

  Although the usage-amount of an aprotic polar solvent is not specifically limited, It is preferable to make it react by 0.1-20 weight times with respect to the sulfur-containing organosilicon compound shown by General formula (1), 0.1-10 The reaction is more preferably performed by weight, and it is particularly preferable that the reaction is performed by 0.5 to 10 times by weight.

  The production method in which the sulfur-containing organosilicon compound represented by the general formula (1) and the acid halide represented by the general formula (9) are reacted may be performed in a nonpolar solvent. Examples of the nonpolar solvent include pentane, hexane, heptane, nonane, decane and the like, and hexane is preferable.

  Although the usage-amount of a nonpolar solvent is not specifically limited, It is preferable to make it react with 0.1-20 weight times with respect to the sulfur-containing organosilicon compound shown by General formula (1), 0.1-10 weight times It is more preferable to make it react with 0.5 to 10 weight times.

  As reaction conditions of this invention, it is preferable to react at -30-120 degreeC, It is more preferable to react at -25-100 degreeC, It is especially preferable to react at -20-80 degreeC. Furthermore, when adding an acid halide, it may be cooled to a range of −30 ° C. to 20 ° C., and the temperature may be increased to 120 ° C., preferably up to 100 ° C., more preferably up to 80 ° C. after the acid halide is added. The reaction time is not particularly limited, but can be 30 minutes to 24 hours.

  The method for producing a sulfur-containing organosilicon compound having two or more thioether groups in the above two examples is preferable in that a complicated synthesis method and an expensive catalyst are not required.

  When the sulfur-containing organosilicon compound having two or more thioether groups of the present invention is blended in the rubber composition, one or more sulfur-containing organosilicon compounds may be blended, and 2 as obtained by the above production method. You may mix | blend as a mixture of the sulfur-containing organosilicon compound of a seed | species or more.

  Examples of the rubber used in the rubber composition containing the sulfur-containing organosilicon compound having two or more thioether groups of the present invention include rubber having an unsaturated bond. Specific examples include natural rubber, polyisoprene rubber, various styrene butadiene copolymer rubbers (SBR), polybutadiene rubber (BR), various acrylonitrile butadiene copolymer rubbers, butyl rubber, chloroprene rubber and other diene rubbers and various ethylenes. Examples include propylene copolymer rubber. The rubbers can be used alone or optionally blended.

  As the filler used in the rubber composition containing the sulfur-containing organosilicon compound having two or more thioether groups of the present invention, silica, clay, talc, surface-modified carbon black and calcium carbonate are preferable, and silica is particularly preferable.

  The amount of filler used in the rubber composition is 5 to 150 parts by weight, preferably 10 to 120 parts by weight, with respect to 100 parts by weight of rubber.

  As a compounding quantity of the sulfur-containing organosilicon compound which has 2 or more of thioether groups of this invention, it is 0.2-30 weight part with respect to 100 weight part of fillers, Preferably it is 1-20 weight part.

  The rubber composition containing the sulfur-containing organosilicon compound having two or more thioether groups of the present invention includes various types of processing aids, anti-aging agents, softeners, plasticizers, vulcanizing agents, A vulcanization accelerator can be mix | blended as needed.

  Further, the rubber composition containing the sulfur-containing organosilicon compound having two or more thioether groups of the present invention can be used in combination with other silane coupling agents, such as vinyltrimethoxysilane, vinylethoxysilane, methacrylate. Roxypropyltrimethoxysilane, methacryloxypropyltriethoxysilane, mercaptopropyltrimethoxysilane, mercaptopropyltriethoxysilane, aminoethylaminopropylmethoxysilane, aminoethylaminopropylethoxysilane, bis-triethoxysilylpropyltetrasulfide, bis- And triethoxysilylpropyl disulfide.

  The rubber composition containing the sulfur-containing organosilicon compound having two or more thioether groups of the present invention can be used after general kneading and further crosslinking.

  EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated concretely, this invention is not restrict | limited to the following Example.

  For the gas chromatography (hereinafter abbreviated as GC) measurement, GC-2014 AFSPL manufactured by Shimadzu Corporation equipped with a column G-205 manufactured by Chemical Substance Evaluation Research Organization and an FID detector was used. The inlet temperature is 280 ° C, the detector side temperature is 320 ° C, the column temperature rise condition is 50 ° C for 2 minutes, then the temperature is raised to 300 ° C at a rate of 10 ° C / minute, and after reaching 300 ° C, the temperature is measured for 15 minutes. did. The carrier gas was helium at a flow rate of 20 ml / min and 30 ml / min when the column temperature reached 300 ° C. The sample injection volume was 0.2 μL.

Implementation synthesis example 1
In a 1000 ml pressure vessel, 400 g of N, N-dimethylformamide (abbreviated as DMF), 77 g (0.5 mol) of 2,2′-thiodietane-1-thiol and 3-chloropropyltriethoxysilane (abbreviated as TESPC) 120 .3 g (0.5 mol) was added, the internal temperature was set to 75 ° C., purged with nitrogen, and 8.9 g (0.52 mol) of ammonia gas was introduced while stirring at 200 rpm. , And pressurized to 0.16 MPa. After 8 hours, the contents were taken out, the produced ammonium chloride salt was separated, and DMF was distilled off to obtain 162 g of a reaction product. Composition analysis from the peak area ratio of the gas chromatograph of this reaction product revealed that 95.8% of a sulfur-containing organosilicon compound having two or more thioether groups (by reaction of TESPC with 2,2′-thiodiethane-1-thiol) It was found that the obtained mercaptosilane compound was 58.6% and the sulfide condensation compound of the mercaptosilane compound was 37.2%).

Implementation synthesis example 2
30 g of methanol, 7.7 g (0.05 mol) of 2,2′-thiodiethane-1-thiol, and 2 g (0.05 mol) of sodium hydroxide were added to a 100 ml three-necked flask and stirred at 57 ° C. for 2 hours. Was distilled off under reduced pressure at 40 ° C. and further dried under reduced pressure at 100 ° C. and 5 torr for 1 hour. Thereafter, 12 g (0.05 mol) of TESPC and 50 g of ethanol were added and stirred at 70 ° C. with a magnetic stirrer. After 6 hours, the reaction solution was filtered, and ethanol was distilled off under reduced pressure to obtain 15.7 g of a reaction product. Composition analysis from the peak area ratio of the gas chromatograph of this reaction product revealed that 78.4% of a sulfur-containing organosilicon compound having two or more thioether groups (by reaction of TESPC with 2,2′-thiodietane-1-thiol). It was found that the obtained mercaptosilane compound was 50.5% and the sulfide condensation compound of the mercaptosilane compound was 27.9%.

Implementation synthesis example 3
27.6 g of the reaction product obtained in Example 1, 35 g of hexane, and 5.3 g (0.05 mol) of triethylamine were added to a 100 ml three-necked flask, and 8.6 g of octyl acid chloride was added at 5 ° C. in a nitrogen atmosphere. 0.05 mol) was added dropwise over 30 minutes, and the mixture was further stirred for 3 hours. Thereafter, filtration and hexane were distilled off to obtain 27.6 g of a reaction product. According to the composition analysis from the peak area ratio of the gas chromatograph of this reaction product, a sulfur-containing organosilicon compound having two or more thioether groups was found to be 88.5% (by reaction of TESPC with 2,2′-thiodiethane-1-thiol). (55.0% product obtained by reaction of the obtained mercaptosilane compound and octyl chloride, 33.5% sulfide condensation compound of mercaptosilane compound obtained by reaction of TESPC and 2,2′-thiodietane-1-thiol) It turns out that.

Comparative Synthesis Example 1
Add DMF 300g, 1,2-ethanedithiol (abbreviated as EDS) 98.7g (1.05mol) and TESPC 240.5g (1mol) to a 1000ml pressure vessel, set the internal temperature to 75 ° C, nitrogen While purging and stirring at 200 rpm, ammonia gas was introduced and pressurized to 0.2 MPa. After 6 hours, the contents were taken out and filtered, and DMF was distilled off to obtain 296 g of a reaction product. Composition analysis from the peak area ratio of the gas chromatograph of this product revealed that 69.4% of the sulfur-containing organosilicon compound having one thioether group (50.7% of the mercaptosilane compound in which TESPC and EDS reacted, the mercaptosilane) The sulfide condensation compound of the compound was 18.7%).

Comparative Synthesis Example 2
An aqueous solution in which 288.6 g (0.5 mol) of TESPC, 15 g of toluene and 113.6 g of 71% sodium hydrosulfide (1.44 mol in terms of sodium hydrosulfide) are dissolved in 154.0 g of ion-exchanged water in a 1000 ml pressurized container. Then, 5.8 g (0.018 mol) of t-butylammonium bromide was added, the internal temperature was set to 75 ° C., purged with nitrogen, and stirred at 200 rpm. After 6 hours, the contents were taken out, transferred to a separatory funnel, the aqueous layer was removed, 15 g of magnesium sulfate was added to the oil layer and left overnight. Thereafter, the low boiling fraction was removed at 70 ° C. under reduced pressure to obtain 251 g of a reaction product. According to the composition analysis from the peak area ratio of the gas chromatograph of this reaction product, the triethoxysilylpropyl mercaptan in which TESPC and sodium hydrosulfide reacted was 92.2%, and the sulfide condensation compound of the mercaptosilane compound was 6.6%. It turns out that.

The compounding agents used in Examples and Comparative Examples are shown below. The compounding agents and blending amounts were determined according to the blending shown in Table 1. The unit is parts by weight.
* 1 "S-SBR SL552" manufactured by JSR Corporation
* 2 “BR-01” manufactured by JSR Corporation
* 3 “Nipsil AQ” manufactured by Tosoh Silica Corporation
* 4 “Sunsen 415” manufactured by Nippon Sun Oil Co., Ltd.
* 5 “NOCRACK PA” manufactured by Ouchi Shinsei Chemical Co., Ltd.
* 6 “Noxeller D” manufactured by Ouchi Shinsei Chemical Co., Ltd.
* 7 “Noxeller CZ” manufactured by Ouchi Shinsei Chemical Co., Ltd.

(A training method)
In a 1.7 L Banbury mixer, mix SBR and BR blended with A at room temperature for 3 minutes, add 1/4 of silica, softener, stearic acid, and anti-aging agent, knead for 5 minutes, and remain Of silica was added, kneaded for 3 minutes, the remaining silica was added, kneaded for 3 minutes, cleanup, further kneaded for 3 minutes, then dropped onto a 12 inch roll and cooled.

  After kneading the above-mentioned A-kneaded mixture with a 7-inch roll at 100 ° C. for 4 minutes, a sulfur-containing organosilicon compound (reaction products obtained in Examples Synthesis Examples 1 to 3, Comparative Synthesis Example 1 and Comparative Synthesis Example 2) is shown. 1 part by weight was added, kneaded for 6 minutes, and used for B kneading on the next day.

(B training method)
B kneading compound was added to the compound obtained above, and kneaded for 6 minutes with a 7-inch roll at 40 ° C., and then subjected to the following test.

(Tensile property test)
A No. 3 dumbbell test piece was punched out from a vulcanized sheet obtained by press vulcanizing the B kneaded compound prepared in the above at 160 ° C. for 20 minutes, and “TENSILON RTA-500” manufactured by ORIENTEC was used. Then, a tensile test was performed according to JIS K6301. The results are shown in Table 2.

(Viscoelastic property test)
A test piece having a width of 4 × length of 40 × thickness of 2 mm was punched out from a vulcanized sheet obtained by press-vulcanizing the B kneaded compound prepared in the above at 160 ° C. for 20 minutes, and manufactured by Seiko Instruments Inc. Measurement was performed with DMS6100 under an excitation condition of an initial load of 1000 mN, a tensile strain of 10 μm, and 10 Hz. The measurement temperature range was −20 ° C. to 80 ° C., and the temperature was increased at a rate of 2 ° C./min. The results are shown in Table 2.

  In Examples 1 to 3, the loss tangent at 60 ° C. in the rolling resistance region of the tire was low, and the tensile properties were also good. On the other hand, in Comparative Example 1, the loss tangent at 60 ° C. was higher than those in Examples 1 to 3. In Comparative Example 2, the loss tangent at 60 ° C. is almost the same as that of Examples 1 to 3, but the tensile properties are not good (100%, absolute value of 300% stress is small), and tire stress Has been shown to be unsuitable for components that require it. Moreover, since the value of 300% stress / 100% stress was small in both Comparative Examples 1 and 2, it was suggested that the reaction between the coupling agent and silica was insufficient.

  The sulfur-containing organosilicon compound of the present invention combines a synthetic rubber or natural rubber with an unsaturated bond with a white filler such as silica, clay or talc or a filler such as surface-modified carbon black blended in the rubber. It is used as a substance to be made. Specifically, it is useful for tires, vibration-proof rubbers and the like.

Claims (14)

  A sulfur-containing organosilicon compound having two or more thioether groups. The sulfur-containing organosilicon compound according to claim 1, which is selected from the group of sulfur-containing organosilicon compounds described in the general formulas (1) to (3).

(In the formula (1), ^{R 1} is a divalent alkyl group, or a phenyl group having 1 to 10 carbon atoms, Y is the general formula (4), the general formula (5), or one having 1 to 8 carbon atoms A silatrane group (N≡ (CH ₂ CH ₂ O) ₃ Si—) optionally substituted with a valent alkyl group, and p is an integer of 2 to 5.

(In the formula (2), ^{R 1} is a divalent alkyl group, or a phenyl group having 1 to 10 carbon atoms, Y is the general formula (4), the general formula (5), or one having 1 to 8 carbon atoms A silatrane group (N≡ (CH ₂ CH ₂ O) ₃ Si—) optionally substituted with a valent alkyl group, p is an integer of 2 to 5, and q is 0 to 8.

(In the formula (3), ^{R 1} is a divalent alkyl group, or a phenyl group having 1 to 10 carbon atoms, Y is the general formula (4), the general formula (5), or one having 1 to 8 carbon atoms A silatrane group (N≡ (CH ₂ CH ₂ O) ₃ Si—) optionally substituted with a valent alkyl group, and R ² is a monovalent alkyl group having 1 to 16 carbon atoms, a phenyl group, a carbon number A group selected from a monovalent alkyl group of 1 to 6 and an aralkyl group having 7 to 12 carbon atoms is an aryl group or a naphthyl group substituted, and p is an integer of 2 to 5.)

(In Formula (4), R < ³ >, R < ⁴ >, R < ⁵ > may be same or different, respectively, a C1-C18 monovalent alkyl group, C1-C18 monovalent alkoxy group, OH group, or _{C n H 2n-1 O -} ((CH 2) m O) is represented n with _r 1-18, m is 1 to 6, r is 1 to 18 polyalkylene glycol monoalkyl An ether group, and at least one of R ³ , R ⁴ , and R ⁵ is an alkoxy group, an OH group, or a polyalkylene glycol monoalkyl ether group.)

(In the formula (5), ^{R 6} is an alkoxy group, OH group of monovalent to 18 carbon atoms, or _C n _H 2n-1 O - represented by _{((CH 2) m O)} r, n is 1 -18, m is a polyalkylene glycol monoalkyl ether group in which 1 to 6 and r is 1 to 18, R ⁷ and R ⁸ may be the same or different from each other, and are divalent having 1 to 8 carbon atoms. An alkyl group, W is —C (═O) —, —O—, —NR ⁹ —, —CR ¹⁰ R ¹¹ —, and R ⁹ , R ¹⁰ , R ¹¹ are each an alkyl group having 1 to 18 carbon atoms or Hydrogen.) A method for producing a sulfur-containing organosilicon compound represented by the general formula (1) and a sulfur-containing organosilicon compound represented by the general formula (2), wherein the halogen-containing organosilicon compound represented by the general formula (6) and the general formula A process for producing a sulfur-containing organosilicon compound comprising reacting the polythiol represented by (7) and / or the polythiol alkali metal salt represented by the general formula (8).

(In the formula (1), ^{R 1} is a divalent alkyl group, or a phenyl group having 1 to 10 carbon atoms, Y is the general formula (4), the general formula (5), or one having 1 to 8 carbon atoms A silatrane group (N≡ (CH ₂ CH ₂ O) ₃ Si—) optionally substituted with a valent alkyl group, and p is an integer of 2 to 5.

(In the formula (2), ^{R 1} is a divalent alkyl group, or a phenyl group having 1 to 10 carbon atoms, Y is the general formula (4), the general formula (5), or one having 1 to 8 carbon atoms A silatrane group (N≡ (CH ₂ CH ₂ O) ₃ Si—) optionally substituted with a valent alkyl group, p is an integer of 2 to 5, and q is 0 to 8.

(In Formula (4), R < ³ >, R < ⁴ >, R < ⁵ > may be same or different, respectively, a C1-C18 monovalent alkyl group, C1-C18 monovalent alkoxy group, OH group, or _{C n H 2n-1 O -} ((CH 2) m O) is represented n with _r 1-18, m is 1 to 6, r is 1 to 18 polyalkylene glycol monoalkyl An ether group, and at least one of R ³ , R ⁴ , and R ⁵ is an alkoxy group, an OH group, or a polyalkylene glycol monoalkyl ether group.)

(In the formula (5), ^{R 6} is an alkoxy group, OH group of monovalent to 18 carbon atoms, or _C n _H 2n-1 O - represented by _{((CH 2) m O)} r, n is 1 -18, m is a polyalkylene glycol monoalkyl ether group in which 1 to 6 and r is 1 to 18, R ⁷ and R ⁸ may be the same or different from each other, and are divalent having 1 to 8 carbon atoms. An alkyl group, W is —C (═O) —, —O—, —NR ⁹ —, —CR ¹⁰ R ¹¹ —, and R ⁹ , R ¹⁰ , R ¹¹ are each an alkyl group having 1 to 18 carbon atoms or Hydrogen.)

(In formula (6), R ¹ and Y are the same as in general formula (1), and X is a halogen atom.)

(In formula (7), p is the same as in general formula (1).)

(In formula (8), M is an alkali metal, and p is the same as in general formula (1).)   The halogen-containing organosilicon compound represented by the general formula (6) is 1-chloromethyldimethylmethoxysilane, 1-chloromethylmethyldiethoxysilane, 1-chloromethyldimethylethoxysilane, 3-chloropropyltrimethoxysilane, 3- Chloropropyltriethoxysilane, 3-chloropropyldimethoxymethylsilane, 3-chloropropylmethyldiethoxysilane, 3-chloropropyldimethylethoxysilane, 1-bromomethyltrimethoxysilane, 1-bromomethyltriethoxysilane, 1-bromo Methylmethyldimethoxysilane, 1-bromomethylmethyldiethoxysilane, 1-bromomethyldimethylmethoxysilane, 1-bromomethyldimethylethoxysilane, 3-bromopropyltrimethoxysilane, 3-bromopropyltrie Xysilane, 3-bromopropylmethyldimethoxysilane, 3-bromopropylmethyldiethoxysilane, 3-bromopropyldimethylethoxysilane, 3-chloropropyltrioctoxysilane, 3-chloropropylmethyldioctoxysilane, 3-chloropropyl Trihexoxysilane, 3-chloropropylmethyldihexoxysilane, 3-chloropropyltridecanoxysilane, 3-chloropropylmethyldecanoxysilane, 3-chloropropyltrioctadecanoxysilane, 3-chloropropylmethyl Dioctadecanoxysilane, 3-chloropropylethoxydiethyleneglycoxysilane, 3-chloropropylmethyldiethyleneglycoxysilane, 3-chloropropyltrimethoxysilane and polyethylene glycol 1-8) Reactant of monobutyl ether, 3-chloropropyltrimethoxysilane and polyethylene glycol (repeating units 1-8) Reactant of monoethyl ether, 3-chloropropyltrimethoxysilane and polyethylene glycol (repeating units 1-8) ) Reaction product of monomethyl ether, reaction product of 3-chloropropyltrimethoxysilane and 2-methyl-1,3-propanediol, reaction of 3-chloropropyltrimethoxysilane and 2,2-dimethyl-1,3-propanediol A reaction product of 3-chloropropyltrimethoxysilane and N-methyldiethanolamine, a reaction product of 3-chloropropyldimethoxymethylsilane and N-methyldiethanolamine, a reaction product of 3-chloropropyltrimethoxysilane and N-butyldiethanolamine, 3-chlorop Reactant pill dimethoxymethyl silane and N- butyl diethanolamine, 3-chloropropyl Sila Trang, and manufacturing method of claim 3 sulfur-containing organosilicon compound according selected from the group consisting of 3-chloromethyl-Sila Trang.   The polythiol represented by the general formula (7) is 2,2′-thiodiethane-1-thiol, 3,6-dithiaoctane-1,8-dithiol, 3,6,9-trithiaundecane-1,11-dithiol, 3 , 6,9,12-tetrathiatetradecane-1,14-dithiol, and the polythiol alkali metal salt represented by the general formula (8) is 2,2′-thiodiethane-1-thiol, 3, Sodium of a compound selected from 6-dithiaoctane-1,8-dithiol, 3,6,9-trithiaundecane-1,11-dithiol, 3,6,9,12-tetrathiatetradecane-1,14-dithiol The method for producing a sulfur-containing organosilicon compound according to claim 3 or 4, which is a salt or a potassium salt.   The method for producing a sulfur-containing organosilicon compound according to any one of claims 3 to 5, wherein the reaction is carried out in an inert gas atmosphere and in a polar solvent.   The method for producing a sulfur-containing organosilicon compound according to any one of claims 3 to 6, wherein the reaction is carried out using a basic substance.   The method for producing a sulfur-containing organosilicon compound according to any one of claims 3 to 7, wherein the reaction is carried out under conditions in the range of normal pressure to 1 MPa. A method for producing a sulfur-containing organosilicon compound represented by the general formula (3), comprising reacting a sulfur-containing organosilicon compound represented by the general formula (1) with an acid halide represented by the general formula (9) A method for producing a sulfur-containing organosilicon compound.

(In the formula (3), ^{R 1} is a divalent alkyl group, or a phenyl group having 1 to 10 carbon atoms, Y is the general formula (4), the general formula (5), or one having 1 to 8 carbon atoms A silatrane group (N≡ (CH ₂ CH ₂ O) ₃ Si—) optionally substituted with a valent alkyl group, and R ² is a monovalent alkyl group having 1 to 16 carbon atoms, a phenyl group, a carbon number A group selected from a monovalent alkyl group of 1 to 6 and an aralkyl group having 7 to 12 carbon atoms is an aryl group or a naphthyl group substituted, and p is an integer of 2 to 5.)

(In Formula (4), R < ³ >, R < ⁴ >, R < ⁵ > may be same or different, respectively, a C1-C18 monovalent alkyl group, C1-C18 monovalent alkoxy group, OH group, or _{C n H 2n-1 O -} ((CH 2) m O) is represented n with _r 1-18, m is 1 to 6, r is 1 to 18 polyalkylene glycol monoalkyl An ether group, and at least one of R ³ , R ⁴ , and R ⁵ is an alkoxy group, an OH group, or a polyalkylene glycol monoalkyl ether group.)

(In the formula (5), ^{R 6} is an alkoxy group, OH group of monovalent to 18 carbon atoms, or _C n _H 2n-1 O - represented by _{((CH 2) m O)} r, n is 1 -18, m is a polyalkylene glycol monoalkyl ether group in which 1 to 6 and r is 1 to 18, R ⁷ and R ⁸ may be the same or different from each other, and are divalent having 1 to 8 carbon atoms. An alkyl group, W is —C (═O) —, —O—, —NR ⁹ —, —CR ¹⁰ R ¹¹ —, and R ⁹ , R ¹⁰ , R ¹¹ are each an alkyl group having 1 to 18 carbon atoms or Hydrogen.)

(In formula (1), R ¹ , Y and p are the same as in formula (3).)

(In formula (9), R ² is the same as in formula (3), and X is a halogen atom.)   The acid halide represented by the general formula (9) is acetic acid chloride, acetic acid bromide, propionic acid chloride, propionic acid bromide, octyl acid chloride, octyl acid bromide, benzoic acid chloride, benzoic acid bromide, para-t-butylbenzoic acid chloride. , Para-t-butylbenzoic acid bromide, p-toluic acid chloride, p-toluic acid bromide, meta-toluic acid chloride, meta-toluic acid bromide, naphthoic acid chloride, naphthoic acid bromide, acetic acid phenyl chloride, phenyl bromide acetate, diphenyl-4- Carboxylic acid chloride, diphenyl-4-carboxylic acid bromide, diphenylacetic acid chloride, diphenylacetic acid bromide, butanoic acid chloride, butanoic acid bromide, pentanoic acid chloride, pentane 10. The acid bromide, hexanoic acid chloride, hexanoic acid bromide, decanoic acid chloride, decanoic acid bromide, dodecanoic acid chloride, dodecanoic acid bromide, hexadecanoic acid chloride, hexadecanoic acid bromide, octadecanoic acid chloride and octadecanoic acid bromide. A process for producing a sulfur-containing organosilicon compound.   The method for producing a sulfur-containing organosilicon compound according to claim 9 or 10, wherein the reaction is carried out using an aprotic polar solvent or a nonpolar solvent as a basic substance and a solvent.   A sulfur-containing organosilicon compound produced by the method for producing a sulfur-containing organosilicon compound according to claim 3.   A rubber composition containing the sulfur-containing organosilicon compound according to claim 1, 2 or 12.   A tire comprising the rubber composition according to claim 13.