JP2817360B2 - Silane compounds - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION (A) Object of the Invention [Industrial Application Field] The present invention relates to a novel silane compound useful as a highly functional monomer and a novel silane compound useful as an intermediate thereof. Things.

[Conventional technology]

Conventionally, compounds having an active silyl group at a terminal have been used in a wide range of fields such as sealing agents and coating agents.

However, in recent years, increasingly high performance, high heat resistance, high mechanical strength, high hardness, and the like have been required, and existing silane compounds are not always satisfactory for these various requirements. .

[Problems to be solved by the invention]

The present invention, in view of the state of the prior art described above, high heat resistance,
It is an object of the present invention to provide a novel silane compound as a monomer exhibiting high functions that can be a functional polymer material having high mechanical strength and high hardness.

(B) Configuration of the Invention [Means for Solving the Problems] The present inventors have conducted various studies in order to achieve the object, and as a result, as a novel highly functional monomer, represented by the following general formula [I] And a compound represented by the following general formula [II] useful as an intermediate thereof.

That is, the present invention provides a compound represented by the following general formula [I] Wherein R ₁ is a hydrogen atom or a methyl group, R ₂ is a lower alkoxy group, R ₃ is a lower alkyl group or a hydrogen atom, and X is -S-, -SO _2- , -O-, -CONH-, -CH = C
_{H -, - CH 2 CH 2} - or (R ₄ and R ₅ are a hydrogen atom, a fluorine atom, a methyl group, an ethyl group, a trifluoromethyl group or a trichloromethyl group and may be the same or different from each other), and n is 1, 2 or 3, and m is 0 or 1. However, this excludes the case where R ₂ is a methoxy group, n is 2, and R ₃ is a methyl group. And a compound represented by the following general formula [II].

[Wherein the meanings of R ₁ , R ₃ , X, n and m are the same as those described in claim 1. R ₂ in the general formula [I] is a methoxy group, an ethoxy group,
A lower alkoxy group such as a propoxy group or a butoxy group, R ₃ is a lower alkyl group such as a methyl group, an ethyl group or a propyl group, or a hydrogen atom, and as the compound of the present invention represented by the general formula (I), For example, there are the following.

That is, di [4- (3-trimethoxysilylpropyloxy) phenyl] sulfide, di [4- (3-dimethoxymethylsilyl-2-methylpropyloxy) phenyl] sulfone, di [4- (3-diethoxyethyl) Silylpropyloxy) phenyl] ether, 4,4'-bis (3-dipropoxymethylsilyl-2-methylpropyloxy) benzanilide, 1,2-bis [4- (3-dimethoxypropylsilylpropyloxy) phenyl] ethylene , 1,2-bis [4- (3-trimethoxysilyl-2)
-Methylpropyloxy) phenyl] ethane, bis [4
-(3-dimethoxymethylsilyl-2-methyl-propyloxy) phenyl] methane, difluoro-bis [4-
(3-dimethoxysilylpropyloxy) phenyl] methane, 1,1-bis [4- (3-tributoxysilyl-2)
-Methylpropyloxy) phenyl] ethane, 2,2-bis [4- (3-trimethoxysilylpropyloxy) phenyl] propane, 2- [4- (3-trimethoxysilylpropyloxy) phenyl] -2'- [4- (3-Triethoxysilylpropyloxy) phenyl] propane, 1,1,1,3,3,3-hexafluoro-2,2-bis [4-
(3-trimethoxysilyl-2-methylpropyloxy) phenyl] propane, 1,1,1,3,3,3-hexachloro-2,2-bis [4- (3-trimethoxysilylpropyloxy) phenyl] Propane, 1,1-bis [4- (3-
Trimethoxysilyl-2-methylpropyloxy) phenyl] propane and 3,3-bis [4- (3-trimethoxysilylpropyloxy) phenyl] pentane.

Examples of the compound of the present invention represented by the general formula [II] include the following.

That is, di [4- (3-trichlorosilylpropyloxy) phenyl] sulfide, di [4- (3-dichloromethylsilyl-2-methylpropyloxy) phenyl] sulfone and di [4- (3-dimethylchlorosilylpropyl) Oxy) phenyl] ether, 4,4'-bis (3-trichlorosilyl-2-methylpropyloxy) benzanilide, 1,2-bis [4- (3-dimethoxypropylsilylpropyloxy) phenyl] ethylene, 1,2 -Bis [4- (3-trichlorosilyl-2-methylpropyloxy) phenyl] ethane, bis [4- (3-dichloromethylsilyl-2-methyl-propyloxy) phenyl]
Methane, difluoro-bis [4- (3-trichlorosilylpropyloxy) phenyl] methane, 1,1-bis [4
-(3-trichlorosilyl-2-methylpropyloxy) phenyl] ethane, 2,2-bis [4- (3-trichlorosilyl-2-methylpropyloxy) phenyl] propane, 2,2-bis [4- ( 3-dichloromethylsilyl-2-methyl-propyloxy) phenyl] propane,
2,2-bis [4- (3-dichloroethylsilylpropyloxy) phenyl] propane, 2- [4- (3-dichloroethylsilylpropyloxy) phenyl] -2'-
[4- (3-dichloromethylsilylpropyloxy) phenyl] propane, 1,1,1,3,3,3-hexafluoro-2,2
-Bis [4- (3-trichlorosilyl-2-methylpropyloxy) phenyl] propane, 1,1,1,3,3,3-hexachloro-2,2-bis [4- (3-trichlorosilylpropyloxy ) Phenyl] propane, 1,1-bis [4-
(3-Dichloromethylsilyl-2-methylpropyloxy) phenyl] propane and 3,3-bis [4- (3-dichloroethylsilylpropyloxy) phenyl] pentane.

Among the compounds represented by the general formula [I] (hereinafter simply referred to as compound [I]), compounds wherein R ₁ is a hydrogen atom are
For example, similarly to the reaction described in JP-A-59-223372, an allyl ether compound [III] such as a reaction represented by the following reaction formula (1) (hereinafter simply referred to as reaction (1)):
It can be easily produced by reacting the compound with the silylating agent [IV] in the presence of chloroplatinic acid hexahydrate.

[Wherein the meanings of R ₂ , R ₃ , X, n and m are the same as those in the general formula [I]. On the other hand, a compound in which R ₁ in the general formula [I] is a methyl group cannot be synthesized by the above reaction (1), and as described below, a compound represented by the general formula [II] (hereinafter simply referred to as a compound [II] ) (Hereinafter, simply referred to as reaction (2) and reaction (3), respectively) represented by reaction formulas (2) and (3).

First, an example of the method for producing the compound [I] in which R ₁ in the general formula [I] is a hydrogen atom will be described in detail.

Dissolve the starting allyl ether compound [III] in an organic solvent such as toluene or benzene and add chloroplatinic acid
In the presence of a radical reaction initiator such as hydrate, azobisisobutyronitrile or benzoyl peroxide, a silylating agent [I
The compound [I] can be easily produced by reacting the compound [V] by dropwise addition. The preferred reaction ratio of the silylating agent [IV] is 2 to 3 mol per 1 mol of the allyl ether compound [III]. The preferred use amount of the radical reaction initiator may be any amount that acts as a catalyst.For example, in the case of chloroplatinic acid hexahydrate, it is 0.05 to 0.2 mmol per 1 mol of the allyl ether compound [III]. do it.

The preferable reaction temperature of the reaction (1) is to prevent coloring.
The temperature is 0 to 110 ° C, more preferably 40 to 60 ° C. Although the reaction (1) is almost completed in about 2 hours, it is desirable to confirm the end of the reaction by gas chromatography, ¹ H-nuclear magnetic resonance spectrum or ¹³ C-nuclear magnetic resonance spectrum.

Preferred examples of the allyl ether compound [III] used in the reaction (1) include 2,2-bis [4- (2-propenyloxy) phenyl] propane, di [4- (2-propenyloxy) phenyl] sulfide, Di [4- (2-propenyloxy) phenyl] sulfone, di [4- (2-
Propenyloxy) phenyl] ether, 4,4'-bis (2-propenyloxy) benzanilide, 1,2-bis [4- (2-propenyloxy) phenyl] ethylene,
1,2-bis [4- (2-propenyloxy) phenyl]
Ethane, bis [4- (2-propenyloxy) phenyl] methane, difluoro-bis [4- (2-propenyloxy) phenyl] methane, 1,1-bis [4- (2-propenyloxy) phenyl] ethane, 1,1,1,3,3,3-hexafluoro-2,2-bis [4- (2-propenyloxy) phenyl] propane, 1,1,1,3,3,3-hexachloro-2,2 -Bis [4- (2-propenyloxy) phenyl] propane, 1,1-bis [4- (2-propenyloxy) phenyl] propane and 3,3-bis [4- (2-propenyloxy) phenyl] pentane Etc.

Preferred examples of the silylating agent [IV] used in the reaction (1) include trimethoxysilane, triethoxysilane, tripropoxysilane, dimethoxymethylsilane, diethoxymethylsilane, dipropoxymethylsilane, dimethylmethoxysilane, dimethylethoxy Examples include silane, trichlorosilane and dichloromethylsilane.

The compound [I] thus obtained can be used as it is as a moisture-curable material without purification, but may be purified by means such as distillation under reduced pressure, if necessary.

Next, an example of the method for producing the compound [I] wherein R ₁ is a methyl group will be described.

By reacting a methallyl ether compound [V] with a silylating agent [VI] in the presence of chloroplatinic acid hexahydrate as shown in the following reactions (2) and (3), the compound [I
Compound I is synthesized by reacting compound II with alcohol VII in the presence of a base.
Can be easily manufactured.

[Wherein the meanings of R ₂ , R ₃ , X, m and n are the same as described above. The method for producing the silane compound [I] in which R ₁ is a methyl group will be described in more detail. The methallyl ether compound [V] as a starting material is dissolved in an organic solvent such as toluene or benzene, and chloroplatinic acid hexahydrate is dissolved. Compound (II) can be easily produced by reacting by adding the silylating agent (VI) dropwise in the presence of a radical reaction initiator such as a product, azobisisobutyronitrile or benzoyl peroxide. . The preferred reaction ratio of the silylating agent [VI] is 2 to 4 mol per 1 mol of the methallyl ether compound [V]. The preferred amount of the radical reaction initiator used is
Any amount that acts as a catalyst may be used. For example, in the case of chloroplatinic acid hexahydrate, the amount may be 0.05 to 0.2 mmol per 1 mol of the methallyl ether compound [V].

The preferred reaction temperature of the reaction (2) is -90 to 110C, more preferably 0 to 60C. Although the reaction (2) is almost completed in about 4 hours, it is desirable to confirm the end of the reaction by gas chromatography, ¹ H-nuclear magnetic resonance spectrum, ¹³ C-nuclear magnetic resonance spectrum or the like.

Preferred examples of the methallyl ether compound [V] used in the reaction (2) include di [4- (2-methyl-2-propenyloxy) phenyl] sulfide and di [4- (2-
Methyl-2-propenyloxy) phenyl] sulfone,
Di [4- (2-methyl-2-propenyloxy) phenyl] ether, 4,4'-bis (2-methyl-2-propenyloxy) benzanilide, 1,2-bis [4- (2-
Methyl-2-propenyloxy) phenyl] ethylene,
2-bis [4- (2-methyl-2-propenyloxy)
Phenyl] ethane, bis [4- (2-methyl-2-propenyloxy) phenyl] methane, difluoro-bis [4- (2-methyl-2-propenyloxy) phenyl] methane, 1,1-bis [4- (2-methyl-2-propenyloxy) phenyl] ethane, 2,2-bis [4-
(2-methyl-2-propenyloxy) phenyl] propane, 1,1,1,3,3,3-hexafluoro-2,2-bis [4-
(2-methyl-2-propenyloxy) phenyl] propane, 1,1,1,3,3,3-hexachloro-2,2-bis [4-
(2-methyl-2-propenyloxy) phenyl] propane, 1,1-bis [4- (2-methyl-2-propenyloxy) phenyl] propane and 3,3-bis [4- (2
-Methyl-2-propenyloxy) phenyl] pentane.

Preferred examples of the silylating agent [VI] used in the reaction (2) include trichlorosilane, dichlorosilane, dichloromethylsilane, dichloroethylsilane, dichloropropylsilane, dimethylchlorosilane, diethylchlorosilane and dipropylchlorosilane.

The compound [II] thus obtained can be used as it is in the next reaction (3) without purification, but may be purified by means such as distillation under reduced pressure, if necessary.

The compound [I] can be easily produced by adding the alcohol [VII] to the compound [II] obtained as described above, further adding a base thereto, and removing a by-produced salt. .

Since the reaction (3) is an exothermic reaction, the reaction temperature is -20.
~ 60 ° C is preferred. Although the reaction (3) is completed in about 4 hours, it is desirable to confirm the termination of the reaction by gas chromatography, ¹ H-nuclear magnetic resonance spectrum or ¹³ C-nuclear magnetic resonance spectrum.

Preferred examples of the alcohol [VII] used in the reaction (3) include methanol, ethanol, n-propanol, iso-propanol, n-butanol, sec-butanol and tert-butanol, and these are used alone or as a mixture. be able to.

The amount of the alcohol [VII] used in the reaction (3) may be equivalent to the chlorine atom of the compound [II], but it is preferable to use an excess amount (1.5 to 5 times equivalent) to accelerate the progress of the reaction.

Preferred examples of the base used in the reaction (3) include an alcohol solution of a solid base such as sodium hydroxide, potassium hydroxide, calcium hydroxide and magnesium hydroxide, and pyridine, triethylamine, trimethylamine, diethylamine and dimethylamine.

In the step of extracting the compound [I] obtained by the reaction (3) with a solvent such as ether, if the base is present in excess, the base is mixed into the solvent together with the compound [I]. In order to obtain the compound (1), the amount of the base used in the reaction (3) is preferably about equivalent to the chlorine atom of the compound [II].

The compound [I] thus obtained can be used as it is as a moisture-curable material without purification other than extraction.
If necessary, purification may be performed by means such as distillation under reduced pressure.

In order to cure the compound [I] of the present invention by a polymerization reaction, the compound [I] is reacted with water to hydrolyze an alkoxy group bonded to Si, followed by dehydration-condensation to polymerize the compound [I]. I just need.

A very small amount of water is required for the curing reaction, and there is sufficient moisture in the air, but water may be added as appropriate.

In order to accelerate the above curing reaction, it is preferable to add a general condensation polymerization accelerator, for example, a compound generally used as a curing catalyst for a sealing agent, for example, a compound such as dibutyltin laurate and a base, for example, triethylamine Alternatively, it is preferable to use pyridine in combination.

The curing reaction proceeds sufficiently at room temperature if the accelerator is used.
It is preferable in that it can further accelerate the curing reaction and volatilize the alcohol generated by the hydrolysis, whereby a cured product having high hardness can be obtained.

The heating temperature may be a temperature not lower than room temperature and not higher than the thermal decomposition temperature of the compound [I]. In general, heating in a temperature range of 40 to 200 ° C. is sufficient.

The heating time may be appropriately adjusted according to the characteristics of the compound [I].

The compound [I] of the present invention can be various useful polymers by itself being moisture-cured alone or by being mixed with various kinds of moisture-curable compounds and cured, and has thermal stability and chemical stability. It can be expected to be applied in various fields as a high-strength and high-hardness polymer material with excellent stability, etc.
Particularly, it is useful as a sealing agent or a coating agent.

(Examples and Comparative Examples)

Hereinafter, the present invention will be described more specifically based on Examples and Comparative Examples.

Example 1 (Synthesis of 2,2-bis [4- (3-trimethoxysilylpropyloxy) phenyl] propane) In a 300 ml three-necked flask equipped with a thermometer, a dropping funnel and a reflux tube, 2,2-bis [4 -(2-propenyloxy) phenyl] propane 30.0 g (0.098 mol), toluene 7
5 ml and 0.005 g of chloroplatinic acid were added and stirring was continued until dissolved. Then 36.8 g (0.300 mol) of trimethoxysilane
And a mixture of 75 ml of toluene was slowly added dropwise.
After completion of the dropwise addition, the reaction was further continued at 55 ° C. for 1 hour. Analysis by ¹ H-NMR spectrum revealed that 2,2-bis [4
The absorption of olefin of-(2-propenyloxy) phenyl] propane had completely disappeared.

After the completion of the reaction, the reaction solution was cooled to room temperature, and toluene and excess trimethoxysilane were concentrated to obtain 2,2.
50.4 g of 2-bis [4- (3-trimethoxysilylpropyloxy) phenyl] propane was obtained (93% yield). The confirmation that the target product was obtained was carried out by a mass spectrum, an infrared absorption spectrum and the like. Was.

(Mass spectrum)

Calculated value m / e = 553 Actual value m / e = 553 [Infrared absorption spectrum] ν = 3060cm ^-1 Aromatic CH stretching ν = 2950cm ^-1 CH stretching ν-2850cm ^-1 CH stretching ^{ν = 1250cm -1 C-O-} C antisymmetric stretch ν = 1185cm ^-1 Si-OCH ₃ of the Si-O stretching ν = 1090cm ^-1 Si-OCH ₃ of the Si-O stretching ν = 1020cm ^-1 C-O- Example 2 (Synthesis of 2,2-bis [4- (3-trichlorosilyl-2-methylpropyloxy) phenyl] propane) A 300 ml three-necked flask equipped with a thermometer, a dropping funnel and a reflux tube was charged with 2. , 2-Bis [4- (2-methyl-2-propenyloxy) phenyl] propane 30.0 g (0.09mo
l), 70 ml of toluene and 0.005 g of chloroplatinic acid were added, and stirring was continued until dissolution. Then 50.0 g of trichlorosilane
(0.37 mol) and a mixture of 70 ml of toluene were slowly added dropwise at 0 ° C., and the reaction was continued at 60 ° C. for 4 hours after the addition was completed. ^When analyzed by ¹ H-NMR spectrum, the olefin absorption of the starting material 2,2-bis [4- (2-methyl-2-propenyloxy) phenyl] propane had completely disappeared.

After completion of the reaction, the reaction solution was cooled to room temperature, and toluene and excess trichlorosilane were concentrated to obtain 2,2.
53.0 g of -bis [4- (1-trichlorosilyl-2-methylpropyloxy) phenyl] propane was obtained (yield 97
%).

Confirmation that the desired product was obtained was confirmed by a mass spectrum and the like.

(Mass spectrum)

Calculated value m / e = 607 Actual value m / e = 607 Example 3 (Synthesis of 2,2-bis [4- (3-trimethoxysilyl-2-methylpropyloxy) phenyl] propane) Thermometer, dropping funnel And a 300 ml three-necked flask equipped with a reflux tube, and the 2,2-bis [4-
(3-trichlorosilyl-2-methylpropyloxy)
Phenyl] propane 15g (0.025mol), methanol 30.4m
1 and kept at 0 ° C. Then 15.2 g of triethylamine
(0.15 mol) was slowly added dropwise, and after completion of the addition, the reaction was further continued at room temperature for 2 hours.

After completion of the reaction, excess methanol was distilled off under reduced pressure, and anhydrous diethyl ether was added to remove triethylamine hydrochloride. After filtration, diethyl ether was distilled off under reduced pressure to give 2,2-bis [4- (3-triethylamine). Methoxysilyl-2-
13.9 g of methylpropyloxy) phenyl] propane was obtained (96% yield).

Confirmation that the target compound was obtained was confirmed by a mass spectrum, an infrared absorption spectrum, and the like.

(Mass spectrum)

Calculated value m / e = 581 Actual value m / e = 581 [Infrared absorption spectrum] ν = 3050 cm ^-1 Aromatic CH stretching ν = 2980 cm ^-1 CH stretching ν-2950 cm ^-1 CH stretching ν = 2850 cm ^-1 CH stretching ^{ν = 1250cm -1 C-O-} C antisymmetric stretch ν = 1182cm ^-1 Si-OCH ₃ of the Si-O stretching ν = 1090cm ^-1 Si-OCH ₃ of the Si-O stretching ν = 1020cm ^-1 C- OC symmetric stretching Example 4 (2,2-bis [4- (3-dichloromethylsilyl-2-
Synthesis of methyl-propyloxy) phenyl] propane) Synthesis was performed in the same manner as in Example 2 except that dichloromethylsilane was used instead of trichlorosilane of Example 2.

Confirmation that the desired product was obtained was confirmed by a mass spectrum and the like.

(Mass spectrum)

Calculated value m / e = 567 measured value m / e = 567 Example 5 (2,2-bis [4- (3-dimethoxymethylsilyl-2)
Synthesis of -methyl-propyloxy) phenyl] propane) In Example 4 instead of 2,2-bis [4- (3-trichlorosilyl-2-methylpropyloxy) phenyl] propane synthesized in Example 2 2,2-bis [4-
(3-Dichloromethylsilyl-2-methyl-propyloxy) phenyl] propane was used in the same manner as in Example 3.

Confirmation that the desired product was obtained was confirmed by a mass spectrum, an infrared absorption spectrum, and the like.

(Mass spectrum)

Calculated value m / e = 549 Measured value m / e = 549 [Infrared absorption spectrum] Comparative Example 1 As a starting material, instead of 2,2-bis [4- (2-propenyloxy) phenyl] propane of Example 1, 2,2-
Compound [I] wherein R ₁ is a methyl group in the above general formula [I] by the same method as in Example 1 except that bis [4- (2-methyl-2-propenyloxy) phenyl] propane is used. However, unlike Example 1, the reaction did not proceed.

REFERENCE EXAMPLE 1 2,2-bis [4- (3-trimethoxysilyl-2-methylpropyloxy) phenyl] propane of Example 3
12.5 parts by weight (hereinafter simply referred to as "part"), MS-20A which is a commercially available oligomer having a molecular weight of 8,000, having no benzene ring in the molecule, having a dimethoxymonomethylsilyl group and a polypropylene oxide skeleton [Kanebuchi Chemical Industry Co., Ltd. 25)
Parts and 0.70 part of dibutyltin laurate were mixed, cured at room temperature for 3 days, and further cured at 50 ° C. for 4 days.

The cured product had a tensile strength of 10.7 kg f / cm ² and a Shore hardness of 60.3. Thermogravimetric analysis (heating rate 20 ° C / min)
As a result, the temperature at which the weight was reduced by 10% in air was 345 ° C.

Comparative Reference Example 1 25 parts of MS-20A and 0.5 part of dibutyltin laurate were mixed, cured at room temperature for 3 days, and further cured at 50 ° C for 4 days.

The cured product had a tensile strength of 3.9 kg f / cm ² and a Shore hardness of 8.5. Thermogravimetric analysis (heating rate 20 ° C / min)
As a result, the temperature at which the weight was reduced by 10% in the air was 250 ° C.

From the above results, it can be seen that the cured product of Reference Example 1 has higher heat resistance, higher mechanical strength, and higher hardness than the cured product of Comparative Example 1.

(C) Effects of the Invention The compound [I] of the present invention provides a resin having high heat resistance, high mechanical strength, and high hardness by curing with moisture, as compared with conventional moisture-curable resins. The compound [II] of the present invention is extremely useful as an intermediate for obtaining a compound in which R ₁ is a methyl group in the general formula [I].

──────────────────────────────────────────────────続 き Continuation of the front page (72) Inventor Kaoru Kimura 1-1, Funami-cho, Minato-ku, Nagoya-shi, Aichi Examiner, Nagoya Research Institute, Toagosei Chemical Industry Co., Ltd. Motohiro Okubo (56) WO, A1) (58) Fields investigated (Int. Cl. ⁶ , DB name) C07F 7/12 C07F 7/18 CA (STN) REGISTRY (STN)

Claims (2)

(57) [Claims] 1. A compound represented by the general formula [I]. Wherein R ₁ is a hydrogen atom or a methyl group, R ₂ is a lower alkoxy group, R ₃ is a lower alkyl group or a hydrogen atom, and X is -S-, -SO _2- , -O-, -CONH-, -CH = C
H-, -CH ₂ CH ₂ - or (R ₄ and R ₅ are a hydrogen atom, a fluorine atom, a methyl group, an ethyl group, a trifluoromethyl group or a trichloromethyl group and may be the same or different from each other), and n
Is 1, 2 or 3, and m is 0 or 1. Where R ₂
Is a methoxy group, n is 2 and R ₃ is a methyl group. ] 2. A compound represented by the general formula [II]. [Wherein the meanings of R ₁ , R ₃ , X, n and m are the same as those described in claim 1. ]