KR20030081204A - Polyorganosilsesquioxane and process for preparing the same - Google Patents

Abstract

PURPOSE: Provided is a poly(organosilsesquioxane) produced by using an organosilanetriol as a starting material, which is convenient to manage and easy to control the velocity of polymerization and has a high regularity, a high function, and various properties. CONSTITUTION: The poly(organosilsesquioxane) represented by the formula 2 is produced by polycondensing cyclic tetraorganosilsesquioxane represented by the formula 4 with a compound represented by the formula (R2O)2Si(R3)2 or X2Si(R3)2 in an organic solvent, wherein each of R1 and R3 is independently hydrogen, C1-C30 substituted or unsubstituted aliphatic hydrocarbon, C1-C30 substituted or unsubstituted aromatic hydrocarbon, C1-C30 substituted or unsubstituted alicyclic hydrocarbon, C1-C30 substituted or unsubstituted silyl, C1-C30 substituted or unsubstituted allyl, C1-C30 substituted or unsubstituted acyl, vinyl, amine, acetate, or alkali metal, R2 is hydrogen, methyl, acetate, sodium, or potassium, X is halogen, l is an integer of 2-300,000 as a multiple of 2, and m and n are integers of 2-300,000.

Description

Polyorganosilsesquioxane and its manufacturing method {Polyorganosilsesquioxane and process for preparing the same}

The present invention relates to a polyorganosilsesquioxane and a method for producing the same, and more particularly, to a polyorganosilsesquioxane and a method for producing the same, which are used as starting materials of triol organosilane.

Recently, with the development of advanced technology field, the development of high-performance multifunctional high-tech materials has been studied in various fields. In particular, research on new polymer materials is a new technology that has been most popular for forming organic or inorganic hybrids such as complexes having a mixed structure of organic and inorganic materials with high functionalization of organic polymers, such as improvement of heat resistance or glass transition temperature (Tg). It is attracting attention.

There are various known organic or inorganic hybrid materials, but since the thermal stability is particularly important between organic polymer and inorganic polymer, polyorganosilsesquioxane, which is a high heat resistant polymer, is most noticed among them. Can be.

Polyorganosilsesquioxanes have been synthesized by Owens Illinois and Gelest since they were first synthesized in Brown et al. (J.Am. Chem . Soc ., 82, 6194 (1960)). Although commercialized under the names of "glass-resin" and "SST-resin," it is difficult to control polymer structure and control molecular weight. .

However, since the improved properties of polyorganosilsesquioxanes are due to a highly regular ladder form structure, research on condensation methods along with the development of a new starting material that is easy to form a ladder structure has been conducted. A method of preparing a representative polyorganosilsesquioxane known to date is a low molecular weight polymer by dehydrating a precursor hydrolyzate obtained by hydrolysis of trichlorosilane or trialkoxysilane under an alkali / acid catalyst. (Mn is about 20,000 to 30,000, and its molecular weight distribution (Mn / Mw) is about 3 to 5) can be easily produced.

First, a conventional method of preparing polyorganosilsesquioxane using trichlorosilane will be described. When hydrolyzing trichlorosilane, the condensation reaction proceeds simultaneously with the hydrolysis, and the oligomer (Mn is 1,000 to 2,000 and PDI is 2 to 5) is not a single structure of silanetriol, but it is complex. It has a variety of structures, it is easy to form a three-dimensional network structure due to the inter-hydroxy group and random self-structure of the oligomer caused by the presence of a hydroxyl group in the molecule in the case of high molecular weight using it Therefore, it has been found to have the following disadvantages. That is, 1) it is impossible to control the structure of the produced polymer, 2) it is difficult to control the molecular weight of the produced polymer and to obtain a high molecular weight polymer, and thus 3) the produced polymer loses its regularity, thereby reducing its solubility in solvents, 4) In particular, the remaining low molecular weight component has a problem that adversely affect the heat resistance and mechanical properties of the polymer.

In addition, the conventional method of preparing polyorganosilsesquioxane using trialkoxysilane also has advantages in that it is easier to handle such as hydrolysis reaction rate control than the trichlorosilane. Molecular defects of oligomers caused by the presence of hydroxy groups and the presence of alkoxy groups have the following disadvantages.

That is, 1) a branched polymer, not a ladder structure, is produced, and 2) the selection and amount of catalyst used, the choice of reaction solvent, and the precise pH control of the reaction solution are necessary, but the adjustment is not easy. There is an unsuitable problem in manufacturing a highly regular silicon ladder-type polymer, such as forming a three-dimensional network structure to form a microgel to some extent.

As described above, the interest in polyorganosilsesquioxane has been extensively studied since the past, but various synthetic methods known to date, such as sol-gel method, ring-opening polymerization method, equilibrium polymerization method, etc. And the condensation process is known to be very complicated through various structural studies, so that the commercially available products such as trade name glass resin, so-called tee-type resin, etc. may also be used as new industrial materials. Due to the problem that can not meet various conditions that can act as a certain limit in practical use.

As a new industrial material device using organic or inorganic hybrid materials, low dielectric constants of about 2 to 3, thermal decomposition start temperature of 400 ° C or higher, excellent thermal stability, low hygroscopicity, low thermal expansion coefficient, and gap filling ability (gap filling) capability) and good adhesiveness.

In order to solve the above-mentioned problems, the inventors used a high-purity organosilanetriol instead of oligomers having various molecular weights and structures, and thus the regularity of the structure could not be controlled by conventional synthetic methods. / Crystalline polyphenylsilsesquioxane was synthesized.

However, there remains a need for polyorganosilsesquioxanes with better high regularity / crystallinity.

The technical problem to be achieved by the present invention is 1) easy to handle, 2) easy to control the polymerization rate, 3) the hydroxy group is uniformly present in the polymer sock end, 4) high-regular R- SiO _3/2 can be introduced, and 5) the structure of polymer crosslinking, in particular, the degree of crosslinking, crosslinking density, etc. can be easily controlled, and 6) chemical reaction for promoting a chemical reaction by unfolding the structure of the polymer. It can facilitate nitriding, and 7) easily form pores at the nanoscale or molecular level in the size of the dispersed phase in the polymer skeleton, and 8) develop and manufacture new precursors that can impart high functionality and various properties to the polymer. By the development of a new high-tech inorganic polymer having excellent physical properties.

In the present invention, it is an object of the present invention to provide a polyorganosilsesquioxane and a method for producing the same for achieving the above technical problem.

The polyorganosilsesquioxane provided by the present invention to solve the object of the present invention is a compound of formula 1, 2 or 3.

Wherein R ₁ represents hydrogen, a substituted or unsubstituted aliphatic hydrocarbon group having 1 to 30 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon group having 1 to 30 carbon atoms, a substituted or unsubstituted alicyclic ring having 1 to 30 carbon atoms Group hydrocarbon group, substituted or unsubstituted silyl group having 1 to 30 carbon atoms, substituted or unsubstituted allyl group having 1 to 30 carbon atoms, substituted or unsubstituted acyl group having 1 to 30 carbon atoms, vinyl group, amine Group, acetate or an alkali metal, n is an integer from 2 to 300,000.)

(Wherein R ₁ is as defined above, R ₃ is as defined above for R ₁ , l is an integer from 2 to 300,000 in multiples of 2, and m and n are integers from 2 to 300,000.)

Wherein R ₁ , R ₃ , l, m and n are as defined above.

The precursor for preparing the compound of Formula 1, 2 or 3 is preferably a cyclic tetraorganosilsesquioxane of the formula (4).

Wherein R ₁ is as defined above.

Method for preparing the cyclic tetraorganosilsesquioxane of Chemical Formula 4, which is a precursor for producing the polyorganosilsesquioxane of the present invention is shown in Scheme 1.

Wherein R ₁ is as defined above.

As shown in Scheme 1, cyclic tetraorga of the formula (4) as a precursor for obtaining the polyorganosilsesquioxane of the present invention by reacting with a catalyst in an organic solvent using the organosilane triol as a starting material It is possible to obtain nosilsesquioxanes. The product produced by the reaction is a compound having a variety of structures in addition to the compound of the formula (4) is obtained, it can be separated and purified by methods such as HPLC, recrystallization method to obtain a high purity compound.

The organic solvent used in the reaction is not particularly limited as long as it is a conventionally used organic solvent, but acetone, toluene, n-hexane, THF or ether is preferable.

The catalyst used in the reaction is preferably NaOH, KOH, NaHCO ₃ or DCC (1,3-dicyclohexylcarbodiimide).

The reaction temperature of the reaction is preferably 3 to 100 ° C, and the reaction time is preferably 1 to 200 hours.

By using the cyclic tetraorgano silsesquioxane of Formula 4 obtained as described above through the reaction of Scheme 2 it is possible to obtain a polyorganosilsesquioxane of the formula 1, 2 or 3 of the target compound.

(Wherein R ₁ , R ₃ , l, m and n are as defined above, R ₂ represents hydrogen, methyl, acetate, sodium or potassium, and X represents halogen.)

As shown in Scheme 2, a polyorganosilsesquioxane of formula (1), (2) or (3) is obtained by polycondensing cyclic tetraorganosilsesquioxane, which is a compound of formula (4), obtained as a precursor in an organic solvent in a conventional manner. Can be.

The (A), (B) or (C) process, which is the polycondensation process of Scheme 2, is not particularly limited, but various methods such as heating, light irradiation, electron beam injection, or microwave irradiation may be used, and when using a catalyst, n It is possible to obtain compounds of high value.

The compound of Chemical Formula 4 used in Scheme 2 is preferably used in the range of 5 to 300 parts by weight, preferably 10 to 100 parts by weight based on 100 parts by weight of the organic solvent. If the amount of the compound of Formula 4 is less than 5 parts by weight, the polycondensation reaction is slow or does not proceed sufficiently, and if it exceeds 300 parts by weight, gelation may occur during the reaction, which is not preferable. The catalyst used to accelerate the process (A), (B) or (C) is not limited in principle, but preferably alkali metal hydroxides such as sodium hydroxide, potassium hydroxide, cesium hydroxide, triethylamine, diethylene tri It is preferable to use at least one substance of amines such as amine, meta-butylamine, para-dimethylamine ethanol, triethanolamine, or quaternary ammonium salts or fluoride. The catalyst for the condensation reaction is preferably used in the range of 0.001 to 5 parts by weight, preferably 0.001 to 1 part by weight based on 100 parts by weight of the compound of Formula 4.

The organic solvent used in the reaction of Scheme 2 is not particularly limited, but it is preferable to use THF, benzene, chlorobenzene, xylene, MIBK, DMF, NMP, 1,4-dioxane, DMAc, acetone or toluene. .

The reaction temperature of the polycondensation process (A), (B) or (C) process used in the reaction scheme 2 is in the range of 50 to 350 ℃, it is preferable to react at 100 to 150 ℃, the reaction time proceeds at this time When using a silver catalyst, it is preferable to adjust in 1 to 50 hours, and when not using a catalyst, it is preferable to make it react in the range of 100 to 350 degreeC for 1 to 30 hours. If the polycondensation temperature is lower than or exceeded, there is a problem that the efficiency of the condensation reaction is not made to an industrial degree.

In addition, when the purity of the compound of Formula 4 for the polycondensation reaction is 90% or more, a polymer having a sufficiently high molecular weight may be obtained by different manipulation methods.

More specifically, each polycondensation process of Scheme 2 is as follows.

In step (A) of Scheme 2, the compound of Formula 1 may be obtained by dehydration of hydroxy at both terminals by polycondensation of the compound of Formula 4 without other adducts.

Step (B) of Scheme 2 reacts the compound of Formula 4, which is a precursor, and (R ₂ O) ₂ Si (R ₃ ) _{2, which} is a compound of Formula 6, or X ₂ Si (R ₃ ) ₂ , which is a compound of Formula 7 As a step, the hydroxy group of the compound of Formula 4 and the alkoxy group of the compound of Formula 6 or X of the compound of Formula 7 may be combined to obtain the compound of Formula 2. In particular, in the case of using the compound of the formula (6) as the reactant, it is preferable to use alkali metal hydroxide as the polycondensation catalyst.

Step (C) of Scheme 2 is a step of reacting a compound of Formula 4 as a precursor with (R ₂ O) ₃ SiR _{3 as} a compound of Formula 8 or X ₃ SiR ₃ as a compound of Formula 7 as a hydroxyl group of the compound of Formula 4 And an alkoxy group of Formula 8 or X of Formula 9 may be combined to obtain a compound of Formula 3. In particular, when the compound of formula 8 is used as a reactant, it is preferable to use an alkali metal hydroxide as the polycondensation catalyst. The polyorganosilsesquioxanes represented by the above formulas 1 to 3 provided in the present invention may be Aromatic hydrocarbons such as toluene, xylene, benzene, chlorobenzene, hydrocarbons such as methylene chloride and chloroethane, ethers such as THF, 1,4-dioxane, diethyl ether and dibutyl ether It is soluble in ketones such as acetone, methyl ethyl ketone and methyl ether ketone, and organic solvents such as esters and dimethylformamide.

As used herein, the terms R ₁ and R ₃ are each independently hydrogen, a substituted or unsubstituted aliphatic hydrocarbon group having 1 to 30 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon group having 1 to 30 carbon atoms, or a carbon atom Substituted or unsubstituted alicyclic hydrocarbon group having 1 to 30 carbon atoms, substituted or unsubstituted silyl group having 1 to 30 carbon atoms, substituted or unsubstituted allyl group having 1 to 30 carbon atoms, substituted or substituted with 1 to 30 carbon atoms, or Unsubstituted acyl group, vinyl group, amine group, acetate or alkali metal, preferably lower alkyl group such as hydrogen, methyl group, ethyl group or propyl group, phenyl group, phenol group, chlorophenyl group, vinyl group, carboxyl group, trimethylsilyl Group, acetate, sodium, potassium and the like, more preferably hydrogen, methyl group, phenyl group, vinyl group, trimethylsilyl group and the like.

Example

Hereinafter, embodiments will be described in detail to illustrate the present invention. However, embodiments according to the present invention may be modified in various forms, and the scope of the present invention will be described in detail below. It should not be construed as limited to Embodiments of the present invention are provided to more completely explain the present invention to those skilled in the art.

Example 1 Preparation of a Compound of Formula 4 (cyclictetraphenylsilsesquioxane) (R _One = Phenyl)

A magnetic stirring device was installed in a 250 ml round bottom flask, followed by flame drying while passing dried nitrogen. After 25 g of phenylsilane triol (PST) and 1.25 g of sodium hydrogencarbonate as a catalyst were dissolved in 80 ml of chloroform, the insolubles were filtered off and the filtrate was concentrated to 1/2. The concentrated chloroform solution was recrystallized at -10 ° C for 3 months to obtain cyclic tetraphenylsilsesquioxane (yield: 88%) as a colorless transparent needle crystal. The obtained needle crystal was vacuum-dried at -10 ° C for 4 hours for analysis. Used as.

¹ H NMR (500 MHz / CDCl ₃ ): δ 7.11-7.8 (m, Si-Ph), 2.2-2.8 (s, Si-OH) ppm

IR (KBr): 3600-3200 (Si-OH), 3080-2940 (CH), 1435 (Si-Ph), 1050 (O-Si-Ph),

1150 (O-Si), 750, 700 (Ph) cm ^-1

²⁹ Si NMR (99.3 MHz / CDCl ₃ ): δ-64.1 ppm (Ph-T ₂ (OH) ₁ )

GPC (PSt): Mn = 640, Mw / Mn = 1.0

XRD: 2θ = 5.71, 7.77 (Si-O), 19.52, 18.12 (Si-Ph)

Example 2: Silox Capping Reaction of Cyclic Tetraphenylsilsesquioxane

Another method for confirming the structure of the cyclic tetraphenylsilsesquioxane obtained in Example 1 will be described.

A 20 ml dropping funnel was connected to a 50 ml round bottom flask and flame dried while passing the dried nitrogen gas. Subsequently, 0.33 g of the cyclic tetraphenylsilsesquioxane obtained in Example 1 was dissolved in 10 ml of distilled cycloxene, and then 0.17 g of catalyst N (CH ₂ CH ₃ ) ₃ was added thereto, and the mixture was stirred at room temperature for 1 hour. After dissolving 0.13 g of (CH ₃ ) ₃ SiCl in 10 ml of cycloxene, the siloxy capping reaction was performed while slowly dropwise using a dropping funnel. When the reaction was completed, the trimethyl salt was filtered off, and the cycloxene was dried in vacuo to give a white reaction product.

¹ H NMR (500 MHz / CDCl ₃ ): δ 7.11-7.8 (m, Si-C ₆ H ₅ ), 0.2 (s, (CH ₃ ) ₃ -Si) ppm

(Ph / Me ₃ ratio; 35.8 / 19.2 ≒ 5/9)

²⁹ Si NMR (99.3 MHz / CDCl ₃ ): δ -37 (s, Si- (CH ₃ ) ₃ ), -83 (s, Ph-T ₃ ) ppm

Example 3: Preparation of Compound (Polyphenylsilsesquioxane) of Formula 1 (R _One = Phenyl)

The Dean-Stark tube was placed in a 50 ml round bottom flask and flame dried in a nitrogen atmosphere. 5 g of cyclic tetraphenylsilsesquioxane and 5.0 mg of potassium hydroxide obtained in Example 1 were placed in a flask, and 38 ml of toluene was added to dissolve cyclic tetraphenylsilsesquioxane. Subsequently, the reaction was carried out at a reflux temperature of toluene for 38 hours. After the reaction, the mixture was added dropwise to methanol, stirred for 30 minutes, and the resulting precipitate was filtered to give a reaction product (yield: 98%) as a white powder.

The product was vacuum dried at 50 ° C. for 10 hours and used as analytical sample.

¹ H NMR (500MHz / CDCl ₃ ): δ 7.11-7.8 (s, Si-Ph) ppm

IR (KBr): 3080-2940 (CH), 1435 (Si-Ph), 1050 (O-Si-Ph), 1150 (O-Si),

750, 700 (Ph) cm ^-1

²⁹ Si NMR (99.3 MHz / CDCl ₃ ): δ -83.7 ppm

XRD: 2θ = 5.71, 7.96 (Si-O), 24.87, 22.69, 19.52, 18.12 (Si-Ph)

Example 4 Preparation of a Compound of Formula 4 (cyclictetra (trimethylsilyl) silsesquioxane) (R _One Trimethylsilyl)

The procedure was the same as in Example 1, except that 1,1,1-trimethyl-2,2,2-triol disilane was used instead of phenylsilane triol as a starting material.

¹ H NMR (500 MHz / CDCl ₃ ): δ 0.1 (s, Si-SiMe ₃ ), 4.4 (s, Si-OH) ppm

²⁹ Si NMR (99.3 MHz / CDCl ₃ ): δ -32 (s, Si-Me) ppm

GPC (PSt): Mn = 490, Mw / Mn = 1.01

Example 5 Photoreaction Preparation of Compound of Formula 1 (Poly (trimethylsilyl) silsesquioxane)

(R _One Trimethylsilyl)

5 g of the cyclic tetra (trimethylsilyl) silsesquioxane obtained in Example 4 was dissolved in 20 ml of cyclohexane and exposed to a low temperature mercury lamp for 3 minutes with vigorous stirring. After the reaction, the reaction product was added dropwise into methanol and stirred for 30 minutes, and the resulting precipitate was filtered to give a reaction product (yield: 97%) as a white powder. The reaction product was dried with nitrogen gas at 3 ° C. and analyzed. Used as a sample. By analyzing these results, it was found that poly (trimethylsilyl) silsesquioxane (R ₁ = trimethylsilyl), in which the reaction product was a compound of formula ( ₁ ), was obtained.

¹ H NMR (500MHz / CDCl ₃ ): δ -0.1-0.4 (s, Si-SiMe ₃ )

²⁹ Si NMR (99.3 MHz / CDCl ₃ ): δ -62.4 to -68.0 (m, Si-Me) ppm

Example 6: Polycondensation Preparation of Compound of Formula 1 (Poly (trimethylsilyl) silsesquioxane) _One Trimethylsilyl)

In the same manner as in Example 3 except that the cyclic trimethylsilyl obtained in Example 4 was used instead of the cyclic tetraphenylsilsesquioxane of Example 3, a reaction product of a white powder (a yield: 98%) was obtained.

GPC (PSt): Mn = 36,000, Mw / Mn = 1.4

¹ H NMR (500MHz / CDCl ₃ ): δ -0.8 to 0.4 (s, Si-SiMe ₃ ) ppm

Example 7: Preparation of Compound of Formula 2 (R _One = Phenyl, R ₃ = Methyl)

A four-neck 1000 ml round bottom flask was equipped with a reflux condenser, a 20 ml / 300 ml dropping funnel and a Dean-Stark tube, and flame dried in a nitrogen atmosphere. 50 g of the cyclic tetraphenylsilsesquioxane obtained in Example 1 was added to a flask and dissolved in 380 ml of toluene. Then, 46 g of dichlorodimethylsilane was added dropwise through a dropping funnel and reacted at room temperature. After the reaction for 4 hours, the reactor was lowered to 3C, 250 ml of secondary distilled water was added dropwise to the reaction solution, and then hydrolyzed for 1 hour. Then, 5 mg of KOH, a polymerization catalyst, was added and then reacted for 38 hours at the reflux temperature of toluene. After the reaction, the mixture was added dropwise to methanol, stirred for 30 minutes, and the precipitate formed was filtered to obtain a reaction product (yield: 96%) as a white powder.

GPC (PSt): Mn = 42,000, Mw / Mn = 1.37

¹ H NMR (500 MHz / CDCl ₃ ): δ -0.8 to 0.4 (s, Si-Me), -7.1 to 7.86 (s, Si-Ph) ppm

²⁹ Si NMR (99.3 MHz / CDCl ₃ ): δ -54.8 (Me-T ₂ ), -80.7 (s, Ph-T ₃ ) ppm

Example 8: Preparation of Compound of Formula 3 (R _One = Phenyl, R ₃ = Methyl)

A four-neck 1000 ml round bottom flask was equipped with a reflux condenser, a 20 ml / 300 ml dropping funnel and a Dean-Stark tube, and flame dried in a nitrogen atmosphere. 50 g of the cyclic tetraphenylsilsesquioxane obtained in Example 1 was added to the flask and dissolved in 380 ml of toluene. Then, 54 g of trichloromethylsilane was added dropwise through a dropping funnel and reacted at room temperature. After the reaction for 1 hour, the reaction apparatus was lowered to 3C, 250 ml of secondary distilled water was added dropwise to the reaction solution, and then hydrolyzed for 1 hour. Then, 5 mg of KOH, which was a polymerization catalyst, was added and then reacted for 38 hours at the toluene reflux temperature. After the reaction, the mixture was added dropwise to methanol, stirred for 30 minutes, and the resulting precipitate was filtered, and a reaction product of a white powder (yield: 98%) was obtained. The reaction product of a white powder was subjected to 1 reaction at 150 ° C. and 4 Torr. It was used as analytical sample after time heat curing.

GPC (PSt): Mn = 42,000, Mw / Mn = 1.37

¹ H NMR (500 MHz / CDCl ₃ ): δ -0.8 to 0.4 (s, Si-Me), -7.1 to 7.86 (s, Si-Ph) ppm

IR (KBr): 3080-2940 (CH), 1600, 1435, 1120 (Si-Ph), 1050, 1150 (O-Si),

750, 700 (Ph), 1275, 800 (Si-Me) cm ^-1

²⁹ Si NMR (99.3 MHz / CDCl ₃ ): δ-56 (Me-T ₂ ), -64.6 (s, Me-T ₃ ), -80.7 (s, Ph-T ₃ ) ppm

Example 9: Preparation of Compound of Formula 2 (R _One = Phenyl, R ₃ = Methyl)

A four-neck 500 ml round bottom flask was equipped with a reflux condenser, a 100 ml dropping funnel and a Dean-Stark tube, and then flame-dried in a nitrogen atmosphere. 50 g of the cyclic tetraphenylsilsesquioxane obtained in Example 1 was added to the flask, 380 ml of toluene was dissolved and 0.5 ml of HCl was added as a reaction catalyst, and 46 g of dimethoxydimethylsilane was slowly added dropwise through a dropping funnel. The reaction was carried out at room temperature for 38 hours. After the reaction, the reaction solution was further reacted for 72 hours at the reflux temperature of toluene. After the reaction, the reaction mixture was added dropwise to methanol, stirred for 30 minutes, and the resulting precipitate was filtered to give a reaction product (yield: 87%) as a white powder.

GPC (PSt): Mn = 28,000, Mw / Mn = 1.62

¹ H NMR (500 MHz / CDCl ₃ ): δ -0.8 to 0.4 (s, Si-Me), -7.1 to 7.8 (s, Si-Ph) ppm

²⁹ Si NMR (99.3 MHz / CDCl ₃ ): δ -54.0 (Me-T ₂ ), -79.4 (s, Ph-T ₃ ) ppm

Example 10 Preparation of a Compound of Formula 3 (R _One = Phenyl, R ₃ = Methyl)

A four-neck 500 ml round bottom flask was equipped with a reflux condenser, a 100 ml dropping funnel and a Dean-Stark tube, and then flame-dried in a nitrogen atmosphere. 50 g of the cyclic tetraphenylsilsesquioxane obtained in Example 1 was added to the flask, 380 ml of toluene was dissolved, and 0.75 ml of HCl was added as a reaction catalyst, and 54 g of trimethoxymethylsilane was slowly added dropwise through a dropping funnel. The reaction was carried out at room temperature for 38 hours. After the reaction, the reaction solution was further reacted for 72 hours at the reflux temperature of toluene. After the reaction, the mixture was added dropwise to methanol, stirred for 30 minutes, and the resulting precipitate was filtered to give a reaction product (yield: 84%) as a white powder.

The reaction product of the white powder was used as an analytical sample after heat curing at 150 ℃, 4 Torr for 1 hour.

GPC (PSt): Mn = 22,000, Mw / Mn = 1.78

¹ H NMR (500 MHz / CDCl ₃ ): δ -0.8 to 0.4 (s, Si-Me), -7.1 to 7.86 (s, Si-Ph) ppm

²⁹ Si NMR (99.3 MHz / CDCl ₃ ): δ -54 (Me-T ₂ ), -62.6 (s, Me-T ₃ ), -79.7 (s, Ph-T ₃ ) ppm

Optimal embodiments of the present invention described above have been disclosed. Although specific terms have been used herein, they are used only for the purpose of describing the present invention and are not intended to limit the scope of the present invention as defined in the meaning or claims.

According to the present invention described above, unlike a polyorganosilsesquioxane obtained by heat condensation of an oligomer obtained by hydrolyzing trichlorosilane or triethoxysilane, a cyclic tetraorga which is a precursor is first reacted with an organosilanetriol. Since polycondensation is obtained after polycondensation of nosyl sesquioxane to obtain polyorganosilsesquioxane, a highly regular ladder polymer can be synthesized due to the structural characteristics of the cyclic tetraorgano silsesquioxane, which is a repeating unit structure.

In this way, since the siloxane bond (Si-O-Si) and the ladder structure can be easily formed in the polymer backbone, high heat resistance can be maintained, and the existence ratio of hydroxy groups to each other or to the defect structure can be reduced. This eliminates the need for heat treatment and allows the introduction of a variety of functional side chains (photosensitive groups, dealkylated reactive groups, etc.), especially changes in the physical properties of polymers and new properties depending on the composition of introduced side chain ratios (e.g. The molecular design of the polymer can be made possible, and the silanol end groups can be uniformly arranged at the end of the polymer, so that the introduction amount of the organic polymer of the organic or inorganic hybrid production can be controlled to easily prepare the organic or inorganic copolymer. Has the advantage.

In particular, the polyorganosilsesquioxane prepared according to the method provided by the present invention has a siloxane bond (Si-O-Si) and a rigid ladder structure (R-O-Si) in the main chain than the polyorganosilsesquioxane prepared by the conventional method. -SiO _3/2 ) has a unique molecular structure containing 90% or more (number of R-SiO _3/2 ÷ (number of hydroxyl groups + silanol terminal groups) x 100), solubility in general organic solvents It exhibits high heat resistance (temperature of pyrolysis starting above 500 ° C), weather resistance, low surface tension, optical transparency, low dielectric constant (less than 3.0) and low absorption rate, excellent gap filling capability, and the like. In addition, different side chains have excellent properties such as adhesion, electrical insulation, drainage, chemical resistance, and transparency to metals such as aluminum, copper, titanium, and glass, and commercial applications utilizing these properties in a wide range of industrial materials. UV curable resins and silane compounds are widely used in the polyorganosilsesquioxane produced by the present invention, but glass resins are widely used in some cases. Examples of the material include polycarbonate, acrylic resin, diethyl glycol bisalkyl carbonate (trade name "CR-39"), and the use thereof includes plastics, sunglasses, safety glasses, dashboards, automobile lamps, aircraft window glass, bulletproof glass, and the like. Can be used. It may also be used for the purpose of heat-treating the spectacle lens with glass resin.

In addition, the polyorganosilsesquioxane obtained according to the present invention is excellent in electrical insulation, heat resistance, low water absorption, flattening effect of spin-on glass (SOG) solution, and is suitable for use in electronic relations. For example, a protective coating film of a thin film, an interlayer insulating film of an LSI multi-impedance wiring, a low dielectric material may be used as a low dielectric material, a multilayer insulating film, a liquid crystal display insulating film, and the like. Since the gap between them is considerably narrow, the film thickness of a coating film formation inevitably becomes thick and the problem which a crack generate | occur | produces is pointed out. Such cracking can be caused by 1) shrinkage stress caused by condensation of hydroxy and inter-hydroxy groups or terminal-silanol groups, and 2) cured film, aluminum wiring, and silicon wafer. It is known to be due to the difference in thermal stress due to the difference in the coefficient of thermal expansion with the silicon wafer, the present invention is low in the presence of hydroxy groups (inter-hydroxy) in the polymer structure, the silanol terminal silicide (silylation ), The introduction of a double bond, a polymer material, in particular, by introducing a polyimide, polyamide, PMMA, polyacryl and the like to block the occurrence of the reaction at the end has the advantage that can solve the conventional problems.

Furthermore, the polyorganosilsesquioxane prepared according to the present invention can be dissolved in various solvents to form a thin film easily, have high hardness for thermosetting, and can form a thin film having good transparency. By commercializing, the long-term reliability of the optical fiber can be improved. Moreover, since it can be used as a material which forms a coating layer on the surface of a resistor, it can be applied also to an electrical material.

And when molding plastic such as urethane RIM (Reactive Injection Molding), it can be used as a metal release agent. It can also be used as a release agent in the manufacture of glass bottles. In addition, the polyorganosilsesquioxane provided in the present invention can be mixed with RTV and used as a tile adhesive for a space shuttle, and can also be used as a binding agent for an optical fiber, and features such as outer coating and heat resistance and corrosion resistance of a space shuttle. It can also be used for heat-resistant paints. End products provided by the present invention listed above will continue to be expanded with the development of the state of the art, so that the scope of application is not limited to the above uses, the expansion of the use will be infinite.

Claims (8)

A compound of formula Wherein R ₁ and R ₃ are each independently hydrogen, a substituted or unsubstituted aliphatic hydrocarbon group having 1 to 30 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon group having 1 to 30 carbon atoms, or 1 to 30 carbon atoms Substituted or unsubstituted alicyclic hydrocarbon group, substituted or unsubstituted silyl group having 1 to 30 carbon atoms, substituted or unsubstituted allyl group having 1 to 30 carbon atoms, substituted or unsubstituted child having 1 to 30 carbon atoms Represents an actual group, a vinyl group, an amine group, an acetate or an alkali metal, l represents an integer of 2 to 300,000, which is a multiple of 2, and m and n represent an integer of 2 to 300,000.) The compound according to claim 1, wherein R ₁ and R ₃ each independently represent hydrogen, methyl group, phenyl group, vinyl group or trimethylsilyl group, l represents an integer of 1,000 to 100,000 which is a multiple of 2, and m and n are 1,000 to 100,000 Compound of formula 2, characterized in that. A process for preparing a compound of formula 2, comprising polycondensation of a compound of formula 4 with a compound of formula 6 or a compound of formula 7 in an organic solvent: Wherein R ₁ and R ₃ are each independently hydrogen, a substituted or unsubstituted aliphatic hydrocarbon group having 1 to 30 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon group having 1 to 30 carbon atoms, or 1 to 30 carbon atoms Substituted or unsubstituted alicyclic hydrocarbon group, substituted or unsubstituted silyl group having 1 to 30 carbon atoms, substituted or unsubstituted allyl group having 1 to 30 carbon atoms, substituted or unsubstituted child having 1 to 30 carbon atoms Represents a real group, a vinyl group, an amine group, an acetate or an alkali metal, R ₂ represents hydrogen, methyl, acetate, sodium or potassium, X represents a halogen, l represents an integer of 2 to 300,000, which is a multiple of 2, m and n represent integers from 2 to 300,000.) The method according to claim 3, wherein the polycondensation reaction is any one selected from heating reaction, light irradiation reaction, microwave irradiation reaction or electron beam irradiation reaction. The method according to claim 3, wherein the amount of the compound of Formula 4 is 5 to 300 parts by weight based on 100 organic solvents. 4. A process according to claim 3, which is further carried out in the presence of a polycondensation reaction catalyst. The polycondensation reaction catalyst according to claim 6, wherein the polycondensation reaction catalyst is sodium hydroxide, potassium hydroxide, cesium hydroxide, triethylamine, diethylene triamine, meta-butylamine, para-dimethylamine ethanol, triethanolamine, quaternary ammonium salts, or fluorine. At least one material selected from the group consisting of cargo. The method of claim 6, wherein the polycondensation reaction catalyst is used in an amount of 0.001 to 5 parts by weight based on 100 parts by weight of the compound of Formula 4.