KR100371070B1 - Polyaliphaticaromaticsilsesquioxane and Method for Preparing the Same - Google Patents

Abstract

The present invention relates to a highly regular polyaliphatic aromatic silsesquioxane represented by the following formula (1) in which two substituents of an aliphatic hydrocarbon group and an aromatic hydrocarbon group are alternately bonded, and a method for producing the same.

<Formula 1>

Where

One of R ₁ and R ₂ is an unsubstituted or substituted monovalent aliphatic hydrocarbon group, and the other is an unsubstituted or substituted monovalent aromatic hydrocarbon group.

The polyaliphatic aromatic silsesquioxane produced through the present invention has a number average molecular weight in the range of about 10,000 to 1,000,000, and has a small molecular weight distribution, molecular weight control and high molecular weight, and structural defects and random structure of the oligomer during condensation polymerization. Because it does not form a three-dimensional network structure due to soluble in organic solvents, it is excellent in heat resistance, combustion resistance and flexibility. This polyaliphatic aromatic silsesquioxane is useful as a heat resistant material, and is useful as a heat resistant coating agent, a protective coating agent of an optical fiber, a coating material of a resistor, and a heat resistant coating material, an adhesive, a release agent, depending on the side chain. In addition, it may be used as a protective film, an interlayer insulating film (LSI), a resist material, a new photosensitive heat resistant material, or the like of a semiconductor.

Description

Polyaliphatic Aromatic Silsesquioxane and Method for Preparing the Compound {Polyaliphaticaromatic silsesquioxane and Method for Preparing the Same}

The present invention relates to a highly regular polyaliphatic aromatic silsesquioxane (polyaliphaticaromatic silsesqui-oxane) in which two substituents, which are excellent in heat resistance, combustion resistance, and flexibility, are alternately bonded, and a method for preparing the same.

Conventional polyorganosilsesquioxanes can be obtained by heating and condensing oligomers obtained by hydrolyzing trichlorosilane or triethoxysilane in a high boiling point solvent such as NMP, DMSO, MIBK under an alkali catalyst (Brown et al. , J. Am. Chem. Soc., 82, 6194 (1960).

However, such a manufacturing method is condensation reaction proceeds simultaneously with hydrolysis, and it is easy to produce oligomer (Mn = 1000-3000, Mw / Mn> 2) which is not precursor (silane triol), and uses this oligomer under alkali catalyst. The polymerized polymer

a. In general, the molecular weight distribution is large, and it is difficult to control the molecular weight and high molecular weight (Mn = 20,000 to 30,000 or less)

b. Due to the structural defects and random structure of the oligomer during condensation polymerization, a problem of insolubility in organic solvents has been pointed out because three-dimensional network structures are formed.

In addition, the method of synthesizing the silicone ladder polymer using phenylsilane triol can obtain a highly regular polymer having a number average molecular weight (Mn) of 1,000 to 1,000,000 and a molecular weight distribution (Mw / Mn) of 2 or less. In order to obtain silane triol with high purity, the manufacturing process is complicated, handling of phenylsilane triol at room temperature is quite difficult, and the yield is very low (yield: 10-20% or less), which is uneconomical (LJ Tyler et al. , J. Am. Chem. Soc., 77, 770 (1955), T. Takiguchi et al., J. Am. Chem. Soc., 81, 2359 (1959) and EC Lee et al., Polymer Journal, 29 (8), 678 (1997)).

As a result of intensive studies, the present inventors have found that by using 1,3-organodisiloxane as a raw material in the production of polyaliphatic aromatic silsesquioxane, the structure of the silicone ladder polymer can be effectively controlled and completed the present invention. It came to the following.

It is an object of the present invention to provide a highly regular polyaliphatic aromatic silsesquioxane alternating polymer in which two substituents are alternately bonded.

Another object of the present invention is to provide a method for producing a highly regular polyaliphatic aromatic silsesquioxane alternating polymer in which an aliphatic hydrocarbon group and an aromatic hydrocarbon group are alternately bonded to a main chain of the silsesquioxane polymer.

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

2 is a ¹ H NMR spectrum of poly (methylphenylsilsesquioxane).

3 is an IR spectrum of poly (methylphenylsilsesquioxane).

Figure 4 is a ¹ H NMR spectrum of 1,1,1-dichlorophenyl-3,3,3-phenyldisodiumlatedisiloxane.

5 is an IR spectrum of 1,1,1-dimethoxymethyl-3,3,3-dihydroxyphenyldisiloxane.

According to the present invention, there is provided a highly regular polyaliphatic aromatic silsesquioxane alternating polymer represented by the following formula (1) in which an aliphatic group and an aromatic group are alternately bonded.

Where

One of R ₁ and R ₂ is an unsubstituted or substituted monovalent aliphatic hydrocarbon group, and the other is an unsubstituted or substituted monovalent aromatic hydrocarbon group.

In the present specification, an "aliphatic hydrocarbon group" is an alkyl group having 1 to 24 carbon atoms, cyclopropyl group, cyclobutyl group, such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, t-butyl group, Alkyl groups, such as a cycloalkyl group, such as a cyclopentyl group and a cyclohexyl group, an allyl group, and a vinyl group, a cycloalkenyl group, etc. are mentioned, A part or all of the hydrogen atoms of these groups are halogen atoms, such as a fluorine atom and a chlorine atom, etc. Can be substituted.

The "aromatic hydrocarbon group" includes an aryl group such as a phenyl group and a tolyl group, and a heteroaryl group containing heteroatoms such as nitrogen, oxygen, and sulfur. Some or all of the hydrogen atoms of these groups are fluorine atoms and chlorine. It may be substituted with a halogen atom such as an atom.

The highly regular polyaliphatic aromatic silsesquioxane represented by the formula (1) has a number average molecular weight in the range of about 10,000 to 1,000,000, and aromatic hydrocarbons such as toluene, xylene, benzene and chlorobenzene, methylene chloride, chloroform, dichloroethylene, trichloro Halogen hydrocarbons such as ethylene and trichloroethane, ethers such as THF, 1,4-dioxane, diethyl ether and dibutyl ether, ketones such as acetone, methyl ethyl ketone and methyl ether ketone, butyl acetate and ethyl Soluble in esters, such as acetate and methyl acetate, and general organic solvent, such as dimethylformamide.

Further, according to the present invention, the highly regular polyaliphatic aromatic silsesqui represented by the formula (1) comprising the condensation reaction of a solution of 1,3-organodisiloxane represented by the formula (2) in an organic solvent A method for producing an oxane alternating polymer is provided.

Where

R ₁ and R ₂ are as defined above,

X is H, Cl, OH, NH ₂ or COOH,

R is H, an alkyl group, acetate, or an alkali metal such as Na and K.

In the above production method, the concentration of 1,3-organodisiloxane in the organic solvent is preferably in the range of 30 to 80% by weight. At a concentration lower than 30% by weight, the condensation reaction is late or the reaction does not proceed sufficiently, and at a concentration of 80% by weight or more, gelation may occur during the reaction.

According to the method for producing the highly regular polyaliphatic aromatic silsesquioxane alternating polymer of the present invention, the condensation reaction can be advanced by heating a 1,3-organodisiloxane solution in an organic solvent, and the reaction temperature is generally 50 ° C. It is -350 degreeC, Preferably it is 100-150 degreeC.

The heat condensation reaction may also be carried out in the presence of a catalyst. Catalysts added to the 1,3-organodisiloxane solution to promote condensation reactions include alkali metal hydroxides such as NaOH, KOH and CsOH, triethylamine, diethylene triamine, m-butylamine, p-dimethylamine ethanol and Amines such as triethanolamine or quaternary ammonium salts and fluorides. The concentration of the condensation reaction catalyst is suitably in the range of 0.01 to 20% by weight relative to 1,3-organodisiloxane.

The reaction time required is 6 to 50 hours when a catalyst is used, and when the catalyst is not used, it is necessary to react for a long time at a high temperature.

In order to obtain a sufficiently high molecular weight polymer by the above method, the purity of 1,3-organodisiloxane must be at least 90%.

The synthesis method is specifically described below with reference to Examples. Of course, the present invention is not limited by these examples.

Example 1

A 10 ml dropping funnel was connected to a 50 ml round bottom flask, equipped with a magnetic stirring device, and flame dried while passing dried nitrogen gas. 20 ml of toluene was put into a 50 ml round bottom flask equipped with a reflux condenser and heated to 110 ° C. 1,1,1-dichlorophenyl-3,3,3-dimethoxymethyldisiloxane [PhCl ₂ Si-0-Si-Me (OMe) ₂ ] (see Fig. 1) was added 7.8 g and 1 drop under nitrogen / 1 The reaction proceeded while dropping at the rate of minutes. After completion of the dropwise addition, the reaction temperature was raised to 120 ° C and allowed to react for 24 hours.

After the reaction, 10 mL of tertiary distilled water was added thereto, followed by further stirring at 100 ° C. for 3 hours, and then the reaction was completed. The reaction mixture solution was dropped into excess methanol, stirred for about 1 to 2 hours, and the resulting precipitate was filtered to give a reaction product of a white powder (yield 92%, 7.18 g). The reaction product was vacuum dried at 110 ° C. for 10 hours to use as analytical sample. The number average molecular weight (Mn) of the produced polymer was 12,000, and the molecular weight distribution (Mw / Mn) was 1.38. The structural analysis of the resulting polymer was analyzed by ¹ H NMR and IR.

^{In 1} H NMR, the chemical shift of Si-CH ₃ group was 0.15 ppm, the chemical shift of Si-OH group was 1.5 ppm, and the chemical shift of Si-Ph group was 7.1-7.6 ppm. The integral ratio of CH ₃ / Ph was 31.12: 53.57, which is consistent with the theoretical 3: 5 ratio (see FIG. 2).

Asymmetric stretching vibrations (theoretical: 1040, 1140 cm ^-1 ) of the siloxane bonds (Si-O-Si), which are characteristic of the silicone ladder polymer, were also identified as double peaks at 1035.5 and 1137.9 cm ^-1 at IR (see Figure 3). .

As a result, it was confirmed that the polymer of the present invention has the structure of Formula 1.

Example 2

The experimental apparatus was the same as that of Example 1.

10 mL of DMSO was placed in a 50 mL round bottom flask equipped with a reflux condenser and heated to 110 ° C. Separately prepared solution of 5 g of 1,1,1-dichloromethyl-3,3,3-phenyldisodiumlatedisiloxane [MeC1 ₂ Si-O-SiPh (ONa) ₂ ] (see FIG. 4) in DMSO After passing through the dried nitrogen gas to the dropping funnel, the reaction was carried out while dropping the prepared solution at a rate of 1 drop / 3 minutes while vigorously stirring. After the dropwise addition, the reaction temperature was raised to 120 ° C. and reacted for 24 hours.

After the reaction, 10 ml of tertiary distilled water was added, followed by further stirring for 3 hours while bubbling with dried C0 ₂ gas to terminate the reaction. The reaction mixture solution was dropped into excess methanol, stirred for another 2 hours, and the resulting precipitate was filtered to give a reaction product of a white powder (yield 90.8%, 4.54 g). The reaction product was vacuum dried at 110 ° C. for 10 hours to use as analytical sample.

The number average molecular weight (Mn) of the produced polymer was 48,000, the molecular weight distribution (Mw / Mn) was 1.51, and the molecular weight distribution was 2 or less.

The structural analysis of the resulting polymer was the same as in Example 1.

Example 3

A dropping funnel was connected to a 10 ml one-necked round bottom flask and a 500 ml three-necked round bottom flask, and each was equipped with a magnetic stirring device, and then flame-dried while passing dried nitrogen gas. In a nitrogen atmosphere, 10 g of 1,1,1-dichlorophenyl-3,3,3-dimethoxymethyldisiloxane was dissolved in 80 ml of toluene, then placed in a 100 ml flask and stirred until the mixed solution reached 3 ° C. After moving to the funnel funnel. 310 ml of distilled water and ice were placed in a 500 ml three-necked round bottom flask, followed by hydrolysis while dropping the mixed solution at a rate of 1 drop / 1 sec while vigorously stirring. After the addition of the dropwise addition, the mixture was further stirred for about 20 to 30 minutes, and the hydrolysis reaction was completed. The reaction solution was transferred to a separatory funnel, the water layer and the toluene layer were separated, and a cooled 70% by weight aqueous sodium hydrogen carbonate solution was added dropwise using a dropping funnel to neutralize hydrochloric acid, the reaction product in the water layer, to pH 7. The precipitate produced from the water layer was filtered using thawing method to obtain 9.4 g (yield: 94% by weight) of hydrolyzate [Ph (OH) ₂ Si-O-SiMe (OMe) ₂ ] (see FIG. 5).

In a 50 ml round bottom flask equipped with a Dean-Stark tube, 9.4 g of the hydrolyzate obtained above was dissolved in 10 ml of toluene, and 0.94 mg (0.01 wt.%) Of a KOH catalyst was added thereto. Polycondensation for hours. After the reaction, the reaction solution was added dropwise to excess methanol, followed by stirring for about 30 minutes, and the resulting precipitate was filtered to obtain 9 g of a reaction product of a white powder (yield: 95.7%). The reaction product was vacuum dried at 110 ° C. for 10 hours to use as analytical sample. The number average molecular weight (Mn) of the produced polymer was 78,000, and the molecular weight distribution (Mw / Mn) was 1.32. The structural analysis of the resulting polymer was the same as in Example 1.

Poly (aliphatic aromatic silsesquioxane) obtained according to the production method of the present invention has a small molecular weight distribution, molecular weight control and high molecular weight, and three-dimensional network structure due to structural defects and random structure of oligomer during polycondensation It is soluble in organic solvents because it does not form and is excellent in heat resistance, combustion resistance and flexibility. This poly (aliphatic aromatic silsesquioxane) is useful as a heat resistant material, and is useful as a heat resistant coating agent, a protective coating agent of an optical fiber, a coating material of a resistor, and a heat resistant coating material, an adhesive, a release agent, depending on the side chain. It can also be used as a protective film, an interlayer insulating film (LSI), a resist material, a new photosensitive heat resistant material, or the like of a semiconductor.

Claims (10)

Highly regular polyaliphatic aromatic silsesquioxane represented by the following formula (1). <Formula 1> Where One of R ₁ and R ₂ is an alkyl group having 1 to 4 carbon atoms in which some or all of the hydrogen atoms are substituted with halogen atoms, an alkyl group having 5 to 24 carbon atoms, cycloalkyl group, in which some or all of the hydrogen atoms are substituted or not substituted with halogen atoms, An alkenyl group or a cycloalkenyl group, the other being a phenyl group in which part or all of a hydrogen atom is substituted with a halogen atom, an aryl group other than a phenyl group in which part or all of a hydrogen atom may be substituted by a halogen atom, a hetero containing hetero atom It is an aryl group. Of the highly ordered polyaliphatic aromatic aliphasesquioxanes represented by the following general formula (1), which comprises condensation reaction of a solution of 1,3-organodisiloxane represented by the following general formula (2) in an organic solvent by heating to 50 to 350 ° C. Manufacturing method. <Formula 1> <Formula 2> In each formula above, One of R ₁ and R ₂ is an alkyl group having 1 to 4 carbon atoms in which some or all of the hydrogen atoms are substituted with halogen atoms, an alkyl group having 5 to 24 carbon atoms, cycloalkyl group, in which some or all of the hydrogen atoms are substituted or not substituted with halogen atoms, An alkenyl group or a cycloalkenyl group, the other being a phenyl group in which part or all of a hydrogen atom is substituted with a halogen atom, an aryl group other than a phenyl group in which part or all of a hydrogen atom may be substituted by a halogen atom, a hetero containing hetero atom Aryl group, X is H, Cl, OH, NH ₂ or COOH, R is H, an alkyl group, acetate or an alkali metal. The method of claim 2 wherein the alkali metal is Na or K. The method according to claim 2, wherein the heating temperature is 100 to 150 ° C. The method according to claim 2, wherein the concentration of the solution of 1,3-organodisiloxane represented by Chemical Formula 2 in the organic solvent is 30 to 80% by weight. The process according to claim 2, further carried out in the presence of a condensation reaction catalyst. 7. The process of claim 6 wherein the condensation reaction catalyst is selected from the group consisting of alkali metal hydroxides, amines, quaternary ammonium salts and fluorides. 8. The method of claim 7, wherein the alkali metal hydroxide is NaOH, KOH or CsOH. The method according to claim 7, wherein the amines are triethylamine, diethylenetriamine, m-butylamine, p-dimethylamineethanol or triethanolamine. The method according to any one of claims 7 to 9, wherein the concentration of the condensation reaction catalyst is in the range of 0.01 to 20% by weight based on 1,3-organosiloxane represented by the formula (2).