High-temperature resistant modified silicon-containing cyanate ester resin as well as preparation method and application thereof

Abstract

The present invention relates to a high-temperature resistant modified silicon-containing cyanate ester resin as well as a preparation method and an application thereof. The preparation method comprises the following steps: adding a mixed solution of hydroxyl silicone oil, a silane coupling agent and an organic solvent into a mixed solution of a tetramethylammonium hydroxide aqueous solution and a polar solvent, performing hydrolytic polycondensation at a temperature of 5-40 C. for 4-8 h, and performing distillation to obtain an epoxy-containing silsesquioxane; performing pre-polymerization on the epoxy-containing silsesquioxane and a cyanate ester resin at a temperature of 50-100 C. for 1-8 h to obtain a modified cyanate ester resin; and uniformly mixing the modified cyanate ester resin and a modified anhydride, thereby obtaining the high-temperature resistant modified silicon-containing cyanate ester resin.

Claims

1. A preparation method of a high-temperature resistant modified silicon-containing cyanate ester resin, comprising the following steps: step (1), adding a first mixed solution into a second mixed solution, performing hydrolytic polycondensation at a temperature of 5-40 C. for 4-8 h, and then performing distillation to obtain an epoxy-containing silsesquioxane; wherein the first mixed solution comprises hydroxyl silicone oil, a silane coupling agent and an organic solvent; the second mixed solution comprises a tetramethylammonium hydroxide aqueous solution and a polar solvent; step (2), performing pre-polymerization on the epoxy-containing silsesquioxane obtained in the step (1) and a cyanate ester resin at a temperature of 50-100 C. for 1-8 h to obtain a modified cyanate ester resin; and step (3), uniformly mixing the modified cyanate ester resin obtained in the step (2) and an anhydride, thereby obtaining the high-temperature resistant modified silicon-containing cyanate ester resin.

2. The preparation method of the high-temperature resistant modified silicon-containing cyanate ester resin according to claim 1, wherein a mass fraction of the tetramethylammonium hydroxide aqueous solution in the second mixed solution is 5-20%.

3. The preparation method of the high-temperature resistant modified silicon-containing cyanate ester resin according to claim 1, wherein the polar solvent is selected from n-butyl alcohol or isopropanol; and the organic solvent is selected from methanol, ethanol, benzene, methylbenzene, xylene or cyclohexane.

4. The preparation method of the high-temperature resistant modified silicon-containing cyanate ester resin according to claim 1, wherein the silane coupling agent is selected from -(2,3-epoxypropoxy) propyl trimethoxysilane or -(3,4-epoxycyclohexyl) ethyl trimethoxysilane.

5. The preparation method of the high-temperature resistant modified silicon-containing cyanate ester resin according to claim 1, wherein the cyanate ester resin is selected from one or more of bisphenol A cyanate ester resin monomers or prepolymers thereof, bisphenol E cyanate ester resins, phenolic cyanate ester resins, bisphenol F cyanate ester resins, bisphenol M cyanate ester resins and dicyclopentadiene cyanate ester resins; and the anhydride is selected from one or more of methyl tetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methyl nadic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, 5-norbornene-2,3-dicarboxylic anhydride, methyl-5-norbornene-2,3-dicarboxylic anhydride, methyl endo-methylene hexahydrophthalic anhydride, glutaric anhydride, terpene acid anhydride, methylcyclohexene tetracarboxylic dianhydride, dodecenyl succinic anhydride, tetrabromophthalic anhydride, tetrachlorophthalic anhydride, methyl tetrabromophthalic anhydride, methyl tetrachlorophthalic anhydride, hexachloro-endo-methylene tetrahydrophthalic anhydride, diglycerol (dehydrated trimellitate) acetic ester, benzenetetracarboxylic anhydride and benzophenonetetracarboxylic dianhydride.

6. The preparation method of the high-temperature resistant modified silicon-containing cyanate ester resin according to claim 1, wherein a feed ratio by weight of the tetramethylammonium hydroxide aqueous solution to the polar solvent to the hydroxyl silicone oil to the silane coupling agent to the organic solvent is (0.5-10):(15-200):1:(4-60):(3-6).

7. The preparation method of the high-temperature resistant modified silicon-containing cyanate ester resin according to claim 1, wherein an adding speed of adding the first mixed solution into the second mixed solution is controlled to be 18-75 g/h.

8. The preparation method of the high-temperature resistant modified silicon-containing cyanate ester resin according to claim 1, wherein a feed ratio by weight of the epoxy-containing silsesquioxane to the cyanate ester resin to the anhydride is 1:(8-10):(13-15).

9. A high-temperature resistant modified silicon-containing cyanate ester resin prepared by the preparation method of claim 1.

10. A method, the method comprising: utilizing the high-temperature resistant modified silicon-containing cyanate ester resin of claim 9 in a carbon fiber compound core conductor.

Description

DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS

(1) The present invention is further described below in detail in combination with specific embodiments. However, the present invention is not limited to the following embodiments.

Embodiment 1

(2) steps: (a) adding 400 g of n-butyl alcohol and 20 g of tetramethylammonium hydroxide aqueous solution (with a mass fraction of 10%) into 1000 mL of three-mouth flask with a thermometer and a condensing tube, stirring and mixing uniformly, dropping 20 g of hydroxyl-terminated polydimethylsiloxane and a mixed solution of 120 g of -(2,3-epoxypropoxy) propyl trimethoxysilane and 80 g of ethanol into the above solution, controlling a dropping speed to complete dropping within 3 h, controlling a reaction temperature to 10 C., performing hydrolytic polycondensation for 6 h, and distilling off residual solvent and small molecules in the system by a rotary evaporator after the reaction is ended, thereby obtaining transparent viscous liquid capable of flowing at a room temperature for later use, i.e., the epoxy-containing silsesquioxane (G-POSS);

(3) (b) pouring 30 g of the viscous liquid (G-POSS) and 270 g of bisphenol A cyanate ester resin into 500 mL of three-mouth flask and stirring uniformly, carrying out a pre-polymerization reaction at a temperature of 80-90 C. for 2 h, cooling the modified resin to the room temperature for later use, and measuring viscosity of the modified resin to be 5300 cps; and

(4) (c) pouring 420 g of modified methyl tetrahydrophthalic anhydride into 2000 ml of beaker, weighing 300 g of the above modified resin and adding into the beaker, uniformly stirring for 5-10 min, and testing various properties.

(5) Test results of main properties of a modified resin cured matter are shown in Table 1.

Embodiment 2

(6) steps: (a) adding 400 g of n-butyl alcohol and 20 g of tetramethylammonium hydroxide aqueous solution (with a mass fraction of 10%) into 1000 mL of three-mouth flask with a thermometer and a condensing tube, stirring and mixing uniformly, dropping 20 g of hydroxyl-terminated polydimethylsiloxane and a mixed solution of 120 g of -(2,3-epoxypropoxy) propyl trimethoxysilane and 80 g of ethanol into the above solution, controlling a dropping speed to complete dropping within 3 h, controlling a reaction temperature to 10 C., performing hydrolytic polycondensation for 6 h, and distilling off residual solvent and small molecules in the system by a rotary evaporator after the reaction is ended, thereby obtaining transparent viscous liquid capable of flowing at a room temperature for later use, i.e., a final product of epoxy-containing silsesquioxane (G-POSS);

(7) (b) pouring 30 g of the viscous liquid (G-POSS) and 270 g of bisphenol F cyanate ester resin into 500 mL of three-mouth flask and stirring uniformly, carrying out a pre-polymerization reaction at a temperature of 80-90 C. for 2 h, cooling the modified resin to the room temperature for later use, and measuring viscosity of the modified resin to be 3050 cps; and

(8) (c) pouring 420 g of modified methyl tetrahydrophthalic anhydride into 2000 ml of beaker, weighing 300 g of the above modified resin and adding into the beaker, uniformly stirring for 5-10 min, and testing various properties.

(9) Test results of main properties of a modified resin cured matter are shown in Table 1.

Embodiment 3

(10) steps: (a) adding 400 g of n-butyl alcohol and 16 g of tetramethylammonium hydroxide aqueous solution (with a mass fraction of 10%) into 1000 mL of three-mouth flask with a thermometer and a condensing tube, stirring and mixing uniformly, dropping 26 g of hydroxyl-terminated polydimethylsiloxane and a mixed solution of 127 g of -(2,3-epoxypropoxy) propyl trimethoxysilane and 90 g of ethanol into the above solution, controlling a dropping speed to complete dropping within 3.5 h, controlling a reaction temperature to 10 C., performing hydrolytic polycondensation for 5 h, and distilling off residual solvent and small molecules in the system by a rotary evaporator after the reaction is ended, thereby obtaining transparent viscous liquid capable of flowing at a room temperature for later use, i.e., a final product of epoxy-containing silsesquioxane (G-POSS);

(11) (b) pouring 30 g of the viscous liquid (G-POSS) and 270 g of bisphenol F cyanate ester resin into 500 mL of three-mouth flask and stirring uniformly, carrying out a pre-polymerization reaction at a temperature of 80-90 C. for 2 h, cooling the modified resin to the room temperature for later use, and measuring viscosity of the modified resin to be 5100 cps; and

(12) (c) pouring 420 g of modified methyl nadic anhydride into 2000 ml of beaker, weighing 300 g of the above modified resin and adding into the beaker, uniformly stirring for 5-10 min, and testing various properties.

(13) Test results of main properties of a modified resin cured matter are shown in Table 1.

Embodiment 4

(14) steps: (a) adding 400 g of n-butyl alcohol and 25 g of tetramethylammonium hydroxide aqueous solution (with a mass fraction of 10%) into 1000 mL of three-mouth flask with a thermometer and a condensing tube, stirring and mixing uniformly, dropping 15 g of hydroxyl-terminated polydimethylsiloxane and a mixed solution of 130 g of -(2,3-epoxypropoxy) propyl trimethoxysilane and 80 g of ethanol into the above solution, controlling a dropping speed to complete dropping within 4 h, controlling a reaction temperature to 10 C., performing hydrolytic polycondensation for 7 h, and distilling off residual solvent and small molecules in the system by a rotary evaporator after the reaction is ended, thereby obtaining transparent viscous liquid capable of flowing at a room temperature for later use, i.e., a final product of epoxy-containing silsesquloxane (G-POSS);

(15) (b) pouring 45 g of the viscous liquid (G-POSS) and 255 g of bisphenol F cyanate ester resin into 500 mL of three-mouth flask and stirring uniformly, carrying out a pre-polymerization reaction at a temperature of 80-90 C. for 3 h, cooling the modified resin to the room temperature for later use, and measuring viscosity of the modified resin to be 4200 cps; and

(16) (c) pouring 420 g of modified methyl nadic anhydride into 2000 ml of beaker, weighing 300 g of the above modified resin and adding into the beaker, uniformly stirring for 5-10 min, and testing various properties.

(17) Test results of main properties of a modified resin cured matter are shown in Table 1.

(18) TABLE-US-00001 TABLE 1 Performance indexes Embodiment 1 Embodiment 2 Embodiment 3 Embodiment 4 Appearance color Yellowish-brown Yellowish-brown Yellowish-brown Yellowish-brown Viscosity (mPa . s/25 C.) 580 425 630 670 Working life (h/25 C.) 8-10 8-10 8-10 8-10 Gelation time (min/200 C.) 14 13 15 15 Glass transition temperature 245 258 265 262 Tg( C.) Tensil test Tensile 90 95 98 97 strength MPa Tensile 2.4 2.3 2.1 2.1 deformation % Tensile 2400 2500 2550 2500 modulus MPa Bending test Bending 75 80 82 85 strength MPa Bending 3.7 3.1 3.2 3.1 deformation % Bending 2400 2460 2510 2520 modulus MPa Compression Compression 210 220 230 235 test strength MPa Compressive 23 21 20 20 deformation % Compression 2200 2340 2460 2510 modulus MPa

Reference Embodiment 1

(19) steps: (a) adding 400 g of n-butyl alcohol and 20 g of tetramethylammonium hydroxide aqueous solution (with a mass fraction of 10%) into 1000 mL of three-mouth flask with a thermometer and a condensing tube, stirring and mixing uniformly, dropping 20 g of hydroxyl-terminated polydimethylsiloxane and a mixed solution of 120 g of -(2,3-epoxypropoxy) propyl trimethoxysilane and 80 g of ethanol into the above solution, controlling a dropping speed to complete dropping within 3 h, controlling a reaction temperature to 10 C., performing hydrolytic polycondensation for 1 h, and distilling off residual solvent and small molecules in the system by a rotary evaporator after the reaction is ended, thereby obtaining transparent viscous liquid capable of flowing at a room temperature for later use, i.e., the epoxy-containing silsesquioxane (G-POSS);

(20) (b) pouring 30 g of the viscous liquid (G-POSS) and 270 g of bisphenol A cyanate ester resin into 500 mL of three-mouth flask and stirring uniformly, carrying out a pre-polymerization reaction at a temperature of 80-90 C. for 2 h, cooling the modified resin to the room temperature for later use, and measuring viscosity of the modified resin to be 4300 cps; and

(21) (c) pouring 420 g of modified methyl tetrahydrophthalic anhydride into 2000 ml of beaker, weighing 300 g of the above modified resin and adding into the beaker, uniformly stirring for 5-10 min, and testing various properties.

(22) Test results of main properties of a modified resin cured matter are shown in Table 2.

Reference Embodiment 2

(23) steps: (a) adding 400 g of n-butyl alcohol and 20 g of tetramethylammonium hydroxide aqueous solution (with a mass fraction of 10%) into 1000 mL of three-mouth flask with a thermometer and a condensing tube, stirring and mixing uniformly, dropping 20 g of hydroxyl-terminated polydimethylsiloxane and a mixed solution of 120 g of -(2,3-epoxypropoxy) propyl trimethoxysilane and 80 g of ethanol into the above solution, controlling a dropping speed to complete dropping within 3 h, controlling a reaction temperature to 0 C., performing hydrolytic polycondensation for 6 h, and distilling off residual solvent and small molecules in the system by a rotary evaporator after the reaction is ended, thereby obtaining transparent viscous liquid capable of flowing at a room temperature for later use, i.e., epoxy-containing silsesquioxane (G-POSS);

(24) (b) pouring 30 g of the viscous liquid (G-POSS) and 270 g of bisphenol A cyanate ester resin into 500 mL of three-mouth flask and stirring uniformly, carrying out a pre-polymerization reaction at a temperature of 80-90 C. for 2 h, cooling the modified resin to the room temperature for later use, and measuring viscosity of the modified resin to be 4100 cps; and

(25) (c) pouring 420 g of modified methyl tetrahydrophthalic anhydride into 2000 ml of beaker, weighing 300 g of the above modified resin and adding into the beaker, uniformly stirring for 5-10 min, and testing various properties.

(26) Test results of main properties of a modified resin cured matter are shown in Table 2.

Reference Embodiment 3

(27) steps: (a) adding 400 g of n-butyl alcohol and 20 g of tetramethylammonium hydroxide aqueous solution (with a mass fraction of 10%) into 1000 mL of three-mouth flask with a thermometer and a condensing tube, stirring and mixing uniformly, dropping 20 g of hydroxyl-terminated polydimethylsiloxane and a mixed solution of 120 g of -(2,3-epoxypropoxy) propyl trimethoxysilane and 80 g of ethanol into the above solution, controlling a dropping speed to complete dropping within 3 h, controlling a reaction temperature to 10 C., performing hydrolytic polycondensation for 6 h, and distilling off residual solvent and small molecules in the system by a rotary evaporator after the reaction is ended, thereby obtaining transparent viscous liquid capable of flowing at a room temperature for later use, i.e., epoxy-containing silsesquioxane (G-POSS);

(28) (b) pouring 30 g of the viscous liquid (G-POSS) and 270 g of bisphenol A cyanate ester resin into 500 mL of three-mouth flask and stirring uniformly, carrying out a pre-polymerization reaction at a temperature of 60 C. for 1 h, cooling the modified resin to the room temperature for later use, and measuring viscosity of the modified resin to be 5100 cps; and

(29) (c) pouring 420 g of modified methyl nadic anhydride into 2000 ml of beaker, weighing 300 g of the above modified resin and adding into the beaker, uniformly stirring for 5-10 min, and testing various properties.

(30) Test results of main properties of a modified resin cured matter are shown in Table 2.

(31) TABLE-US-00002 TABLE 2 Reference Reference Reference Performance embodiment embodiment embodiment indexes 1 2 3 Appearance color Yellowish- Yellowish- Yeowish- brown brown brown Viscosity(mPa . s/25 C.) 430 420 500 Working life(h/25 C.) 8-10 8-10 8-10 Gelation time (min/200 C.) 15 16 14 Glass transition temperature 225 210 230 Tg( C.) Tensile Tensile strength 80 75 87 test MPa Tensile 1.9 1.7 2.1 deformation % 4 Tensile modulus 2050 1900 2250 MPa Bending Bending 60 45 70 test strength MPa Bending 2.9 2.5 3.4 deformation % Bending 1900 1750 2260 modulus MPa Com- Compression 175 150 190 pression strength MPa test Compressive 18 16 21 deformation % Compression 1850 1500 2170 modulus MPa

(32) The present invention is described above in detail, intended to enable those skilled in the art to know and implement contents of the present invention, not intended to limit a protection scope of the present invention. All equivalent changes or modifications made according to spiritual essence of the present invention should be included in the protection scope of the present invention.