JPH07286045A - Production of polyheterosiloxane - Google Patents

Abstract

PURPOSE:To produce a polyheterosiloxane which has specific units as the essential units and is solvent-sol. by subjecting a specific metal compd. and a solvent- sol. silicate compd. to hydrolysis and condensation in the presence of a carboxylic acid, etc., and adding a specific organosilane to the resulting product to further conduct hydrolysis and condensation. CONSTITUTION:A polyheterosiloxane is produced by subjecting a metal compd. of the formula: MA4 (wherein M is Ti or Zr; and A is halogen, alkoxy, or acyloxy) to partial hydrolysis and condensation in the presence of at least one compd. selected from the group consisting of carboxylic acids, phenols, and diketones and adding a solvent-sol. silicate compd. to the resulting product to further conduct hydrolysis and condensation or by subjecting a solvent-sol. silicate compd. to partial hydrolysis and condensation, then adding a metal compd. of the formula: MA4 to the resulting product to conduct hydrolysis and condensation, and adding an organosilane of the formula: R<1>3SiX (wherein R<1> is H, alkyl, alkenyl, aryl, etc.; and X is OH, alkoxy, etc.) to further conduct hydrolysis and condensation.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a solvent-soluble polyheterosiloxane containing MO ₂ (M represents a titanium atom or zirconium atom) unit and a SiO ₂ unit as essential components. More specifically, it relates to a method for producing polyheterosiloxane useful as an additive for improving the properties of polysiloxane.

[0002]

_2. Description of the Related Art Polysiloxanes containing SiO ₂ units as constituents include trimethylsilyl units and SiO ₂ units.
So-called MQ resin composed of units has been known for a long time. This polysiloxane is soluble in an ordinary organic solvent, and as a typical production method thereof, 1) a method of neutralizing a water-soluble silicate such as water glass and then adding an excess of trimethylchlorosilane (for example, US Pat. 2676182 and 2814601), 2) A method of co-hydrolyzing tetraalkoxysilane and trimethylchlorosilane in the presence of an acidic catalyst (for example, JP-A-61-195129) is known.

On the other hand, a polyheterosiloxane containing a metal atom other than silicon has the atom incorporated into a siloxane unit through a covalent bond, and its physical and chemical properties are greatly different from those of a normal polysiloxane. Has been extensively studied. As a typical production method thereof, a mixture of alkoxysilanes and M (OR) _n (M is a metal atom other than silicon, R is an alkyl group, and 2 ≦ n ≦ 6) is hydrolyzed in an organic solvent. The so-called sol-gel method in which the solvent is removed after condensation is well known. By this method, polyheterosiloxane containing various kinds of metal atoms (for example, titanium, zirconium, aluminum, tin, vanadium, niobium, etc.) can be prepared, but cracks are generated during solvent removal. , Phase separation often occurs, and handling is complicated. Furthermore, since the product after solvent removal is no longer soluble in organic solvents, the resulting polyheterosiloxane has limited processing methods, and is mainly used for coating. On the other hand, Japanese Patent Application Laid-Open No. 5-78489 by Abe et al. Describes the synthesis of polyzirconosiloxane. However, bis (2,4-pentanedionate) zirconium diisopropoxide and bis (2,2,2) are used as starting materials. It is a reaction that uses a special starting material such as 4-hexanedionato) zirconium diisopropoxide. So far, MO ₂
No method has been reported for easily producing a polyheterosiloxane soluble in an organic solvent, which contains units (M represents a titanium atom or a zirconium atom) and SiO ₂ units as essential components.

[0004]

DISCLOSURE OF THE INVENTION Problems to be Solved by the Invention
Another object of the present invention is to provide a method for producing a polyheterosiloxane soluble in an organic solvent, which contains ₂ (M represents a titanium atom or zirconium atom) unit and a SiO ₂ unit as essential components.

[0005]

The present inventors have arrived at the present invention as a result of intensive studies to solve the above problems. That is, the present invention, in the presence of one or more compounds selected from carboxylic acids, phenols and diketones,
A method for producing a polyheterosiloxane, which comprises advancing the reaction of the following a) or b) and further adding an organic silane represented by the following formula (2) for hydrolysis and condensation. a) A reaction in which a metal compound represented by the following formula (1) is partially hydrolyzed and condensed, and then solvent-soluble silicates are added to further promote hydrolysis and condensation. b) A reaction in which the solvent-soluble silicates are partially hydrolyzed and condensed, and then a metal compound represented by the following formula (1) is added to promote hydrolysis and condensation together.

(1) MA ₄ (in the formula, M represents a titanium atom or a zirconium atom, A represents a halogen group, an alkoxy group or an acyloxy group) (2) R ¹ ₃ SiX (in the formula, R ¹ is respectively Independently hydrogen atom, alkyl group,
A substituted alkyl group, an alkenyl group, an aryl group or a substituted aryl group, and X represents a hydroxy group, an alkoxy group, an acyloxy group, or an acylamido group)

The metal compound represented by MA ₄ used in the present invention is a precursor for forming MO ₂ (M represents a titanium atom or a zirconium atom) unit, and is a halide, alkoxide or acyloxide of titanium or zirconium metal. Is. Specific examples thereof include titanium tetrachloride, tetraethoxy titanium, tetrapropoxy titanium, tetraisopropoxy titanium, tetrabutoxy titanium, tetraacetoxy titanium, zirconium tetrachloride, tetraethoxy zirconium, tetrapropoxy zirconium, tetraisopoxy zirconium, tetrabutoxy. Examples include zirconium. When A is a carbon-containing group, it preferably has 4 or less carbon atoms.

The solvent-soluble silicates used in the reaction a) or the reaction b) in the method for producing a polyheterosiloxane of the present invention means Si (OR) ₄
(R represents an alkyl group, a substituted alkyl group, an alkenyl group, an aryl group, a substituted aryl group, an acyl group or a metal atom. When R is a carbon atom-containing group, the number of carbon atoms is preferably 6 or less. Recommended)), a partial hydrolyzate of Si (OR) ₄ and a silicate obtained by neutralizing a water-soluble silicate. The solvent-soluble silicates used in the reaction a) or the reaction b) in the method for producing a polyheterosiloxane of the present invention are preferably Si (OR) ₄ or a partial hydrolyzate of Si (OR) _4. used. The Si
Specific examples of (OR) ₄ include tetramethoxysilane,
Examples thereof include tetraethoxysilane, tetra-n-propoxysilane, tetra-n-butoxysilane, tetrakis (2-methoxyethoxy) silane, tetraallyloxysilane, tetraphenoxysilane, silicon tetraacetate and sodium orthosilicate. The Si
Examples of the partial hydrolyzate of (OR) ₄ include these partial hydrolysates. Considering the economical efficiency and availability of the compound, tetramethoxysilane and tetraethoxysilane are preferable.

The point of the present invention is that the hydrolysis and condensation of the metal compound represented by MA ₄ are carried out in the presence of one or more compounds selected from carboxylic acids, phenols and diketones. . The presence of these compounds can control the hydrolysis / condensation of the metal compound MA ₄ to produce the desired polyheterosiloxane. Examples of the carboxylic acids used here include acetic acid, propionic acid, n-butyric acid, acrylic acid, methacrylic acid, benzoic acid, 2-methylbenzoic acid, 4-methylbenzoic acid, phthalic acid and terephthalic acid. Acetic acid, propionic acid, acrylic acid, methacrylic acid, and benzoic acid are preferably used because they are easily available. Examples of phenols include phenol, chlorophenols and cresols. Further, examples of the diketones include acetylacetone, dipivaloylmethane, benzoylacetone and the like, and acetylacetone and its derivatives are preferable from the viewpoint of easy availability and low cost. The amount of these compounds used varies depending on the type of compound used,
It is preferably 10 mol% or more and 400 mol% or less with respect to the metal compound represented by MA ₄ . If it is less than 10 mol%, the hydrolysis / condensation of MA ₄ cannot be sufficiently controlled. 40
If the amount exceeds 0 mol%, these compounds are simply wasted.

On the other hand, the amount of water used during the hydrolysis / condensation is the minimum amount required for hydrolyzing / condensing all the hydrolyzable groups of the metal compound MA ₄ and the compound forming the SiO ₂ unit. 80, for stoichiometry
It is preferably from mol% to 150 mol%. If the amount of water used is out of this range, hydrolysis / condensation is insufficient, or insoluble polymers are produced, which is not preferable. It is recommended that this hydrolysis / condensation reaction be carried out in the presence of a suitable organic solvent. The organic solvent used here is not particularly limited as long as it dissolves the metal compound MA ₄ , but a water-soluble organic solvent such as tetrahydrofuran, 1,4-dioxane or dimethylformamide is preferable. In the method for producing a polyheterosiloxane of the present invention as described above, the solvent-soluble silicates used in the reaction a) or the reaction b) are Si (OR) ₄ and Si (OR) ₄ . One or more kinds selected from the partial hydrolyzate of _{4 and} the silicates obtained by neutralizing the water-soluble silicate are used. Among them, particularly in the reaction of b), Si (O 2
When the partial hydrolyzate of R) ₄ is used, it does not necessarily need to undergo further hydrolysis / condensation because it has a structure in which the partial hydrolysis of Si (OR) ₄ has already progressed. The same applies to the case of using silicates obtained by neutralizing the organic silicate.

Further, in the method for producing a polyheterosiloxane of the present invention, after MO ₂ (M represents a titanium atom or zirconium atom) unit and a SiO ₂ unit are formed, R ¹ ₃ SiX (in the formula, R ¹ Each independently represent a hydrogen atom, an alkyl group, a substituted alkyl group, an alkenyl group, an aryl group or a substituted aryl group, X represents a hydroxy group, an alkoxy group, an acyloxy group or an acylamide group, and m is 0 or 1. .) Is added and hydrolyzed and condensed to form a solvent-soluble polyheterosiloxane. When the substituent R ¹ is a carbon atom-containing group, the number of carbon atoms is preferably 6 or less. Specific examples of the substituent R ¹ include a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an n-hexyl group, a chloromethyl group, a vinyl group and a phenyl group, but a hydrogen atom, a methyl group, A vinyl group and a phenyl group are preferable from the economical viewpoint. When the substituent X is a carbon atom-containing group, the number of carbon atoms is preferably 3 or less. Specific examples of the substituent X are preferably a hydroxy group, a methoxy group, an ethoxy group, an acetoxy group and an acetamide group.

Specific organic silanes include trimethylhydroxysilane, trimethylmethoxysilane, trimethylethoxysilane, trimethylsilylacetate, trimethylsilylacetamide, dimethylhydroxysilane, dimethylethoxysilane, dimethylsilylacetate, dimethylsilylacetamide, vinyldimethylhydroxysilane, Vinyldimethylmethoxysilane, vinyldimethylethoxysilane, vinyldimethylsilylacetate, vinyldimethylsilylacetamide, phenyldimethylhydroxysilane, phenyldimethylethoxysilane, phenyldimethylacetoxysilane, diphenylmethylhydroxysilane, diphenylmethylethoxysilane, diphenylvinylhydroxysilane, Diphenyl vinyl ethoxy Such as emissions, and the like. The addition amount of these silanes is not particularly limited, but the metal compound M
The amount used of A ₄ is preferably 10 mol% or more.

The finally produced polyheterosiloxane
There are no particular restrictions on the composition of the ₂ Unit (M) and Si
O₂ The ratio of the unit (Si) is 0.01 ≦ mol fraction.
The range of (M) / (Si) ≦ 100 is preferable.

In the production of the polyheterosiloxane of the present invention, the MO ₂ unit and the SiO ₂ unit can be formed simultaneously, or can be formed stepwise. In order to stabilize the quality of the obtained polyheterosiloxane, it is more preferable to form it in stages.
As an example, a metal compound represented by MA ₄ is hydrolyzed and condensed with a predetermined amount of water in the presence of one or more compounds selected from carboxylic acids, phenols and diketones, and then tetraalkoxysilane. the hydrolysis and condensation is added, then added an organic silane represented by R ¹ ₃ SiX, and a method of hydrolysis and condensation. The reaction temperature in this manufacturing process is -80 ° C or higher and 100 ° C.
The following is preferable, and -80 ° C or more and 50 ° C or less is more preferable.

[0015]

EXAMPLES In order to describe the present invention more specifically, examples will be described below, but these examples do not limit the present invention.

(Example 1) 2.5 g (7.65 mmol) of zirconium tetrapropoxide and 1.8 g of acetic acid were dissolved in 10 ml of tetrahydrofuran and ice-cooled in a cooling bath. A mixture of water (275 mg, 15.3 mmol) and tetrahydrofuran (5 ml) was slowly added dropwise to this solution. After stirring the reaction solution for 10 minutes, tetramethoxysilane (2.3 g, 15.1 mmol) was added, and then a solution of water (550 mg, 30.6 mmol) in tetrahydrofuran (5 ml) was slowly added dropwise. After removing the cooling bath, the mixture was stirred at room temperature for 1 hour, 4.3 g of trimethylsilyl acetate was added, and the mixture was further stirred for 2 hours. The reaction solvent and unreacted trimethylsilylacetate were removed to obtain a pale yellow solid (3.10 g).

IR: 1100 cm ^-1 (Si-O-Si),
918 cm ^-1 (Zr-O-Si). ¹ H NMR (CDCl ₃ solvent, CHCl ₃ standard, δ =
7.24ppm): 0.11 (Si-CH 3), 2.10
_{(CO-CH 3), 1.50~2.50} (OC 3 H
₇ ). ²⁹ Si NMR (CD ₃ COCD ₃ solvent, TMS standard,
δ = 0 ppm): 8.6 (Si-CH ₃ ), -92 to -11
3 (SiO ₂ , SiOCH ₃ ).

Example 2 A pale yellow solid was obtained in the same manner as in Example 1 except that 0.67 g of methacrylic acid was used in place of 1.8 g of acetic acid to obtain a pale yellow solid (3.20 g).

IR: 1100 cm ^-1 (Si-O-Si),
920 cm ^-1 (Zr-O-Si). ¹ H NMR (CDCl ₃ solvent, CHCl ₃ standard, δ =
7.24ppm): 0.11 (Si-CH 3), 1.50-
_{2.50 (OC 3 H 7),} 5.20-6.40 (CH 2
= C (CH _3)). ²⁹ Si NMR (CD ₃ COCD ₃ solvent, TMS standard,
δ = 0 ppm): 8.7 (Si-CH ₃ ), -90 to -11
3 (SiO ₂ , SiOCH ₃ ).

(Example 3) 1.3 g of zirconium tetrapropoxide and 0.4 g of acetylacetone were dissolved in 8 ml of tetrahydrofuran and ice-cooled in a cooling bath. A mixture of water (139 mg) and tetrahydrofuran (5 ml) was slowly added dropwise to this solution. The reaction solution was stirred for 10 minutes, tetramethoxysilane (2.3 g) was added, and then a solution of water (550 mg) and acetic acid (470 mg) in tetrahydrofuran (4 ml) was slowly added dropwise. After removing the cooling bath, the mixture was stirred at room temperature for 4 hours, 4.3 g of trimethylsilyl acetate was added, and the mixture was further stirred for 14 hours. Removal of the reaction solvent and unreacted trimethylsilylacetate gave a pale yellow solid (1.51 g).

IR: 1100 cm ^-1 (Si-O-Si),
922 cm ^-1 (Zr-O-Si). ¹ H NMR (CD ₃ COCD ₃ solvent, TMS standard, δ
= 0ppm): 0.13 (Si- CH 3), 2.10 (CO
-CH _3, a trace amount), 1.50-2.20 (OC ₃ H
₇ ). ²⁹ Si NMR (CD ₃ COCD ₃ solvent, TMS standard,
δ = 0 ppm): 8.1 (Si-CH ₃ ), -90 to -11
5 (SiO ₂ , SiOCH ₃ ).

(Example 4) Titanium tetrabutoxide 3.
8 g of acetic acid and 0.67 g of acetic acid were dissolved in 8 ml of tetrahydrofuran and ice-cooled in a cooling bath. Water (390 mg) in this solution
A mixture of and tetrahydrofuran (5 ml) was slowly added dropwise. The reaction solution was stirred for 30 minutes, tetramethoxysilane (1.81 g) was added, and then a solution of water (430 mg) in tetrahydrofuran (4 ml) was slowly added dropwise.
After removing the cooling bath, the mixture was stirred at room temperature for 4 hours, 3.4 g of trimethylsilyl acetate was added, and the mixture was further stirred for 15 hours. A yellow liquid was obtained by removing the reaction solvent and unreacted trimethylsilylacetate (2.78).
g).

IR: 1100 cm ^-1 (Si-O-Si),
925 cm ^-1 (Ti-O-Si). ¹ H NMR (CD ₃ COCD ₃ solvent, TMS standard, δ
= 0ppm): 0.20 (Si- CH 3), 0.90 (CH
_{3), 1.10-2.20 (OC 3 H} 6, CO-CH
_{3), 3.70 (OCH 3)} . ²⁹ Si NMR (CD ₃ COCD ₃ solvent, TMS standard,
δ = 0 ppm): 11.1 (Si-CH ₃ ), -95 to -1
15 (SiO ₂ , SiOCH ₃ ).

(Example 5) Titanium tetrabutoxide 2.
3 g and 0.40 g of acetic acid were dissolved in 5 ml of tetrahydrofuran and ice-cooled in a cooling bath. Water (240 mg) in this solution
A mixture of and tetrahydrofuran (5 ml) was slowly added dropwise. The reaction solution was stirred for 30 minutes, tetramethoxysilane (1.1 g) was added, and then a solution of water (270 mg) in tetrahydrofuran (4 ml) was slowly added dropwise. After removing the cooling bath, the mixture was stirred at room temperature for 4 hours, an ether solution of 2.0 g of trimethylhydroxysilane was added, and the mixture was further stirred for 15 hours. Removal of the reaction solvent and unreacted trimethylhydroxysilane gave a yellow liquid (1.67 g).

IR: 1100 cm ^-1 (Si-O-Si),
922 cm- ¹ (Ti-O-Si). ¹ H NMR (CD ₃ COCD ₃ solvent, TMS standard, δ
= 0ppm): 0.20 (Si- CH 3), 0.92 (CH
_{3), 1.10-2.30 (OC 3 H} 6, CO-CH
_{3), 3.70 (OCH 3)} . ²⁹ Si NMR (CD ₃ COCD ₃ solvent, TMS standard,
δ = 0 ppm): 11.3 (Si-CH ₃ ), -95 to -1
15 (SiO ₂ , SiOCH ₃ ).

Example 6 Zirconium tetrapropoxide (2.5 g, 7.65 mmol) and 1.8 g of acetic acid were dissolved in 10 ml of tetrahydrofuran and cooled with ice. A mixture of water (275 mg, 15.3 mmol) and tetrahydrofuran (5 ml) was slowly added dropwise to this solution. After stirring the reaction solution for 10 minutes, silicate 40 (manufactured by Tama Chemical Industry Co., Ltd., polysilicic acid ester mixture, SiO ₂ content of about 4)
0%) (5 g, 33 mmol as SiO ₂ ), water (9
A solution of (00 mg) in tetrahydrofuran (10 ml) was slowly added dropwise. After removing the cooling bath, the mixture was stirred at room temperature for 1 hour, 4.3 g of trimethylsilyl acetate was added, and the mixture was further stirred for 2 hours. Removal of the reaction solvent and unreacted trimethylsilyl acetate gave a pale yellow solid (4.15 g).

IR: 1100 cm ^-1 (Si-O-Si),
919 cm ^-1 (Zr-O-Si). ¹ H NMR (CDCl ₃ solvent, CHCl ₃ standard, δ =
7.24ppm): 0.11 (Si-CH 3), 2.10
_{(CO-CH 3), 1.50-2.50} (OC
₃ H ₇ ). ²⁹ Si NMR (CD ₃ COCD ₃ solvent, TMS standard,
δ = 0 ppm): 8.6 (Si-CH ₃ ), -91 to -11
3 (SiO ₂ , SiOCH ₃ ).

Example 7 Silicate 40 (5 g, Si
33 mmol of O ₂ ) in tetrahydrofuran (10
ml) solution of water (900 mg) in tetrahydrofuran (5 m
l) The solution was added and stirred at room temperature for 1 hour. The reaction solution was ice-cooled, and a separately prepared solution of zirconium tetrapropoxide (2.5 g, 7.65 mmol) and 1.8 g of acetic acid in tetrahydrofuran (10 ml) was slowly added. A mixture of water (275 mg, 15.3 mmol) and tetrahydrofuran (5 ml) was slowly added dropwise to this solution. After the reaction solution was stirred for 30 minutes, the cooling bath was removed, the mixture was stirred at room temperature for 1 hour, 4.3 g of trimethylsilylacetate was added, and the mixture was further stirred for 2 hours. Removal of the reaction solvent and unreacted trimethylsilyl acetate gave a pale yellow solid (4.15 g).

IR: 1100 cm ^-1 (Si-O-Si),
919 cm ^-1 (Zr-O-Si). ¹ H NMR (CDCl ₃ solvent, CHCl ₃ standard, δ =
7.24ppm): 0.11 (Si-CH 3), 2.10
_{(CO-CH 3), 1.60-2.60} (OC
₃ H ₇ ). ²⁹ Si NMR (CD ₃ COCD ₃ solvent, TMS standard,
δ = 0 ppm): 8.6 (Si-CH ₃ ), -91 to -11
3 (SiO ₂ , SiOCH ₃ ).

Comparative Example 1 When a reaction was carried out in the same manner as in Example 1 except that 1.8 g of acetic acid was not used, a white precipitate was formed during the dropwise addition of the mixture of water and tetrahydrofuran. This precipitate was insoluble in organic solvents.

[0031]

INDUSTRIAL APPLICABILITY As described above, the method for producing polyheterosiloxane disclosed in the present invention is simple and gives a product soluble in a solvent, so that the degree of freedom of the processing method can be increased. it can. Furthermore, since the polyheterosiloxane of the present invention contains TiO ₂ or SiO ₂ units in the molecule, it is also useful as an additive for improving the properties of the polysiloxane, such as heat resistance.

Claims (2)

[Claims] 1. The following a) in the presence of one or more compounds selected from carboxylic acids, phenols and diketones:
Alternatively, a method for producing a polyheterosiloxane, which comprises advancing the reaction of b) and further adding an organic silane represented by the following formula (2) for hydrolysis and condensation. a) A reaction in which a metal compound represented by the following formula (1) is partially hydrolyzed and condensed, and then solvent-soluble silicates are added to further promote hydrolysis and condensation. b) A reaction in which the solvent-soluble silicates are partially hydrolyzed and condensed, and then a metal compound represented by the following formula (1) is added to promote hydrolysis and condensation together. (1) MA ₄ (In the formula, M represents a titanium atom or a zirconium atom,
A is a halogen group, an alkoxy group or acyloxy _{^{group) (2) R 1 3 SiX}} ( wherein, R ¹ is each independently a hydrogen atom, an alkyl group,
A substituted alkyl group, an alkenyl group, an aryl group or a substituted aryl group, and X represents a hydroxy group, an alkoxy group, an acyloxy group, or an acylamido group) 2. The solvent-soluble silicates are Si (O 2).
R) ₄ (R represents an alkyl group, a substituted alkyl group, an alkenyl group, an aryl group, a substituted aryl group, an acyl group or a metal atom), a partial hydrolyzate of the Si (OR) ₄ and a water-soluble silicate The method for producing a polyheterosiloxane according to claim 1, wherein the polyheterosiloxane is one or more selected from silicates obtained by neutralizing.