JP2002348378A - Novel polyorganosilsesquioxane and process for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To produce a polyorganosilsesquioxane that is excellent in heat resistance, combustion resistance and flexibility; that has a small molecular weight distribution and is capable of controlling the molecular weight and making the molecular weight higher; and that will not form a three-dimensional network structure due to a structural defect and a random structure of an oligomer during condensation polymerization and therefore is soluble in a general organic solvent. SOLUTION: The polyorganosilsesquioxane has the formula (wherein R1 and R2 each independently denote a hydrogen atom, a 1-30C alkyl group, a 5-30C substituted or unsubstituted aromatic group, a 1-30C substituted or unsubstituted aryl group, a 3-30C substituted or unsubstituted cyclic compound residue, a 1-30C substituted or unsubstituted acyl group, a vinyl group, an amine residue or an acetic residue and n denotes either 1 or an integer of more than 1).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a highly ordered polyorganosilsesquioxane having excellent heat resistance, flame resistance and flexibility, wherein the same or different types of substituents are alternately bonded. And a method of manufacturing the same.

[0002]

2. Description of the Related Art Conventional polyorganosilsesquioxanes are obtained by hydrolyzing trichlorosilane or triethoxysilane in the presence of an alkali catalyst to obtain high molecular weight oligomers such as N-methylpyrrolidone, dimethylsulfoxide and methyl. It is obtained by heating polycondensation in a high viscosity solvent such as isopropenyl ketone [Bro
wn et al., J. Am. Chem. Soc., 82, 6194 (1960)].
However, in the above-described production method, the condensation reaction proceeds simultaneously with the hydrolysis, so that not the precursor (silanetriol), but an oligomer (Mn = 1000 to 3000, Mw / Mn> 2) tends to be generated. Polymers polymerized under the alkali catalyst using oligomers have the following disadvantages. 1) Generally, the molecular weight distribution is large, and it is difficult to control the molecular weight and increase the molecular weight (Mn = 20,000 to 30,000 or less). 2) It is insoluble in organic solvents because it is easy to form a three-dimensional network due to structural defects and random structure of the oligomer that is a hydrolyzate. Further, a method of synthesizing a silicone ladder polymer from phenylsilanetriol
[LJ Tyler et al., J. Am. Chem. Soc., 77, 770 (1
955), T. Takiguchi et al., J. Am. Chem. Soc., 81, 2
359 (1959), EC Lee et al., Polymer Journal, 29
(8), 678 (1997)] has a number average molecular weight (Mn) of 1,000.
~ 1,000,000, a highly ordered polymer having a molecular weight distribution (Mw / Mn) of 2 or less can be obtained, but the production process is complicated to obtain silanetriol with high purity, and it is difficult to handle phenylsilanetriol at room temperature. In addition, there is a problem that the yield is extremely low (10 to 20% or less), which is uneconomical.

[0003]

SUMMARY OF THE INVENTION In order to solve such problems, the present inventors have made it easy to handle and easily introduce R and R'-SiO _3/2 into the main chain of a polymer. A new molecular model was designed and the polymerization method was examined.

[0004]

The structure of the present invention is as follows. (1) The polyorganosilsesquioxane of the present invention is represented by the following general formula.

Embedded image (Wherein R ₁ and R ₂ are a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted aromatic group having 5 to 30 carbon atoms, a substituted or unsubstituted allyl group having 1 to 30 carbon atoms, A substituted or unsubstituted cyclic compound residue having 3 to 30 carbon atoms, a substituted or unsubstituted acyl group having 1 to 30 carbon atoms, a vinyl group, an amine residue, or an acetic acid residue is independently shown, and n is 1 and Any of the above integers is shown.) (2) As the alkyl group, a methyl group, an ethyl group,
A propyl group and the like can be exemplified, and the aromatic group is preferably a phenyl group, a halogenated phenyl group or the like. (3) The method for producing the polyorganosilsesquioxane of the present invention is produced from 1,3-organodisiloxane represented by the following general formula.

Embedded image (Wherein X is a hydrogen atom, a chlorine atom, a hydroxyl group,
Represents an amino group or a carboxy group; R is a hydrogen atom,
Alkyl group, acetic acid residue, sodium or potassium metal. (4) The condensation reaction is carried out in the absence of a catalyst or in the presence of at least one catalyst selected from the group consisting of an alkali metal hydroxide, an amine, a quaternary ammonium salt, and a fluoride. It is characterized in that it is performed below. (5) Examples of the alkali metal hydroxide include sodium hydroxide, potassium hydroxide and cesium hydroxide. Examples of the amine include triethylamine, diethylenetriamine, m-butylamine, p-dimethylamineethanol, and triethanol. Amines and the like are preferred. (6) The concentration of the condensation catalyst is in the range of 0.01 to 20% by weight based on 1,3-organodisiloxane.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention relates to a method of using a 1,3-organodisiloxane represented by the above general formula (2) as a raw material for controlling the structure of a silicone ladder polymer. , A new polymerization method. In the present invention, the 1.3-organodisiloxane is soluble in common organic solvents, and the resulting polymer is aromatic hydrocarbons such as toluene, xylene, benzene and chlorobenzene; methylene chloride , Chloroform, dichloroethylene, trichloroethylene, halogenated hydrocarbons such as trichloroentane; tetrahydrofuran,
Ethers such as 1,4-dioxane, diethyl ether, dibutyl ether; acetone, methyl ethyl ketone,
Ketones such as methyl ether ketone; soluble in esters such as butyl acetate, ethyl acetate and methyl acetate and common organic solvents such as dimethylformamide. Further, it is desirable to use the 1,3-organodisiloxane in a concentration of 30 to 80% by weight. 30
When the concentration is lower than the weight%, the condensation reaction is slow and a sufficient reaction does not proceed. On the other hand, if the concentration is higher than 80% by weight, gelation may occur during the reaction. The catalyst which promotes the condensation reaction by being added to the 1,3-organodisiloxane solution may be used freely, but alkali metal hydroxides such as sodium hydroxide, potassium hydroxide and cesium hydroxide, triethylamine, It is preferable to use amines such as diethylenetriamine, m-butylamine, p-dimethylamine, ethanol and triethanolamine, or quaternary ammonium salts, fluoride and the like. The concentration of the condensation catalyst is from 0.01 to 1,3-organodisiloxane.
Suitable for use in the range of 20% by weight. According to the present invention, the 1,3-organodisiloxane solution can be heated to cause the condensation reaction to proceed. The preferred reaction temperature is 50
The reaction can be carried out in the range of -350 ° C, more preferably in the range of 100-150 ° C. The reaction time can be adjusted in the range of 6 to 50 hours when a catalyst is used, but when no catalyst is used, the reaction needs to be performed at a high temperature for a long time. When the 1,3-organodisiloxane has a purity of 90% or more, a polymer having a sufficiently high molecular weight can be obtained by the above operation. Thus, the present invention will be described in more detail based on the following synthesis examples, but the present invention is not limited to these.

[0006]

EXAMPLES Synthesis Example 1 A dropping funnel (10 ml) was connected to a single-necked round-bottomed flask (50 ml), a magnet stirrer was attached, and the mixture was flame-dried while adding dried nitrogen gas. A round bottom flask (50 ml) equipped with a reflux condenser was charged with toluene (20 ml) and heated at 110 ° C. 7.8 g of 1,1,1-dichlorophenyl-3,
3,3-dimethoxymethyldisiloxane [PhCl ₂ Si-O-Si-Me (O
Me) ₂ ] (see FIG. 1) was added dropwise at a rate of 1 drop / 1 minute under a nitrogen atmosphere to allow the reaction to proceed. After the completion of the dropwise addition, the reaction temperature was raised to 120 ° C., and the reaction was allowed to proceed for another 24 hours. After completion of the reaction, 10 ml of tertiary distilled water was added to add 10 ml.
The mixture was stirred at 0 ° C. for 3 hours to complete the reaction. The reaction mixture solution was added dropwise to an excessive amount of methanol, and stirred for about 1 to 2 hours. The resulting precipitate was filtered to obtain a white powder as a reaction product (yield: 92%, 7.18 g). The reaction product is
It was vacuum dried at 110 ° C. for 10 hours and used as an analysis sample. The number average molecular weight (Mn) of the produced polymer is 12,0
The molecular weight distribution (Mw / Mn) was 1.38. Structural analysis of the produced polymer was performed by ¹ H NMR and IR. According to ¹ H NMR, the chemical shift of the Si-CH ₃ group is 0.15 ppm, the chemical shift of the Si-OH group is 1.5 ppm, and the chemical shift of the Si-Ph group is 7.1-7.6 ppm.
Respectively. In particular, the CH ₃ / Ph integration ratio is 31.12:
53.57, consistent with the ratio of the theoretical values (3: 5) (see FIG. 2). In addition, the obtained polymer shows that the asymmetric stretching vibration (theoretical values: 1040, 1140 cm ^-1 ) of the siloxane bond (Si-O-Si), which is a characteristic of the ladder in IR, is double at 1035.5 and 1137.9 cm ^-1 . A peak was observed (see FIG. 3). As a result, it was confirmed that the polymer of the present invention had the structure of Chemical Formula 1.

Synthesis Example 2 The experimental apparatus was mounted in the same manner as in Synthesis Example 1. A round bottom flask (50 ml) equipped with a reflux condenser was charged with 10 ml of dimethyl sulfoxide and heated at 110 ° C. 5 g of 1,1,1-dichloromethyl-3,3,3-phenyldisodiumemelate disiloxane [MeCl ₂ Si—O—SiPh (ONa) ₂ ] (see FIG. 4) produced by another method was converted to dimethyl sulfoxide. The solution dissolved in (1) was transferred to a dropping funnel while passing dry nitrogen gas through, while stirring vigorously, the produced solution was gradually dropped (1).
Drops / 3 minutes). After the addition was completed, the reaction temperature was raised to 120 ° C., and the reaction was allowed to proceed for 24 hours. The number average molecular weight (Mn) of the produced polymer is 12,000, and the molecular weight distribution (Mw /
Mn) was 1.38. After completion of the reaction, 10 ml of tertiary distilled water was added, and the mixture was further stirred and reacted for 3 hours while bubbling with dried carbon dioxide gas. The reaction mixture solution was added dropwise to an excessive amount of methanol, and stirred for about 2 hours. The generated precipitate was filtered to obtain a white powder as a reaction product (yield: 90.8%, 4.54 g). The reaction product is
The sample was vacuum-dried at 10 ° C. for 10 hours and used as an analytical sample. The number average molecular weight (Mn) of the produced polymer is 48,000,
The molecular weight distribution (Mw / Mn) was 3 or less as 1.51. The structural analysis of the produced polymer was the same as in Synthesis Example 1.

Synthesis Example 3 One-necked round bottom flask (10 ml) and three-necked round bottom flask (500 m
A dropping funnel was connected to l), and a magnetic stirrer was attached to each of them. Then, the mixture was flame-dried while passing dried nitrogen gas. Under a nitrogen atmosphere, 10 g of 1,1,1-dichlorophenyl-
After dissolving 3,3,3-dimethoxymethyldisiloxane in 80 ml of toluene, the mixture was placed in a 100 ml flask, stirred until the temperature of the mixed solution reached 3 ° C., and then transferred to a dropping funnel. Add 310 ml of distilled water and 500 ml of ice to a three-necked round bottom flask, and slowly add the mixed solution while stirring vigorously.
(1 drop / 1 second) to carry out a hydrolysis reaction. After dropping,
The mixture was stirred for about 20-30 to terminate the hydrolysis reaction. The reaction solution was transferred to a separatory funnel, and after separating the aqueous layer and the toluene layer, the aqueous layer was cooled with hydrochloric acid as a reaction by-product.
Neutralized to pH 7 with a 1% by weight aqueous sodium hydrogen carbonate solution. The hydrolyzate is obtained by filtering the precipitate generated from the aqueous layer by the thawing method and filtering the hydrolyzate [Ph (OH) ₂ Si-O-SiMe (OM
e) ₂ ] (see FIG. 5) to obtain 9.4 g (yield: 94% by weight). In a round bottom flask (50 ml) equipped with a Dean-Stark tube, 9.4 g of the hydrolyzate
The resultant was dissolved in ml of toluene, and 0.94 mg (0.01% by weight) of KOH was added thereto, followed by polycondensation at 120 ° C. for 16 hours. After the completion of the reaction, the reaction solution was dropped into an excessive amount of methanol, and the generated precipitate was filtered to obtain 9 g (yield: 95.7%) of a reaction product as a white powder. The reaction product is vacuum
After drying, it was used as an analytical sample. The number average molecular weight (Mn) of the produced polymer is 78,000, and the molecular weight distribution (Mw / Mn) is
1.32. Structural analysis of the polymer produced is Synthesis Example 1.
Was the same as

[0009]

The polyorganosilsesquioxane obtained by the production method of the present invention is useful as a heat-resistant material. The heat-resistant coating material, the protective coating material for optical fibers, the coating material for a resistor and the like are used depending on the side chain. It is a useful material for heat-resistant paints, adhesives, mold release agents, etc. In addition, semiconductor protective film, interlayer insulating film
(LSI), resist material, new heat-resistant photoresist,
And it can be used as a functional photonic material.

[Brief description of the drawings]

FIG. 1 is a ¹ H NMR spectrum of 1,1,1-dichlorophenyl-3,3,3-dimethoxyloxane.

FIG. 2 shows ¹ HN of the polymer produced in Synthesis Example 1 of the present invention.
It is an MR spectrum.

FIG. 3 is an IR spectrum of the polymer produced in Synthesis Example 1 of the present invention.

FIG. 4 is a ¹ H NMR spectrum of 1,1,1-dichloromethyl-3,3,3-phenyldisodiumate disiloxane.

FIG. 5 is an IR spectrum of the polymer produced in Synthesis Example 3 of the present invention.

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Song San Juan South Korea Seoul Nowong-hak Haye-dong 288 Hyundai 2-cha apartment 211-503 Apartment 102-301 (72) Inventor Yun Chang Yi South Korea Incheon Bupyung-ksi Byung-dong 182 14-2 (72) Inventor Song Pyong-Hong South Korea Seoul Dongdaemun-ku Fe-Gi-dong Sinhyundai Apartment 9-1406 F term (reference) 2H025 AA10 AB17 BC50 CB33 4J035 BA12 CA01N CA022 CA032 CA052 CA102 CA172 CA192 EB01 EB03

Claims (6)

[Claims] 1. A polyorganosilsesquioxane represented by the following general formula: Embedded image (Wherein R ₁ and R ₂ are a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted aromatic group having 5 to 30 carbon atoms, a substituted or unsubstituted allyl group having 1 to 30 carbon atoms, A substituted or unsubstituted cyclic compound residue having 3 to 30 carbon atoms, a substituted or unsubstituted acyl group having 1 to 30 carbon atoms, a vinyl group, an amine residue, or an acetic acid residue is independently shown, and n is 1 and Indicates one of the above integers.) 2. The polyorgano according to claim 1, wherein the alkyl group is a methyl group, an ethyl group, or a propyl group, and the aromatic group is a phenyl group or a halogenated phenyl group. Silsesquioxane. 3. The method for producing a polyorganosilsesquioxane according to claim 1, wherein the polyorganosilsesquioxane is formed from a 1,3-organodisiloxane represented by the following general formula. Embedded image (Wherein X is a hydrogen atom, a chlorine atom, a hydroxyl group,
Represents an amino group or a carboxy group; R is a hydrogen atom,
Alkyl group, acetic acid residue, sodium or potassium metal. ) 4. The condensation reaction is carried out in the absence of a catalyst or at least one catalyst selected from the group consisting of an alkali metal hydroxide, an amine, a quaternary ammonium salt, and a fluoride. The method according to claim 3, wherein the method is performed in the presence. 5. The alkali metal hydroxide is sodium hydroxide, potassium hydroxide or cesium hydroxide, and the amine is triethylamine, diethylenetriamine, m-butylamine, p-dimethylamineethanol, or triethanolamine. The method according to claim 3, wherein: 6. The method according to claim 3, wherein the concentration of the condensation catalyst is in the range of 0.01 to 20% by weight based on 1,3-organodisiloxane.