JP3008822B2 - (Poly) stannosiloxane and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a base for a curable resin such as a coupling agent, a plasticizer, an antistatic agent, a primer, a coating agent, a sealing agent, an adhesive, an adhesive, a curing catalyst for a silicone resin or an organic resin. The present invention relates to a (poly) stannosiloxane which is useful as a precursor of a sintered body such as ceramics and glass, and a method for producing the same.

[0002]

2. Description of the Related Art
Examples of stanosiloxane include co-hydrolysis of tin chloride and chlorosilane, reaction of alkyl metal silanolate with tin chloride, reaction of distanoxane with silanol (Th
e Chemistry of organotin
Compounds, R.A. C. Poller, Logo
s Press Ltd. , 1970), a dealcoholation reaction between a tin alkoxide and a silanol [Y. Abe, et a
l. Bull. Chem. Soc. Jpn. , 45 ,
1258 (1972)]
Are known.

[0003] However, Sn-OS by these methods is used.
For the formation of the i-bond, condensable silanol or hydrolysis
It is necessary to use unstable raw materials such as chlorosilane
there were. R ’_ThreeSiOSnR ''_Three ... (5) (R 'and R "are an alkyl group or an aryl group)

[0004]

Embedded image (R ′ is a tert-butyl group, R ′ ″ is a tri-ter
t-butoxysilyl group)

On the other hand, a dehydrochlorination reaction between tin chloride and silicic acid [A. Kasgoz, et al. , J. et al. Cerami
c Soc. Jpn. , 100 , 763 (1992)]
The following formula (7) obtained by the following is also known.

[0006]

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However, this method has the drawback that the physical properties of the product, the molecular weight distribution and the Sn / Si molar ratio vary depending on the reaction conditions such as the type of solvent, reaction temperature and reaction time. In addition, the polystannosiloxane obtained by this method exists stably only in the solvent, and when the solvent is removed, it becomes a gel and becomes a solid insoluble in the solvent. Could not.

[0008] The present invention has been made in view of the above circumstances,
An object of the present invention is to provide a novel (poly) stannosiloxane effectively used for various uses and a method for producing the same.

[0009]

The present inventors have made intensive studies to achieve the above object, and as a result, have found that a tin compound represented by the following formula (3) and a cyclo compound represented by the following formula (4) are obtained. A novel stanosiloxane represented by the following formula (1) can be produced by reacting with trisiloxane, and a polystyrene represented by the following formula (2) can be produced by hydrolyzing and condensing the stanosiloxane. It has been found that tanosiloxane can be obtained.

[0010]

Embedded image (Wherein, R ¹ and R ² are the same or different and have 1 to 1 carbon atoms)
20 unsubstituted or cyano group or halogen atom substituted 1
A monovalent hydrocarbon group, R ³ is a hydrogen atom or a group similar to R ¹ , R is the same or different and is an unsubstituted or cyano group, an alkoxy group or a halogen atom-substituted monovalent hydrocarbon group having 1 to 10 carbon atoms or hydrogen Represents an atom, and a and b are 0 or an integer of 1 or more, but a and b are not simultaneously 0. n is an integer of 2 or more. )

Accordingly, the present invention provides a method for converting a stanosiloxane represented by the above formula (1), a polystanosiloxane represented by the above formula (2), a tin compound represented by the formula (3) and a cyclotrisiloxane represented by the formula (4) Provided are a method for producing a stanosiloxane of the formula (1) to be reacted, and a method for producing a polystanosiloxane of the formula (2) in which the stanosiloxane of the formula (1) is hydrolyzed and polycondensed.

Hereinafter, the present invention will be described in more detail. The (poly) stanosiloxane of the present invention contains S
It has an n-O-Si bond and a trisiloxane unit and is represented by the following formulas (1) and (2).

[0013]

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Here, R ¹ and R ² may be the same or different from each other, and each represents an alkyl group such as a methyl group, an ethyl group, a propyl group or a butyl group, a cycloalkyl group such as a cyclohexyl group, a vinyl group, Alloyl group, alkenyl group such as hexenyl group, aryl group such as phenyl group, tolyl group, or cyanoethyl in which part or all of hydrogen atoms bonded to carbon atoms of these groups are substituted with cyano group, halogen atom, etc. Group, 3-chloropropyl group,
An unsubstituted or substituted monovalent hydrocarbon group having 1 to 20 carbon atoms selected from a 3,3,3-trifluoropropyl group and the like, and preferably an alkyl group having 1 to 10 carbon atoms. Also,
R ³ represents a hydrogen atom or the same group as R ¹ . R is an alkyl group such as a methyl group, an ethyl group, a propyl group or a butyl group, a cycloalkyl group such as a cyclohexyl group, an aryl group such as a phenyl group or a tolyl group, an alkenyl group such as a vinyl group, an allyl group, or a hexenyl group; Or a cyanoethyl group, a 2-methoxyethyl group, a 3-chloropropyl group, in which a part or all of the hydrogen atoms bonded to the carbon atoms of these groups are substituted with a cyano group, an alkoxy group, a halogen atom, or the like. Or an unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms or a hydrogen atom selected from a 3,3-trifluoropropyl group and the like. The two R groups bonded to the Si atom may be the same or different.

Further, although a and b are 0 or an integer of 1 or more, a and b do not become 0 at the same time. Preferably 1
≦ a + b ≦ 33. n is an integer of 2 or more, and the upper limit of n differs depending on the degree of condensation by hydrolysis and polycondensation, which will be described later, and is preferably n ≦ 1000, particularly preferably n ≦ 100.

As the stanosiloxane of the above formula (1), those represented by the following formula can be exemplified. In the formula, Me represents a methyl group, Bu represents a butyl group, and Oc represents an octyl group.

[0017]

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These stanosiloxanes are hydrolyzed and condensed.
Polystannosi of formula (2) obtained by polymerization
Loxane is represented by the following average composition formula
Can be illustrated. HO-[(Bu_TwoSnO)₁− (Me_TwoSiO)₆]_x-H HO-[(Bu_TwoSnO)₁− (Me_TwoSiO)_{twenty four}]_x-H HO-[(Bu_TwoSnO)₁− ((CF_ThreeCH_TwoCH_Two) M
e SiO)₆]_x-H

The stanosiloxane of the formula (1) of the present invention is
The following formula (3) R^Two _TwoSn (OR¹)_Two ... (3) (R¹, R^TwoHas the same meaning as described above. )
An organotin dialkoxide and the following formula (4) (R _TwoSiO)_Three … (4) (R Has the same meaning as described above. )
Can be obtained by reacting
You.

Here, the diorganotin dialkoxide of the formula (3) includes dibutyltin dimethoxide, dioctyltin dimethoxide, dibutyltin dipropoxide and the like. The cyclotrisiloxane of the formula (4) includes Hexamethylcyclotrisiloxane, hexaethylcyclotrisiloxane, hexaphenylcyclotrisiloxane, 1,3,5-triphenyl-1,3,5
-Trimethylcyclotrisiloxane, 1,3,5-trivinyl-1,3,5-trimethylcyclotrisiloxane, 1,3,5-tri (3,3,3-trifluoropropyl) -1,3,5- Trimethylcyclotrisiloxane, 1-phenyl-1,3,3,5,5-pentamethylcyclotrisiloxane, 1,1-diphenyl-3,3
5,5-tetramethylcyclotrisiloxane, 1-
(3,3,3-trifluoropropyl) -1,3,3
5,5-pentamethylcyclotrisiloxane and the like.

In order to produce the stanosiloxane of the formula (1) of the present invention, the reaction between the diorganotin dialkoxide of the formula (3) and the cyclotrisiloxane of the formula (4) may be carried out as follows. .

For example, diorganotin dialkoxide or a mixture of two or more thereof is added to cyclotrisiloxane or a mixture of two or more thereof in an atmosphere of an inert gas such as dry nitrogen or dry argon; Add cyclotrisiloxane to the dialkoxide and add
The reaction is carried out at a temperature of 300 ° C, preferably at room temperature to 150 ° C. At this time, an organic solvent can be used if necessary. Examples of the organic solvent include hydrocarbon solvents such as hexane, octane, toluene, and xylene, alcohols such as isopropanol and butanol, butyl acetate, esters such as ethyl acetate, diethyl ether, and the like.
Ether solvents such as diisopropyl ether, dibutyl ether and dioxane, and ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone can be used.

The charge ratio of diorganotin dialkoxide and cyclotrisiloxane may be arbitrary, and the molar ratio of Sn / Si can be 0.1 / 99.9 to 99.9 / 0.1. A stanosiloxane bond (Sn-O
In order to more effectively eliminate the generation of a component not containing -Si bond), the ratio is preferably set to 1/99 to 25/75.

After completion of the reaction, if necessary, a part or all of the hydrolyzable group at the terminal of the stanosiloxane molecule of the formula (1) obtained is hydrolyzed and polycondensed to obtain the polystano compound of the formula (2). A siloxane can be obtained. For this purpose, water or a mixture of water and an organic solvent is added to the above reaction mixture, and a hydrolysis reaction is performed at a temperature of room temperature to 200 ° C. to obtain a condensation product.

In this way, a product containing the (poly) stannosiloxane is obtained, which is optionally heated and / or
Alternatively, volatile components can be removed under reduced pressure to obtain the (poly) stanosiloxane of the present invention.

The (poly) stannosiloxane of the present invention obtained as described above is effectively used, for example, in the following applications. Curing catalyst for condensation-curable silicone resins Heat-resistant and scratch-resistant coatings, sealing agents, adhesives, adhesives, etc. Additives to silicone resins Higher refractive index of cured film, electrical conductivity, antistatic properties Effective for imparting, increasing film hardness, scratch resistance, etc. Catalyst for curing epoxy monomer / epoxy resin, vinyl ether monomer / oligomer, cyclic ether monomer / oligomer Plasticizer for vinyl chloride resin Precursor for sintered bodies such as ceramics and glass Olefin polymerization Catalyst precursor

[0027]

According to the present invention, when producing the (poly) stannosiloxanes of the above formulas (1) and (2),
A cyclic siloxane that can be easily handled can be used as a raw material, and the molar ratio of Sn / Si is determined by the ratio of diorganotin dialkoxide to cyclotrisiloxane at the time of charging.
Since no hydrolysis, condensation reaction, or catalyst is required for the formation of the Sn—O—Si bond, the physical properties, molecular weight distribution, and Sn / Si molar ratio of the product do not vary depending on the reaction conditions.
There is an advantage that a component not containing a Sn—O—Si bond is hardly generated in one molecule. Further, the (poly) stannosiloxane of the present invention thus obtained is a fluid liquid even when the solvent is removed, and is easily mixed with other components.
Since it has a trisiloxane unit in the molecule, it has good compatibility with other silicone resins, has two alkoxy groups in the molecule, and can use this to form a curable composition. Further, the (poly) stannosiloxane of the present invention can be used alone or as a cured product as a base material. It is also useful as a polymerization / curing catalyst for monomers or resins (epoxides, vinyl ethers, cyclic ether-containing monomers and oligomers) curable by tin-based Lewis acid catalysts. Further, the (poly) stannosiloxane of the present invention has excellent solubility in a silicone resin and exhibits curability.

[0028]

EXAMPLES The present invention will be described below in detail with reference to examples and comparative examples, but the present invention is not limited to the following examples.

Example 1 A 500 mL four-necked flask equipped with a stirrer, a cooler, a thermometer and a dropping funnel was charged with 267 g of hexamethylcyclotrisiloxane and heated to 80 ° C. in a nitrogen atmosphere. 177 g of dibutyltin dimethoxide was added dropwise thereto, and the mixture was heated and stirred at 80 ° C. for 4 hours. After confirming the disappearance of hexamethylcyclotrisiloxane by gas chromatography, 120
Volatile components were distilled off at 4 ° C and 4 mmHg. Product 3 obtained
68 g of a liquid having a viscosity of 325 cp was confirmed to be a stanosiloxane represented by the following average composition formula from a ¹ H-NMR spectrum (FIG. 1) and an IR spectrum (FIG. 2).

[0030]

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Example 2 178 g of hexamethylcyclotrisiloxane was charged into a 300 mL four-necked flask equipped with a stirrer, a cooler, a thermometer and a dropping funnel, and heated to 80 ° C. under a nitrogen atmosphere. 59.6 g of dibutyltin dimethoxide was added dropwise thereto, and the mixture was heated and stirred at 80 ° C. for 4 hours. After confirming the disappearance of hexamethylcyclotrisiloxane by gas chromatography, 12
Volatile components were distilled off at 0 ° C. and 4 mmHg. 214 g of the obtained product was a liquid having a viscosity of 244 cp, and it was confirmed by ¹ H-NMR spectrum (FIG. 3) and IR spectrum (FIG. 4) that it was a stanosiloxane represented by the following average composition formula.

[0032]

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Example 3 Hexamethylcyclotrisiloxane (213 g) was charged into a 1 L four-necked flask equipped with a stirrer, a cooler, a thermometer and a dropping funnel, and heated to 80 ° C. in a nitrogen atmosphere. 35.4 g of dibutyltin dimethoxide was added dropwise thereto, and the mixture was heated and stirred at 80 ° C. for 4 hours.
After confirming the disappearance of hexamethylcyclotrisiloxane by gas chromatography, the mixture was cooled to room temperature. Water / methanol solution (22g / 22g)
Was added and stirred at room temperature for 2 hours. 500 mL of toluene
To remove residual water by azeotropic dehydration.
Volatile components were distilled off at 20 ° C. and 4 mmHg. 220 g of the obtained product was a raw rubber-like semi-solid, and it was confirmed by ¹ H-NMR spectrum (FIG. 5) and IR spectrum (FIG. 6) that it was a polystannosiloxane represented by the following average composition formula. Its polystyrene equivalent number average molecular weight is 420
It was 0.

[0034]

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Example 4 1,3,5-Tri (3,3,3-trifluoropropyl) -1,1 was placed in a 100 mL four-necked flask equipped with a stirrer, a cooler, a thermometer and a dropping funnel. 3,5-trimethylcyclotrisiloxane 6
5.6 g was charged and heated to 80 ° C. in a nitrogen atmosphere. 20.7 g of dibutyltin dimethoxide was added dropwise thereto, and 8
The mixture was heated and stirred at 0 ° C. for 4 hours. After confirming that 1,3,5-tri (3,3,3-trifluoropropyl) -1,3,5-trimethylcyclotrisiloxane had disappeared by gas chromatography, 120 ° C., 4 mmHg
The volatiles were distilled off. The obtained product (78.2 g) was a liquid having a viscosity of 380 cp, and it was confirmed by ¹ H-NMR spectrum (FIG. 7) and IR spectrum (FIG. 8) that it was a stanosiloxane represented by the following average composition formula.

[0036]

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Example 5 1,3,5-Tri (3,3,3-trifluoropropyl) -1,1 was placed in a 100 mL four-necked flask equipped with a stirrer, a cooler, a thermometer and a dropping funnel. 3,5-trimethylcyclotrisiloxane 1
41 g were charged and heated to 80 ° C. under a nitrogen atmosphere. Here, 44.3 g of dibutyltin dimethoxide was added dropwise,
The mixture was heated and stirred at 4 ° C. for 4 hours. After confirming that 1,3,5-tri (3,3,3-trifluoropropyl) -1,3,5-trimethylcyclotrisiloxane had disappeared by gas chromatography, a water / methanol solution (2
7g / 27g) and stirred at room temperature for 2 hours. 12
Volatile components were distilled off at 0 ° C. and 4 mmHg. 176 g of the obtained product was a raw rubber-like semi-solid, and it was confirmed by ¹ H-NMR spectrum (FIG. 9) and IR spectrum (FIG. 10) that it was a polystannosiloxane represented by the following average composition formula.

[0038]

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[Brief description of the drawings]

FIG. 1 is a ¹ H-NMR spectrum of a stanosiloxane of Example 1.

FIG. 2 is an IR spectrum of the stanosiloxane of Example 1.

FIG. 3 is a ¹ H-NMR spectrum of a stanosiloxane of Example 2.

FIG. 4 is an IR spectrum of the stanosiloxane of Example 2.

FIG. 5 shows ¹ H-NM of the polystannosiloxane of Example 3.
It is an R spectrum.

FIG. 6 is an IR spectrum of the polystannosiloxane of Example 3.

FIG. 7 is a ¹ H-NMR spectrum of the stanosiloxane of Example 4.

FIG. 8 is an IR spectrum of the stanosiloxane of Example 4.

FIG. 9 shows ¹ H-NM of the polystannosiloxane of Example 5.
It is an R spectrum.

FIG. 10 is an IR spectrum of the polystannosiloxane of Example 5.

──────────────────────────────────────────────────続 き Continuation of front page (56) References JP-A-8-231728 (JP, A) JP-A-62-223264 (JP, A) JP-B-43-14928 (JP, B1) JP-B-41-41 4970 (JP, B1) US Patent 3,287,285 (US, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C07F 7/22 C07F 7/18 C08G 77/04 C08G 77/22 C08G 79/00 C08G 77/42 CAPLUS (STN) REGISTRY (STN) WPIDS (STN)

Claims (4)

(57) [Claims] 1. A stanosiloxane represented by the following formula (1). Embedded image (Wherein, R ¹ and R ² are the same or different and have 1 to 1 carbon atoms)
20 unsubstituted or cyano group or halogen atom substituted 1
A valent hydrocarbon group and R are the same or different and have 1 to 1 carbon atoms;
0 represents an unsubstituted or cyano group, an alkoxy group or a halogen atom-substituted monovalent hydrocarbon group or a hydrogen atom;
Is 0 or an integer of 1 or more, but a and b are not simultaneously 0. ) 2. A polystannosiloxane represented by the following formula (2). Embedded image (Wherein, R ² , R, a and b have the meanings defined in claim 1. R ³ represents a hydrogen atom or a group similar to R ¹ defined in claim 1, and n is an integer of 2 or more.) Is.) 3. A following formula _{^{(3) R 2 2 Sn (}} OR 1) 2 ... (3) ( wherein, R ¹ and R ^2. Showing the meanings defined in claim 1) and the tin compound represented by the Wherein R is a cyclotrisiloxane represented by the following formula (4): (R ² SiO) ₃ (4) (wherein R has the meaning defined in claim 1). 2. The method for producing a stanosiloxane according to 1. 4. The method according to claim 2, wherein the stanosiloxane of the formula (1) is hydrolyzed and polycondensed.