JP4662042B2 - Bisorganoxysilane compound having amino group protected by silyl group and method for producing the same - Google Patents

Description

  The present invention relates to a bisorganoxysilane compound having an amino group protected by a silyl group, useful as a polymer modifier, a coating additive, an adhesive, a silane coupling agent, a surface treatment agent, and the like, and a method for producing the same.

  Organoxysilane compounds in which amino groups are protected are useful as polymer modifiers, coating additives, adhesives, silane coupling agents, surface treatment agents, etc., and in particular, organoxysilanes in which amino groups are protected with silyl groups. Silane compounds are suitable for use in the above applications because they are easy to protect and deprotect.

  Examples of such organoxysilane compounds in which an amino group is protected with a silyl group include N, N- (bistrimethylsilyl) aminopropylsilane compounds described in Japanese Patent No. 3414134 (Patent Document 1). It is disclosed that it is useful as a modifier for silicone oil.

  JP-A No. 2003-171418 (Patent Document 2) discloses a compound having a protected primary amino group and an alkoxysilyl group, that is, an N, N- (bistrimethylsilyl) aminopropylsilane compound, which is a styrene- A compound capable of introducing an amino group into the terminal chain of living polymerization of butadiene anion polymerization. An amino group-containing styrene-butadiene rubber produced using this compound as an anionic polymerization terminal modifier contains silica and carbon black. It is disclosed that it is useful as a base polymer for tires.

  Furthermore, such an organoxysilane compound in which an amino group is protected with a silyl group is also useful as an additive for paints and adhesives. For example, by adding it to an epoxy resin, an amino-based silane coupling agent can be added. One-component curable composition with effects (adhesion and reinforcement), that is, a stable composition that does not show reactivity in a system where moisture is blocked, but is deprotected by hydrolysis when in contact with moisture Thus, the amino group is regenerated and an amino-based silane coupling agent is added to obtain a composition having the same effect.

  As described above, organoxysilane compounds in which the amino group is protected with a silyl group can prevent the functional group itself from reacting due to the protection of the functional group when the polymer is modified or when a paint or adhesive is added. Then, it is useful because the functional group can be regenerated and introduced quantitatively and efficiently by subsequent deprotection. However, known organoxysilane compounds in which an amino group is protected with a silyl group have only one organoxysilyl group per molecule, so that, for example, when used as a polymer modifier, a polymer filler In particular, the interaction with silica is weak, and when it is used as a paint or an adhesive additive, there is a problem that sufficient adhesion and reinforcement cannot be obtained.

Japanese Patent No. 3414134 JP 2003-171418 A

  The present invention has been made in view of the above circumstances. A polymer modifier that has a strong interaction with a filler, a paint that can provide sufficient adhesion and reinforcement, and an amino group that is useful as an adhesive additive is a silyl group. It is an object to provide a protected bisorganoxysilane compound.

（式中、Ｒは炭素数１〜１０の直鎖状又は分岐状の２価炭化水素基、Ｒ¹、Ｒ²、Ｒ³、Ｒ⁴は炭素数１〜１０の１価炭化水素基、Ｒ⁵は水素原子又はメチル基であり、ｎは０、１又は２である。）
で示されるシリル基で保護されたアミノ基を有するビスオルガノキシシラン化合物が、高分子変性剤として用いた場合、フィラーとの相互作用がより強くなり、接着剤添加剤として用いた場合、接着性、補強性がより向上することを知見し、本発明を完成するに至ったものである。 As a result of intensive studies to achieve the above object, the present inventor has the following general formula (1) that can be obtained by the following method.

(In the formula, R is a linear or branched divalent hydrocarbon group having 1 to 10 carbon atoms, R ¹ , R ² , R ³ , and R ⁴ are monovalent hydrocarbon groups having 1 to 10 carbon atoms, R ⁵ is a hydrogen atom or a methyl group, and n is 0, 1 or 2.)
When the bisorganoxysilane compound having an amino group protected with a silyl group represented by is used as a polymer modifier, the interaction with the filler becomes stronger, and when used as an adhesive additive, The inventors have found that the reinforcing property is further improved and have completed the present invention.

（式中、Ｒは炭素数１〜１０の直鎖状又は分岐状の２価炭化水素基、Ｒ¹、Ｒ²、Ｒ³、Ｒ⁴は炭素数１〜１０の１価炭化水素基、Ｒ⁵は水素原子又はメチル基であり、ｎは０、１又は２である。）
で示されるシリル基で保護されたアミノ基を有するビスオルガノキシシラン化合物。
（ＩＩ）下記一般式（２）

（式中、Ｒ、Ｒ¹、Ｒ²、Ｒ³、Ｒ⁵は（Ｉ）に記載された通りの意味を有する。）
で示される化合物と、下記一般式（３）
ＨＳｉ（ＣＨ₃）_n（ＯＲ⁴）_3-n （３）
（式中、Ｒ⁴、ｎは（Ｉ）に記載された通りの意味を有する。）
で示されるハイドロジェンシラン化合物とを白金触媒下で反応させることを特徴とする（Ｉ）記載のシリル基で保護されたアミノ基を有するビスオルガノキシシラン化合物の製造方法。
（ＩＩＩ）一般式（２）で示される化合物１モルに対し、一般式（３）で示される化合物１〜４モル、白金触媒０．０００００１〜０．０１モルを用いて、反応温度２０〜１００℃、反応時間１〜２０時間で反応させる（ＩＩ）記載の製造方法。 Accordingly, the present invention provides the following silane compound and a method for producing the same.
(I) The following general formula (1)

(In the formula, R is a linear or branched divalent hydrocarbon group having 1 to 10 carbon atoms, R ¹ , R ² , R ³ , and R ⁴ are monovalent hydrocarbon groups having 1 to 10 carbon atoms, R ⁵ is a hydrogen atom or a methyl group, and n is 0, 1 or 2.)
A bisorganoxysilane compound having an amino group protected with a silyl group represented by
(II) The following general formula (2)

(In the formula, R, R ¹ , R ² , R ³ and R ⁵ have the meanings described in (I).)
And a compound represented by the following general formula (3)
HSi (CH ₃ ) _n (OR ⁴ ) _3-n (3)
(Wherein R ⁴ and n have the meanings described in (I).)
The method for producing a bisorganoxysilane compound having an amino group protected by a silyl group according to (I), wherein the hydrogensilane compound is reacted with a hydrogensilane compound represented by formula (I) in the presence of a platinum catalyst.
(III) The reaction temperature is 20 to 100 using 1 to 4 moles of the compound represented by the general formula (3) and 0.000001 to 0.01 mole of the platinum catalyst with respect to 1 mole of the compound represented by the general formula (2). The production method according to (II), wherein the reaction is carried out at a temperature of 1 ° C. for 1 to 20 hours.

  According to the present invention, by using a bisorganoxysilane compound having an amino group protected by a silyl group, when used as a polymer modifier, the interaction with the filler can be made stronger, and the adhesive When used as an additive, it is possible to further improve the adhesion and reinforcing properties.

（式中、Ｒは炭素数１〜１０の直鎖状又は分岐状の２価炭化水素基、Ｒ¹、Ｒ²、Ｒ³、Ｒ⁴は炭素数１〜１０の１価炭化水素基、Ｒ⁵は水素原子又はメチル基であり、ｎは０、１又は２である。）
で示されるシリル基で保護されたアミノ基を有するビスオルガノキシシラン化合物である。 The compound of the present invention has the following general formula (1)

(In the formula, R is a linear or branched divalent hydrocarbon group having 1 to 10 carbon atoms, R ¹ , R ² , R ³ , and R ⁴ are monovalent hydrocarbon groups having 1 to 10 carbon atoms, R ⁵ is a hydrogen atom or a methyl group, and n is 0, 1 or 2.)
And a bisorganoxysilane compound having an amino group protected with a silyl group.

Here, R is a linear or branched divalent hydrocarbon group having 1 to 10 carbon atoms, an alkylene group such as a methylene group, an ethylene group, a trimethylene group or a tetramethylene group, or an arylene group such as a phenylene group. And an aralkylene group. R ¹ , R ² , R ³ , and R ⁴ are monovalent hydrocarbon groups having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, such as linear, branched or cyclic alkyl groups, alkenyl groups, and aryl groups. Is mentioned. Specifically, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, pentyl group, cyclopentyl group, hexyl group, cyclohexyl group, heptyl group, octyl group, decyl group, vinyl Group, allyl group, methallyl group, butenyl group, phenyl group and the like.

Specific examples of the bisorganoxysilane compound having an amino group protected with a silyl group according to the present invention are as follows.
Bis [3- (trimethoxysilyl) propyl] trimethylsilylamine, bis [3- (methyldimethoxysilyl) propyl] trimethylsilylamine, bis [3- (dimethylmethoxysilyl) propyl] trimethylsilylamine, bis [3- (triethoxysilyl) ) Propyl] trimethylsilylamine, bis [3- (methyldiethoxysilyl) propyl] trimethylsilylamine, bis [3- (dimethylethoxysilyl) propyl] trimethylsilylamine, bis [3- (trimethoxysilyl) propyl] triethylsilylamine, Bis [3- (methyldimethoxysilyl) propyl] triethylsilylamine, bis [3- (dimethylmethoxysilyl) propyl] triethylsilylamine, bis [3- (triethoxysilyl) propyl] trie Rusilylamine, bis [3- (methyldiethoxysilyl) propyl] triethylsilylamine, bis [3- (dimethylethoxysilyl) propyl] triethylsilylamine, bis [3- (trimethoxysilyl) propyl] t-butyldimethylsilylamine Bis [3- (methyldimethoxysilyl) propyl] t-butyldimethylsilylamine, bis [3- (dimethylmethoxysilyl) propyl] t-butyldimethylsilylamine, bis [3- (triethoxysilyl) propyl] t- Butyldimethylsilylamine, bis [3- (methyldiethoxysilyl) propyl] t-butyldimethylsilylamine, bis [3- (dimethylethoxysilyl) propyl] t-butyldimethylsilylamine, bis [3- (trimethoxysilyl) ) Propyl] Torii Propylsilylamine, bis [3- (methyldimethoxysilyl) propyl] triisopropylsilylamine, bis [3- (dimethylmethoxysilyl) propyl] triisopropylsilylamine, bis [3- (triethoxysilyl) propyl] triisopropylsilyl Amine, bis [3- (methyldiethoxysilyl) propyl] triisopropylsilylamine, bis [3- (dimethylethoxysilyl) propyl] triisopropylsilylamine, bis [3- (trimethoxysilyl) butyl] trimethylsilylamine, bis [3- (methyldimethoxysilyl) butyl] trimethylsilylamine, bis [3- (dimethylmethoxysilyl) butyl] trimethylsilylamine, bis [3- (triethoxysilyl) butyl] trimethylsilylamine, bis [3- (methyldiethoxysilyl) butyl] trimethylsilylamine, bis [3- (dimethylethoxysilyl) butyl] trimethylsilylamine, bis [3- (trimethoxysilyl) butyl] triethylsilylamine, bis [3- (methyldimethoxy) Silyl) butyl] triethylsilylamine, bis [3- (dimethylmethoxysilyl) butyl] triethylsilylamine, bis [3- (triethoxysilyl) butyl] triethylsilylamine, bis [3- (methyldiethoxysilyl) butyl] Triethylsilylamine, bis [3- (dimethylethoxysilyl) butyl] triethylsilylamine, bis [3- (trimethoxysilyl) butyl] t-butyldimethylsilylamine, bis [3- (methyldimethoxysilyl) butyl] t- Butyldimethyl Rilamine, bis [3- (dimethylmethoxysilyl) butyl] t-butyldimethylsilylamine, bis [3- (triethoxysilyl) butyl] t-butyldimethylsilylamine, bis [3- (methyldiethoxysilyl) butyl] t-butyldimethylsilylamine, bis [3- (dimethylethoxysilyl) butyl] t-butyldimethylsilylamine, bis [3- (trimethoxysilyl) butyl] triisopropylsilylamine, bis [3- (methyldimethoxysilyl) Butyl] triisopropylsilylamine, bis [3- (dimethylmethoxysilyl) butyl] triisopropylsilylamine, bis [3- (triethoxysilyl) butyl] triisopropylsilylamine, bis [3- (methyldiethoxysilyl) butyl ] Triisopropylsil Amines, bis [3- (dimethylethoxysilyl) butyl] triisopropylsilylamine, bis [3- (trimethoxysilyl) -2-methylpropyl] trimethylsilylamine, bis [3- (methyldimethoxysilyl) -2-methylpropyl ] Trimethylsilylamine, bis [3- (dimethylmethoxysilyl) -2-methylpropyl] trimethylsilylamine, bis [3- (triethoxysilyl) -2-methylpropyl] trimethylsilylamine, bis [3- (methyldiethoxysilyl) -2-methylpropyl] trimethylsilylamine, bis [3- (dimethylethoxysilyl) -2-methylpropyl] trimethylsilylamine, bis [3- (trimethoxysilyl) -2-methylpropyl] triethylsilylamine, bis [3- (Methyl dimethyl Toxisilyl) -2-methylpropyl] triethylsilylamine, bis [3- (dimethylmethoxysilyl) -2-methylpropyl] triethylsilylamine, bis [3- (triethoxysilyl) -2-methylpropyl] triethylsilylamine, Bis [3- (methyldiethoxysilyl) -2-methylpropyl] triethylsilylamine, bis [3- (dimethylethoxysilyl) -2-methylpropyl] triethylsilylamine, bis [3- (trimethoxysilyl) -2 -Methylpropyl] t-butyldimethylsilylamine, bis [3- (methyldimethoxysilyl) -2-methylpropyl] t-butyldimethylsilylamine, bis [3- (dimethylmethoxysilyl) -2-methylpropyl] t- Butyldimethylsilylamine, bis [3- (tri Toxisilyl) -2-methylpropyl] t-butyldimethylsilylamine, bis [3- (methyldiethoxysilyl) -2-methylpropyl] t-butyldimethylsilylamine, bis [3- (dimethylethoxysilyl) -2- Methylpropyl] t-butyldimethylsilylamine, bis [3- (trimethoxysilyl) -2-methylpropyl] triisopropylsilylamine, bis [3- (methyldimethoxysilyl) -2-methylpropyl] triisopropylsilylamine, Bis [3- (dimethylmethoxysilyl) -2-methylpropyl] triisopropylsilylamine, bis [3- (triethoxysilyl) -2-methylpropyl] triisopropylsilylamine, bis [3- (methyldiethoxysilyl) -2-methylpropyl] triisopropyl Silyl amine, bis [3- (dimethylethoxy silyl) -2-methylpropyl] triisopropylsilyl amine.

（式中、Ｒ、Ｒ¹、Ｒ²、Ｒ³、Ｒ⁵は上記と同様である。）
で示される化合物と、下記一般式（３）
ＨＳｉ（ＣＨ₃）_n（ＯＲ⁴）_3-n （３）
（式中、Ｒ⁴、ｎは上記と同様である。）
で示されるハイドロジェンシラン化合物とを白金触媒下で反応させる方法が例示される。 A method for producing a bisorganoxysilane compound having an amino group protected by a silyl group represented by the general formula (1) is, for example, the following general formula (2):

(In the formula, R, R ¹ , R ² , R ³ and R ⁵ are the same as above.)
And a compound represented by the following general formula (3)
HSi (CH ₃ ) _n (OR ⁴ ) _3-n (3)
(Wherein R ⁴ and n are the same as above)
The method of making it react with the hydrogen silane compound shown by platinum catalyst under a platinum catalyst is illustrated.

  Specific examples of the compound represented by the general formula (2) include diallyltrimethylsilylamine, diallyltriethylsilylamine, diallyl t-butyldimethylsilylamine, diallyltriisopropylsilylamine, bis (1-butenyl) trimethylsilylamine, Bis (1-butenyl) triethylsilylamine, bis (1-butenyl) t-butyldimethylsilylamine, bis (1-butenyl) triisopropylsilylamine, dimethallyltrimethylsilylamine, dimethallyltriethylsilylamine, dimethallyl t-butyldimethyl Illustrative are silylamine and dimethallyltriisopropylsilylamine. These compounds are known substances and can be prepared by known methods of protecting dialkenylamine with triorganoxysilane.

  Specific examples of the hydrogensilane compound represented by the general formula (3) used in the above reaction include trimethoxysilane, methyldimethoxysilane, dimethylmethoxysilane, triethoxysilane, methyldiethoxysilane, and dimethylethoxysilane. Is exemplified.

  The compounding ratio of the compound represented by the general formula (2) and the hydrogensilane compound represented by the general formula (3) is not particularly limited, but from the viewpoint of reactivity and productivity, the compound represented by the general formula (2). The range of 1 to 4 mol, particularly 1.5 to 2.5 mol of the hydrogen silane compound represented by the general formula (3) is preferable with respect to 1 mol.

  Examples of the platinum catalyst used in the above reaction include chloroplatinic acid, an alcohol solution of chloroplatinic acid, a toluene-1, xylene solution of platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex, tetrakistri. Examples include phenylphosphine platinum, dichlorobistriphenylphosphine platinum, dichlorobisacetonitrile platinum, dichlorobisbenzonitrile platinum, dichlorocyclooctadiene platinum, and the like.

  Although the usage-amount of a platinum catalyst is not specifically limited, 0.000001-0.01 mol with respect to 1 mol of compounds shown by General formula (2) from the point of reactivity and productivity, especially 0.00001-0.001. A molar range is preferred.

  Although the reaction temperature of the above reaction is not particularly limited, it is preferably 0 to 120 ° C, particularly preferably 20 to 100 ° C, and the reaction time is preferably 1 to 20 hours, particularly preferably 1 to 10 hours.

  In addition, although the said reaction advances even without a solvent, a solvent can also be used. Solvents used include hydrocarbon solvents such as pentane, hexane, cyclohexane, heptane, isooctane, benzene, toluene and xylene, ether solvents such as diethyl ether, tetrahydrofuran and dioxane, and ester solvents such as ethyl acetate and butyl acetate. And aprotic polar solvents such as acetonitrile and N, N-dimethylformamide, and chlorinated hydrocarbon solvents such as dichloromethane and chloroform. These solvents may be used alone or in combination of two or more.

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

[Synthesis Example 1] Synthesis of diallyltrimethylsilylamine In a flask equipped with a stirrer, a reflux condenser, a dropping funnel and a thermometer, 48.6 g (0.5 mol) of diallylamine, 55.7 g (10.55 mol) of triethylamine, hexane 250 ml was charged, and 57.0 g (0.52 mol) of trimethylchlorosilane was added dropwise at 20 to 40 ° C. over 2 hours, followed by stirring at that temperature for 2 hours. The formed salt was removed by filtration and the filtrate was distilled. As a fraction having a boiling point of 72 ° C./5 kPa, 67.1 g of diallyltrimethylsilylamine was obtained (yield 79%).

[Example 1] Synthesis of bis [3- (triethoxysilyl) propyl] trimethylsilylamine In a flask equipped with a stirrer, a reflux condenser, a dropping funnel and a thermometer, 33.9 g (0.2 mol) of diallyltrimethylsilylamine, 0.26 g of a toluene solution (platinum content 3% by mass) of platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex was charged and heated to 70 ° C. After the internal temperature was stabilized, 65.7 g (0.4 mol) of triethoxysilane was added dropwise over 4 hours, and the mixture was stirred at that temperature for 3 hours. The reaction solution was distilled to obtain 50.0 g of a fraction having a boiling point of 132 to 133 ° C./0.05 kPa.

The mass spectrum, ¹ H-NMR spectrum (deuterated chloroform solvent) and IR spectrum of the obtained fraction were measured. The results of the mass spectrum are shown below. FIG. 1 shows a chart of ¹ H-NMR spectrum, and FIG. 2 shows a chart of IR spectrum.
Mass spectrum m / z 497,482,306,163,73
From the above results, it was confirmed that the obtained compound was bis [3- (triethoxysilyl) propyl] trimethylsilylamine.

Example 2 Synthesis of bis [3- (methyldiethoxysilyl) propyl] trimethylsilylamine In a flask equipped with a stirrer, reflux, dropping funnel and thermometer, 33.9 g (0.2 mol) of diallyltrimethylsilylamine. Then, 0.26 g of a toluene solution of platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum content 3% by mass) was charged and heated to 70 ° C. After the internal temperature was stabilized, 53.7 g (0.4 mol) of methyldiethoxysilane was added dropwise over 4 hours and stirred at that temperature for 1 hour. The reaction solution was distilled to obtain 58.1 g of a fraction having a boiling point of 117-119 ° C./0.04 kPa.

The mass spectrum, ¹ H-NMR spectrum (deuterated chloroform solvent) and IR spectrum of the obtained fraction were measured. The results of the mass spectrum are shown below. FIG. 3 shows a chart of ¹ H-NMR spectrum, and FIG. 4 shows a chart of IR spectrum.
Mass spectrum m / z 437, 422, 276, 133, 73
From the above results, it was confirmed that the obtained compound was bis [3- (methyldiethoxysilyl) propyl] trimethylsilylamine.

1 is a ¹ H-NMR spectrum of a silane compound obtained in Example 1. 2 is an IR spectrum of the silane compound obtained in Example 1. 2 is a ¹ H-NMR spectrum of a silane compound obtained in Example 2. 3 is an IR spectrum of the silane compound obtained in Example 2.

Claims (3)

The following general formula (1)

(In the formula, R is a linear or branched divalent hydrocarbon group having 1 to 10 carbon atoms, R ¹ , R ² , R ³ , and R ⁴ are monovalent hydrocarbon groups having 1 to 10 carbon atoms, R ⁵ is a hydrogen atom or a methyl group, and n is 0, 1 or 2.)
A bisorganoxysilane compound having an amino group protected with a silyl group represented by The following general formula (2)

(In the formula, R, R ¹ , R ² , R ³ and R ⁵ have the meanings described in claim 1).
And a compound represented by the following general formula (3)
HSi (CH ₃ ) _n (OR ⁴ ) _3-n (3)
(Wherein R ⁴ and n have the meanings described in claim 1).
The method for producing a bisorganoxysilane compound having an amino group protected by a silyl group according to claim 1, wherein the hydrogensilane compound is reacted with a hydrogensilane compound represented by formula (1) in the presence of a platinum catalyst. Using 1 to 4 mol of the compound represented by the general formula (3) and 0.000001 to 0.01 mol of the platinum catalyst with respect to 1 mol of the compound represented by the general formula (2), the reaction temperature is 20 to 100 ° C. The manufacturing method of Claim 2 made to react in time 1 to 20 hours.

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