CN101899156B - Preparation method of multichain trapezoidal polyalkyl silsesquioxane - Google Patents

Abstract

The invention discloses a preparation method of multi-chain ladder polyalkylsilsesquioxane, comprising: using trialkoxysilane and chlorosilane as a precursor, using carboxylic acid or Lewis acid as a catalyst, in an organic solvent, Obtained by non-hydrolytic condensation polymerization at a reaction temperature of 0-110°C. The multi-chain ladder polyalkylsilsesquioxane of the present invention has a highly regular structure, a narrow molecular weight distribution, excellent thermal stability and mechanical-mechanical properties, and can be widely used in many special functional polymer materials, nano Composite materials, interlayer insulating layers inside microelectronic devices, polymer catalysts, and substrates for optoelectronic information polymer nonlinear optical materials, etc. The invention has the characteristics of simple production process, less energy consumption, mild conditions, low cost, easy realization of large-scale production and application, and environmental friendliness, and is easy to adjust the molecular weight and side group of multi-chain trapezoidal polyalkylsilsesquioxane And the types of end groups to meet the needs of different applications.

Description

A kind of preparation method of multi-chain ladder polyalkylsilsesquioxane

technical field

The invention relates to the preparation technology of multi-chain ladder polyalkylsilsesquioxane.

Background technique

Double-chains ladderpolyalkylsilsesquioxanes (Double-chains ladderpolyalkylsilsesquioxanes, referred to as: LPSQs), because it has both an inorganic double main chain skeleton and an organic side/end group at the molecular level, it has excellent thermal stability and excellent mechanical properties. - Mechanical properties; in addition, LPQSs have good film-forming properties, low swelling, and better radiation resistance and dielectric properties. It can be widely used in many special functional polymer materials, nanocomposite materials, internal interlayer insulating layers of microelectronic devices, polymer catalysts and substrates of photoelectric information polymer nonlinear optical materials, etc. In recent years, organosilicon polymer materials, nanocomposites, internal interlayer insulating layers and insulating coatings of microelectronic devices based on double-chain ladder polysilsesquioxane have gradually become one of the research hotspots of organosilicon polymers.

Brown and his collaborators used the so-called "equilibrium condensation method" to successfully synthesize double-chain ladder polyphenylsilsesquioxane for the first time. Due to the high reaction temperature used and the specific reaction mechanism, their ladder structure has been questioned. Zhang Rongben and others proposed a "step-by-step coupling polymerization method" to overcome the shortcomings of the method used by Brown et al. to obtain a highly regular ladder structure. The method is characterized in that the so-called "template molecule" needs to be used in the early stage of the synthesis process: diamine. Using cyclotetrasiloxane tetraol as the starting monomer, Unno and colleagues synthesized highly regular five-ring ladder polymers through the combination of "stepwise condensation reaction of silanol and chlorosilane" and "dechlorination of benzene". Silsesquioxane. Although the above-mentioned methods can successfully obtain trapezoidal polysilsesquioxanes with relatively regular structures, they all belong to hydrolysis and polycondensation methods, which generally have high activity of reactive monomers, many steps, and complicated operations, and some are only suitable for silanes with special structures. Monomer raw materials are not suitable for large-scale production and application. Therefore, it is necessary to develop a new method for preparing multi-chain ladder polyalkylsilsesquioxanes with simple process, rapid reaction, low cost and high efficiency.

Contents of the invention

The purpose of the present invention is to overcome the deficiencies of the existing technology for preparing multi-chain ladder polyalkylsilsesquioxanes, and provide a simple, easy, low-cost, convenient and environmentally friendly polyalkylene compound suitable for industrial production of multi-chain ladder polyalkyl silsesquioxanes. Process for the preparation of silsesquioxanes.

In order to achieve the above object, the present invention adopts the following technical solutions:

A preparation method of multi-chain ladder polyalkylsilsesquioxane, using trialkoxysilane and chlorosilane as precursor, carboxylic acid or Lewis acid as catalyst, in organic solvent, reaction temperature 0-110°C Under non-hydrolytic condensation polymerization.

In the above preparation method, the trialkoxysilane is preferably phenyltrimethoxysilane, phenyltriethoxysilane, isopropyltrimethoxysilane, isopropyltriethoxysilane, aminopropyl Trimethoxysilane, Aminopropyltriethoxysilane, Ethyltriethoxysilane, Ethyltrimethoxysilane, Vinyltrimethoxysilane, Vinyltriethoxysilane, Allyltrimethoxy One or a mixture of silane, allyltriethoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane.

In the above preparation method, the chlorosilane is preferably methyltrichlorosilane, ethyltrichlorosilane, propyltrichlorosilane, vinyltrichlorosilane, dimethyldichlorosilane, tetrachlorosilane, phenyltrichlorosilane, One or a mixture of chlorosilane, allyltrichlorosilane, isopropyltrichlorosilane, cyclohexyltrichlorosilane.

In the above preparation method, when 7.1 to 40 parts by weight of trialkoxysilane and 7.5 to 60 parts by weight of trichlorosilane are used as precursors, the multi-chain ladder polyalkylsilsesquioxane obtained is as follows: I) as shown;

Wherein, R ₁ or R ₂ is methyl, phenyl, isopropyl or aminopropyl, R is hydrogen, methyl or ethyl, and n=100-200.

When 7.1-60 parts by weight of trialkoxysilane and 3.5-40 parts by weight of tetrachlorosilane are used as precursors, the obtained multi-chain ladder polyalkylsilsesquioxane is shown in formula (II);

Wherein, R ₁ is methyl, phenyl, isopropyl or aminopropyl, R is hydrogen, methyl or ethyl, and n=100-200.

When 7.1-60 parts by weight of trialkoxysilane and 3.5-40 parts by weight of dichlorosilane are used as precursors, the obtained multi-chain ladder polyalkylsilsesquioxane is shown in formula (III);

Wherein, R ₁ or R ₂ is methyl, phenyl, isopropyl or aminopropyl, R is hydrogen, methyl or ethyl, and n=100-200.

In the above preparation method, the catalyst is preferably one or a mixture of trichloroacetic acid, trifluoroacetic acid, AlCl ₃ , FeCl ₃ , TiCl ₄ , ZrCl ₄ , BCl ₃ , and the dosage is 0.05-4 parts by weight .

In the above preparation method, the organic solvent is preferably one or a mixture of acetone, methyl isobutyl ketone, tetrahydrofuran, toluene, benzene, 1,4-dioxane, and carbon tetrachloride. It is 100-400 parts by weight.

The preparation method of above-mentioned multi-chain ladder polyalkylsilsesquioxane comprises the following steps:

(1) Dissolving trialkoxysilane in 65% to 95% by weight of an organic solvent at 0 to 110°C, after mixing evenly, adding a carboxylic acid or Lewis acid catalyst under vigorous stirring;

(2) After reacting for 3 to 24 hours at 0 to 110°C, slowly add chlorosilane dropwise, and the dropwise addition is completed within 3 to 12 hours;

(3) 0～110℃, continue to react for 20～120 hours;

(4) After the reaction is finished, filter with suction, and carry out vacuum distillation on the filtrate. The distillation temperature starts from room temperature and rises to 60°C when no fraction flows out. , until no distillate flows out, the distillation residue is dissolved with an organic solvent, and slowly added to 400-2000 parts by weight of anhydrous methanol to obtain a white precipitate, filtered with suction, and the filter cake is vacuum-dried at 50-110° C. for 12-48 hours.

In order to control the product structure, the following steps are added between the above preparation method step (3) and step (4): dropwise adding a mixed liquid of 2 to 5 parts by weight of pure water and 35% to 5% by weight of an organic solvent, 3 to 5 parts by weight of an organic solvent The dropwise addition is completed within 18 hours, continue to react for 24-64 hours, install an oil-water separator and raise the reaction temperature to 100-120°C for 5-10 hours, and wash the reaction solution with saturated NaCl aqueous solution to neutral and anhydrous Na ₂ SO ₄ Dry for 12-24 hours.

Compared with the prior art, the present invention has the following beneficial effects:

From the mechanism of non-hydrolytic condensation polymerization, it can be known that the reaction speed of non-hydrolytic condensation polymerization is slow and easy to control, and the reaction between trialkoxysilane and polychlorosilane precursor can be conveniently regulated: first, disiloxane with a defined structure is generated Second, the use of steric hindrance to regulate the reaction between alkoxysilane and chlorosilane is used to control the molecular structure of the multi-chain ladder. If the second-step condensation adopts hydrolysis condensation reaction, the silanol groups generated by the hydrolysis reaction of the disiloxane intermediate can self-assemble through hydrogen bonds to form a multi-chain ladder-shaped polyalkylsilsesquioxide with regular structure alkyl.

The multi-chain ladder polyalkylsilsesquioxane prepared by the present invention has a highly regular structure, a narrow molecular weight distribution, and excellent thermal stability and mechanical-mechanical properties, and can be widely used in many special functional polymers Materials, nanocomposites, interlayer insulating layers inside microelectronic devices, polymer catalysts, and substrates for optoelectronic information polymer nonlinear optical materials, etc. The non-hydrolytic condensation polymerization method designed in the present invention has the characteristics of simple production process, less energy consumption and time, mild conditions, low preparation cost, easy realization of large-scale production and application, and environmental friendliness. The molecular weight, side group and end group type of alkylsilsesquioxane can meet the needs of different applications.

Description of drawings

The X-ray diffraction figure of Fig. 1 double-chain ladder polymethylphenylsilsesquioxane;

The infrared spectrogram of Fig. 2 double-chain ladder polymethylphenylsilsesquioxane;

Fig. 3 ²⁹ Si NMR spectrum of double-chain ladder polymethylphenylsilsesquioxane.

Detailed ways

The technical solutions of the present invention will be further described below in conjunction with examples, but are not limited to these examples.

Example 1

Dissolve 10 parts of phenyltrimethoxysilane in 100 parts of anhydrous methyl isobutyl ketone, stir and mix evenly, then add 1.5 parts of trichloroacetic acid and react at 20°C for 5 hours. Then dropwise add a mixed solution of 11 parts of methyltrichlorosilane and 20 parts of anhydrous methyl isobutyl ketone, dropwise addition is completed in 4 hours, continue to react for 60 hours, and distill under reduced pressure: the distillation temperature starts from room temperature, until there is no distillate Raise the temperature to 60°C when flowing out, and then raise the temperature to 80°C when no fraction flows out, and finally raise the temperature to 110°C until no fraction flows out. Dissolve the distillation residue completely with 50 parts of methyl isobutyl ketone, slowly drop it into 500 parts of anhydrous methanol to gradually produce a large amount of white precipitate, filter it with suction, and dry the filter cake under vacuum at 60°C for 24 hours to obtain a white powder polymethyl ketone Phenylsilsesquioxane products. The X-ray diffraction pattern of the double-chain ladder polymethylphenylsilsesquioxane product of gained is as shown in Figure 1, and the infrared spectrum of the double-chain ladder polymethylphenylsilsesquioxane product of gained is as shown in Figure 2, The ²⁹ Si NMR spectrum of the obtained double-chain ladder polymethylphenylsilsesquioxane product is shown in FIG. 3 .

Example 2

Dissolve 10 parts of phenyltrimethoxysilane in 100 parts of anhydrous methyl isobutyl ketone, stir and mix evenly, then add 1.5 parts of trichloroacetic acid and react at 10°C for 5 hours. Then add dropwise the mixed solution of 11 parts of methyltrichlorosilane and 15 parts of anhydrous methyl isobutyl ketone, dropwise addition is completed in 4 hours, continue to react for 60 hours, and distill under reduced pressure: the distillation temperature starts from the greenhouse first, until there is no distillate Raise the temperature to 60°C when flowing out, and then raise the temperature to 80°C when no fraction flows out, and finally raise the temperature to 110°C until no fraction flows out. Dissolve the distillation residue completely with 50 parts of toluene, slowly drop it into 500 parts of anhydrous methanol to gradually produce a large amount of white precipitate, filter it with suction, and dry the filter cake in vacuum at 60°C for 36 hours to obtain a white powder double-chain trapezoidal polymethylbenzene base silsesquioxane products.

Example 3

Dissolve 10 parts of phenyltrimethoxysilane in 100 parts of anhydrous methyl isobutyl ketone, stir and mix evenly, then add 1.5 parts of trichloroacetic acid and react at 20°C for 5 hours. Then dropwise add a mixed solution of 11 parts of methyltrichlorosilane and 15 parts of anhydrous methyl isobutyl ketone, drop it in 12 hours, continue to react for 80 hours, and distill under reduced pressure: the distillation temperature starts from the greenhouse, until there is no distillate Raise the temperature to 60°C when flowing out, and then raise the temperature to 80°C when no fraction flows out, and finally raise the temperature to 110°C until no fraction flows out. Dissolve the distillation residue completely with 50 parts of methyl isobutyl ketone, slowly drop it into 500 parts of anhydrous methanol to gradually produce a large amount of white precipitate, filter it with suction, and dry the filter cake under vacuum at 60°C for 48 hours to obtain a white powder polymethyl ketone Phenylsilsesquioxane products.

Example 4

Dissolve 10 parts of phenyltrimethoxysilane in 100 parts of anhydrous methyl isobutyl ketone, stir and mix evenly, then add 1.5 parts of trichloroacetic acid and react at 0°C for 5 hours. Then dropwise add a mixed solution of 11 parts of methyltrichlorosilane and 20 parts of anhydrous methyl isobutyl ketone, drop it in 5 hours, continue to react for 120 hours, and distill under reduced pressure: the distillation temperature starts from the greenhouse first, to Raise the temperature to 60°C when no fraction flows out, then raise the temperature to 80°C when no fraction flows out, and finally raise the temperature to 110°C until no fraction flows out. Dissolve the distillation residue completely with 50 parts of methyl isobutyl ketone, slowly drop it into 500 parts of anhydrous methanol to gradually produce a large amount of white precipitate, filter it with suction, and dry the filter cake in vacuum at 110°C for 24 hours to obtain a white powder double-chain trapezoid Polymethylphenylsilsesquioxane products.

Example 5

Dissolve 20 parts of aminopropyltrimethoxysilane in 150 parts of anhydrous toluene, stir and mix evenly, then add 2 parts of trichloroacetic acid and react at 20°C for 5 hours. Then dropwise add a mixed solution of 11 parts of silicon tetrachloride and 40 parts of anhydrous toluene, dropwise addition is completed in 6 hours, after continuing to react for 60 hours, vacuum distillation: the distillation temperature starts from the greenhouse, and heats up when no fraction flows out to 60°C, and then to 80°C when no fraction flows out, and finally to 110°C until no fraction flows out. Dissolve the distillation residue completely with 50 parts of toluene, slowly drop it into 800 parts of anhydrous methanol to gradually produce a large amount of white precipitate, filter it with suction, and dry the filter cake in vacuum at 80°C for 12 hours to obtain a white powder triple-chain trapezoidal polyaminopropyl Silsesquioxane products.

Example 6

Dissolve 20 parts of cyclohexyltrimethoxysilane in 150 parts of anhydrous toluene, stir and mix evenly, then add 4 parts of trichloroacetic acid and react at 20°C for 5 hours. Then dropwise add a mixed solution of 11 parts of diethyldichlorosilane and 40 parts of anhydrous toluene, and the dropwise addition is completed in 6 hours. After continuing to react for 60 hours, vacuum distillation: the distillation temperature starts from the greenhouse until no fraction flows out. The temperature was raised to 60°C, and then to 80°C when no fraction flowed out, and finally to 110°C until no fraction flowed out. Dissolve the distillation residue completely with 50 parts of toluene, slowly drop it into 800 parts of anhydrous methanol to gradually produce a large amount of white precipitate, filter it with suction, and dry the filter cake in vacuum at 80°C for 24 hours to obtain a white powder bridged double-chain trapezoidal polycyclic ring Hexylsilsesquioxane products.

Example 7

Under the condition of 20°C, 20 parts of cyclohexyltrimethoxysilane and 0.05 part of ferric trichloride were sequentially added to 150 parts of anhydrous toluene, and then mixed uniformly by magnetic force, and reacted for 4 hours. 11 parts of diethyldichlorosilane were added dropwise, and the addition was completed in 5 hours, and the reaction was continued at 20°C for 36 hours. A mixed liquid of 10 parts of water and 40 parts of toluene was added dropwise, and the addition was completed in 12 hours, and the reaction was continued at 20°C for 24 hours. Install an oil-water separator and raise the reaction temperature to 110°C for 5 hours. Suction filtration, the filtrate was washed with saturated NaCl aqueous solution until neutral, and dried by adding anhydrous Na ₂ SO ₄ for 12 h. Suction filtration, the filtrate is subjected to vacuum distillation, the distillation temperature starts from room temperature, and the temperature is raised to 60°C when no fraction flows out, and then the temperature is raised to 80°C when no fraction flows out, and finally the temperature is raised to 110°C until no fraction flows out. Dissolve the distillation residue with an organic solvent, slowly drop it into 800 parts of anhydrous methanol to gradually produce a large amount of white precipitate, filter it with suction, and dry the filter cake under vacuum at 80°C for 48 hours to obtain a white powder bridged double-chain trapezoidal polycyclohexyl silicon Sesquioxane products.

Example 8

At 20°C, add 10 parts of methyltrimethoxysilane and 0.05 part of ferric chloride to 100 parts of anhydrous toluene in sequence, mix well, react for 8 hours, add 11 parts of methyltrichlorosilane dropwise, add dropwise for 5 hours After completion, the reaction was continued at 20°C for 36h. A mixed liquid of 6 parts of water and 10 parts of toluene was added dropwise, and the addition was completed in 8 hours, and the reaction was continued at 20° C. for 48 hours. An oil-water separator was installed, the reaction temperature was raised to 100° C., and the reaction was carried out for 8 hours. Suction filtration, the filtrate was washed with saturated NaCl aqueous solution until neutral, and dried by adding anhydrous Na ₂ SO ₄ for 24 h. Suction filtration, the filtrate is subjected to vacuum distillation, the distillation temperature starts from room temperature, and the temperature is raised to 60°C when no fraction flows out, and then the temperature is raised to 80°C when no fraction flows out, and finally the temperature is raised to 110°C until no fraction flows out. The distillation residue was dissolved in an organic solvent, and the filtrate was slowly dropped into 500 parts of anhydrous methanol to gradually produce a large amount of white precipitate, filtered by suction, and the filter cake was vacuum-dried at 110°C for 24 hours to obtain a white powder double-chain trapezoidal polymethylsilane Hemioxane products.

Claims (9)

1. a preparation method of multi-chain ladder polyalkylsilsesquioxane, is characterized in that comprising the following steps: (1) Dissolving trialkoxysilane in 65% to 95% by weight of an organic solvent at 0 to 110°C, after mixing evenly, adding a carboxylic acid or Lewis acid catalyst under vigorous stirring; (2) After reacting for 3 to 24 hours at 0 to 110°C, slowly add chlorosilane dropwise, and the dropwise addition is completed within 3 to 12 hours; (3) 0～110℃, continue to react for 20～120 hours; (4) After the reaction is finished, filter with suction, and carry out vacuum distillation on the filtrate. The distillation temperature starts from room temperature and rises to 60°C when no fraction flows out. , until no distillate flows out, the distillation residue is dissolved with an organic solvent, and slowly added to 400-2000 parts by weight of anhydrous methanol to obtain a white precipitate, filtered with suction, and the filter cake is vacuum-dried at 50-110° C. for 12-48 hours. 2. The preparation method according to claim 1, characterized in that the trialkoxysilane is phenyltrimethoxysilane, phenyltriethoxysilane, isopropyltrimethoxysilane, isopropyltrimethoxysilane, Ethoxysilane, Aminopropyltrimethoxysilane, Aminopropyltriethoxysilane, Ethyltriethoxysilane, Ethyltrimethoxysilane, Vinyltrimethoxysilane, Vinyltriethoxy One or a mixture of silane, allyltrimethoxysilane, allyltriethoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane. 3. The preparation method according to claim 1, wherein said chlorosilane is methyltrichlorosilane, ethyltrichlorosilane, propyltrichlorosilane, vinyltrichlorosilane, dimethyldichlorosilane , tetrachlorosilane, phenyltrichlorosilane, allyltrichlorosilane, isopropyltrichlorosilane, cyclohexyltrichlorosilane or a mixture of several. 4. The preparation method according to claim 1, 2 or 3, characterized in that: when 7.1 to 40 parts by weight of trialkoxysilane and 7.5 to 60 parts by weight of trichlorosilane are used as precursors, the obtained Multi-chain ladder polyalkylsilsesquioxane as shown in formula (I); Wherein, R ₁ or R ₂ is methyl, phenyl, isopropyl or aminopropyl, R is hydrogen, methyl or ethyl, and n=100-200. 5. The preparation method according to claim 1, 2 or 3, characterized in that: when 7.1-60 parts by weight of trialkoxysilane and 3.5-40 parts by weight of tetrachlorosilane are used as precursors, the obtained The multi-chain ladder polyalkylsilsesquioxane is shown in formula (II);

Wherein, R ₁ is methyl, phenyl, isopropyl or aminopropyl, R is hydrogen, methyl or ethyl, and n=100-200. 6. The preparation method according to claim 1, 2 or 3, characterized in that: when 7.1-60 parts by weight of trialkoxysilane and 3.5-40 parts by weight of dichlorosilane are used as precursors, the obtained The multi-chain ladder polyalkylsilsesquioxane is shown in formula (III);

Wherein, R ₁ or R ₂ is methyl, phenyl, isopropyl or aminopropyl, R is hydrogen, methyl or ethyl, and n=100-200. 7. The preparation method according to claim 1, characterized in that the catalyst is one or a mixture of trichloroacetic acid, trifluoroacetic acid, AlCl ₃ , FeCl ₃ , TiCl ₄ , ZrCl ₄ , BCl ₃ , the dosage is 0.05 to 4 parts by weight. 8. The preparation method according to claim 1, wherein the organic solvent is one of acetone, methyl isobutyl ketone, tetrahydrofuran, toluene, benzene, 1,4-dioxane, and carbon tetrachloride. One or several mixtures, the dosage is 100-400 parts by weight. 9. The preparation method according to claim 1, characterized in that the following steps are added between step (3) and step (4): dropwise adding 2 to 5 parts by weight of pure water and 35% to 5% by weight of an organic solvent Add the mixed liquid within 3 to 18 hours, continue to react for 24 to 64 hours, install an oil-water separator and raise the reaction temperature to 100 to 120°C for 5 to 10 hours, and wash the reaction liquid with saturated NaCl aqueous solution until neutral , Dry with anhydrous Na ₂ SO ₄ for 12-24 hours.

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