CN113337075B - Two-component polysiloxane modified phenolic resin and preparation method thereof - Google Patents
Two-component polysiloxane modified phenolic resin and preparation method thereof Download PDFInfo
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- CN113337075B CN113337075B CN202110471966.3A CN202110471966A CN113337075B CN 113337075 B CN113337075 B CN 113337075B CN 202110471966 A CN202110471966 A CN 202110471966A CN 113337075 B CN113337075 B CN 113337075B
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- C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
- C08L61/04—Condensation polymers of aldehydes or ketones with phenols only
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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Abstract
The invention discloses a two-component polysiloxane modified phenolic resin and a preparation method thereof, belonging to the technical field of phenolic resin, wherein cross-linked polysiloxane and polysiloxane nano microspheres are added into a phenolic resin material; the cross-linked polysiloxane is a cross-linked network structure, and the elasticity and toughness of the phenolic resin can be fully improved after the phenolic resin is added; the polysiloxane nanometer microspheres are of a micro-nano structure, a large number of pores are contained in the polysiloxane nanometer microspheres, and a large number of microporous structures with excellent mechanical properties can be introduced into the resin after the phenolic resin is added, so that the phenolic resin has better flexibility.
Description
Technical Field
The invention relates to the technical field of phenolic resin, in particular to two-component polysiloxane modified phenolic resin and a preparation method thereof.
Background
The phenolic resin is a high-performance and multipurpose functional polymer material obtained by performing polycondensation reaction on a phenolic compound and formaldehyde. The phenolic resin contains a rigid benzene ring structure, and the benzene rings are connected through flexible methylene, so that the material has excellent high temperature resistance, acid and alkali resistance, flame retardance and the like, and is widely applied to the building industry, the transportation industry and the manufacturing industry.
The addition of the phenolic resin into the tire rubber can obviously improve the mechanical strength and hardness of the rubber and endow the tire rubber with good aging resistance, so that the phenolic resin is widely applied to radial tires, steel wire coating rubber, bead filler and the like of automobiles. However, when preparing tire rubber, the compatibility of the phenolic resin and other auxiliary materials is general, which causes the inner structure of the tire to be uneven and the quality of the tire product to be unstable. In addition, the phenolic resin has high brittleness, and the toughness of the product is easily reduced after the phenolic resin is added into the tire rubber, so that the service life of the rubber is shortened. Therefore, the modification of the performance of the phenolic resin material is urgently needed in the industry, the toughness of the phenolic resin material is improved on the basis of ensuring the mechanical strength and the hardness of the phenolic resin material, and meanwhile, the compatibility of the phenolic resin and auxiliary materials for tire rubber is improved.
Disclosure of Invention
In order to solve the problems, the performance of the phenolic resin material is modified, the toughness of the phenolic resin material is improved on the basis of ensuring the mechanical strength and the hardness of the phenolic resin material, and meanwhile, the compatibility of the phenolic resin and auxiliary materials for tire rubber is improved.
In order to achieve the purpose, the invention is realized by the following technical scheme:
the two-component polysiloxane modified phenolic resin comprises the following raw materials in parts by weight: 110-120 parts of phenol, 70-80 parts of formaldehyde aqueous solution, 24-33 parts of cross-linked polysiloxane, 15-28 parts of polysiloxane nano microspheres, 8-15 parts of benzoxazine and 0.05-0.4 part of organic acid;
the mass concentration of the formaldehyde aqueous solution is 20-35%;
the organic acid is formic acid or dodecyl benzene sulfonic acid;
wherein the cross-linked polysiloxane is prepared according to the following method:
heating phenyl tri (dimethylsiloxy) silane and tetramethylammonium hydroxide to 70 ℃ under the protection of nitrogen, dropwise adding 1, 2-bis (trimethoxysilylethane) and 3-mercaptopropyl methyldimethoxysilane to obtain a mixed solution, ensuring the temperature of the mixed solution to be 70-90 ℃ in the dropwise adding process, heating to 110-120 ℃ after dropwise adding, and stirring for reacting for 1-3 hours to obtain crosslinked polysiloxane;
wherein the mass ratio of phenyltri (dimethylsiloxy) silane to tetramethylammonium hydroxide to 1, 2-bistrimethoxysilyl ethane to 3-mercaptopropylmethyldimethoxysilane is 100-110: 0.04-0.12: 42-50: 33 to 38;
the polysiloxane nano-microsphere is prepared by the following method:
adding vinyltriethoxysilane, graphene, deionized water and polyethylene pyrrolidone into a reaction bottle, starting stirring, heating to 25-40 ℃, adjusting the pH value to 3.5-5.5 with a hydrochloric acid aqueous solution, stirring for reaction for 1-3 hours, adding ammonia water to adjust the pH value to 6.5-8.0, centrifuging, filtering, and obtaining a filter cake which is polysiloxane nanosphere;
the mass ratio of the vinyltriethoxysilane to the graphene to the deionized water to the polyvinylpyrrolidone is 80-120: 10-15: 500-800: 0.5 to 2;
the polyvinyl pyrrolidone is polyvinyl pyrrolidone K30 or polyvinyl pyrrolidone K90;
the molar concentration of the hydrochloric acid aqueous solution is 2-4 mol/L;
the mass concentration of the ammonia water is 25-28%.
Preferably, the mass fraction of the formaldehyde aqueous solution is 25-30%.
Preferably, the organic acid is dodecylbenzene sulfonic acid.
Preferably, the polyvinyl pyrrolidone is polyvinyl pyrrolidone K90.
Preferably, the mass ratio of the phenyltri (dimethylsiloxy) silane to the tetramethylammonium hydroxide to the 1, 2-bistrimethoxysilyl ethane to the 3-mercaptopropylmethyldimethoxysilane is 108: 0.05: 45: 35.
the invention also comprises a preparation method of the double-component polysiloxane modified phenolic resin, which comprises the following steps in parts by weight:
adding 110-120 parts of phenol, 70-80 parts of formaldehyde aqueous solution and 8-15 parts of benzoxazine into a reaction kettle, heating to 50-90 ℃, adding 0.05-0.4 part of organic acid, stirring for reaction for 0.5-1.5 hours, adding 24-33 parts of cross-linked polysiloxane and 15-28 parts of polysiloxane nano microspheres, heating to 120-140 ℃, stirring for reaction for 1-2 hours, reducing the vacuum degree in the reaction kettle to 0-0.05 MPa, and stopping the reaction until the temperature of the reaction liquid reaches 150 ℃ to obtain the two-component polysiloxane modified phenolic resin;
the mass concentration of the formaldehyde aqueous solution is 20-35%;
the organic acid is formic acid or dodecyl benzene sulfonic acid;
wherein the cross-linked polysiloxane is prepared according to the following method:
heating phenyl tri (dimethylsiloxy) silane and tetramethylammonium hydroxide to 70 ℃ under the protection of nitrogen, dropwise adding 1, 2-bis (trimethoxysilylethane) and 3-mercaptopropyl methyldimethoxysilane to obtain a mixed solution, ensuring the temperature of the mixed solution to be 70-90 ℃ in the dropwise adding process, heating to 110-120 ℃ after dropwise adding, and stirring for reacting for 1-3 hours to obtain crosslinked polysiloxane;
wherein the mass ratio of phenyltri (dimethylsiloxy) silane to tetramethylammonium hydroxide to 1, 2-bistrimethoxysilyl ethane to 3-mercaptopropylmethyldimethoxysilane is 100-110: 0.04-0.12: 42-50: 33 to 38;
the polysiloxane nano-microsphere is prepared by the following method:
adding vinyltriethoxysilane, graphene, deionized water and polyethylene pyrrolidone into a reaction bottle, starting stirring, heating to 25-40 ℃, adjusting the pH value to 3.5-5.5 with a hydrochloric acid aqueous solution, stirring for reaction for 1-3 hours, adding ammonia water to adjust the pH value to 6.5-8.0, centrifuging, filtering, and obtaining a filter cake which is polysiloxane nanosphere;
the mass ratio of the vinyltriethoxysilane to the graphene to the deionized water to the polyvinylpyrrolidone is 80-120: 10-15: 500-800: 0.5 to 2;
the polyvinyl pyrrolidone is polyvinyl pyrrolidone K30 or polyvinyl pyrrolidone K90;
the molar concentration of the hydrochloric acid aqueous solution is 2-4 mol/L;
the mass concentration of the ammonia water is 25-28%.
Compared with the prior art, the invention has the following advantages:
according to the two-component polysiloxane modified phenolic resin, cross-linked polysiloxane and polysiloxane nano microspheres are added into a phenolic resin material; the crosslinked polysiloxane is a crosslinked network structure, and the elasticity and toughness of the phenolic resin can be fully improved after the phenolic resin is added; the polysiloxane nanometer microspheres are of a micro-nano structure, a large number of pores are contained in the polysiloxane nanometer microspheres, and a large number of microporous structures with excellent mechanical properties can be introduced into the resin after the phenolic resin is added, so that the phenolic resin has better flexibility.
In addition, the cross-linked polysiloxane and the polysiloxane nano microspheres contain a large number of silane structures, have excellent biocompatibility with various auxiliary materials used in the preparation process of tire rubber, and can effectively prevent the problems of non-uniform tire internal structures and unstable tire product quality caused by poor compatibility of phenolic resin.
Detailed Description
The invention is further described with reference to specific examples.
Example 1
A two-component polysiloxane modified phenolic resin is composed of the following raw materials: 110kg of phenol, 70kg of formaldehyde aqueous solution, 24kg of cross-linked polysiloxane, 15kg of polysiloxane nano microspheres, 8kg of benzoxazine and 0.05kg of organic acid;
the mass concentration of the formaldehyde aqueous solution is 20%;
the organic acid is formic acid;
wherein the cross-linked polysiloxane is prepared according to the following method:
heating phenyl tri (dimethylsiloxy) silane and tetramethylammonium hydroxide to 70 ℃ under the protection of nitrogen, dropwise adding 1, 2-bis (trimethoxysilylethane) and 3-mercaptopropyl methyldimethoxysilane to obtain a mixed solution, ensuring the temperature of the mixed solution to be 70-75 ℃ in the dropwise adding process, heating to 110 ℃ after the dropwise adding is finished, and stirring for reacting for 1 hour to obtain crosslinked polysiloxane;
wherein the mass ratio of phenyltri (dimethylsiloxy) silane, tetramethylammonium hydroxide, 1, 2-bis (trimethoxysilylethane) and 3-mercaptopropylmethyldimethoxysilane is 100: 0.04: 42: 33;
the polysiloxane nano-microsphere is prepared by the following method:
adding vinyltriethoxysilane, graphene, deionized water and polyethylene pyrrolidone into a reaction bottle, stirring, heating to 25 ℃, adjusting the pH value to 3.5 with hydrochloric acid aqueous solution, stirring for reaction for 1 hour, adjusting the pH value to 6.5 with ammonia water, centrifuging, filtering, and obtaining a filter cake which is polysiloxane nanospheres;
wherein the mass ratio of the vinyltriethoxysilane to the graphene to the deionized water to the polyethylene pyrrolidone is 80: 10: 500: 0.5;
the polyvinyl pyrrolidone is polyvinyl pyrrolidone K30;
the molar concentration of the hydrochloric acid aqueous solution is 2 mol/L;
the mass concentration of the ammonia water is 25 percent.
Example 2
A two-component polysiloxane modified phenolic resin is composed of the following raw materials: 120kg of phenol, 80kg of formaldehyde aqueous solution, 33kg of cross-linked polysiloxane, 28kg of polysiloxane nano microspheres, 15kg of benzoxazine and 0.4kg of organic acid;
the mass concentration of the formaldehyde aqueous solution is 35%;
the organic acid is dodecyl benzene sulfonic acid;
wherein the cross-linked polysiloxane is prepared according to the following method:
heating phenyl tri (dimethylsiloxy) silane and tetramethylammonium hydroxide to 70 ℃ under the protection of nitrogen, dropwise adding 1, 2-bis (trimethoxysilylethane) and 3-mercaptopropyl methyldimethoxysilane to obtain a mixed solution, ensuring the temperature of the mixed solution to be 70-90 ℃ in the dropwise adding process, heating to 120 ℃ after the dropwise adding is finished, and stirring for reacting for 3 hours to obtain crosslinked polysiloxane;
wherein the mass ratio of phenyltri (dimethylsiloxy) silane to tetramethylammonium hydroxide to 1, 2-bistrimethoxysilyl ethane to 3-mercaptopropylmethyldimethoxysilane is 110: 0.12: 50: 38;
the polysiloxane nano-microsphere is prepared by the following method:
adding vinyltriethoxysilane, graphene, deionized water and polyethylene pyrrolidone into a reaction bottle, starting stirring, heating to 40 ℃, adjusting the pH value to 5.5 by using a hydrochloric acid aqueous solution, stirring for reaction for 3 hours, adjusting the pH value to 8.0 by adding ammonia water, centrifuging, filtering, and obtaining a filter cake which is polysiloxane nanospheres;
wherein the mass ratio of the vinyltriethoxysilane, the graphene, the deionized water to the polyethylene pyrrolidone is 120: 15: 800: 2;
the polyvinyl pyrrolidone is polyvinyl pyrrolidone K90;
the molar concentration of the hydrochloric acid aqueous solution is 4 mol/L;
the mass concentration of the ammonia water is 28%.
Example 3
A two-component polysiloxane modified phenolic resin is prepared from the following raw materials: 112kg of phenol, 78kg of formaldehyde water solution, 28kg of cross-linked polysiloxane, 20kg of polysiloxane nano microspheres, 12kg of benzoxazine and 0.2kg of organic acid;
the mass concentration of the formaldehyde aqueous solution is 25%;
the organic acid is formic acid;
wherein the cross-linked polysiloxane is prepared according to the following method:
heating phenyl tri (dimethylsiloxy) silane and tetramethylammonium hydroxide to 70 ℃ under the protection of nitrogen, dropwise adding 1, 2-bis (trimethoxysilylethane) and 3-mercaptopropyl methyldimethoxysilane to obtain a mixed solution, ensuring the temperature of the mixed solution to be 70-80 ℃ in the dropwise adding process, heating to 115 ℃ after dropwise adding, and stirring for reacting for 1.5 hours to obtain crosslinked polysiloxane;
wherein the mass ratio of phenyltri (dimethylsiloxy) silane to tetramethylammonium hydroxide to 1, 2-bistrimethoxysilyl ethane to 3-mercaptopropylmethyldimethoxysilane is 105: 0.08: 45: 35;
the polysiloxane nano-microsphere is prepared by the following method:
adding vinyltriethoxysilane, graphene, deionized water and polyethylene pyrrolidone into a reaction bottle, stirring, heating to 30 ℃, adjusting the pH value to 4.5 by using a hydrochloric acid aqueous solution, stirring for reacting for 1.5 hours, adjusting the pH value to 7.5 by adding ammonia water, centrifuging, filtering, and obtaining a filter cake which is polysiloxane nanospheres;
wherein the mass ratio of the vinyltriethoxysilane to the graphene to the deionized water to the polyvinyl pyrrolidone is 105: 12: 600: 1.2;
the polyvinyl pyrrolidone is polyvinyl pyrrolidone K30;
the molar concentration of the hydrochloric acid aqueous solution is 2.5 mol/L;
the mass concentration of the ammonia water is 26%.
Example 4
A two-component polysiloxane modified phenolic resin is prepared from the following raw materials: 115kg of phenol, 76kg of formaldehyde aqueous solution, 30kg of cross-linked polysiloxane, 25kg of polysiloxane nano-microspheres, 10kg of benzoxazine and 0.2kg of organic acid;
the mass concentration of the formaldehyde aqueous solution is 30 percent;
the organic acid is formic acid;
wherein the cross-linked polysiloxane is prepared according to the following method:
heating phenyl tri (dimethylsiloxy) silane and tetramethylammonium hydroxide to 70 ℃ under the protection of nitrogen, dropwise adding 1, 2-bis (trimethoxysilylethane) and 3-mercaptopropyl methyldimethoxysilane to obtain a mixed solution, ensuring the temperature of the mixed solution to be 80-85 ℃ in the dropwise adding process, heating to 115 ℃ after dropwise adding, and stirring for reacting for 2.5 hours to obtain crosslinked polysiloxane;
wherein the mass ratio of phenyltri (dimethylsiloxy) silane to tetramethylammonium hydroxide to 1, 2-bistrimethoxysilyl ethane to 3-mercaptopropylmethyldimethoxysilane is 108: 0.10: 48: 35;
the polysiloxane nano-microsphere is prepared by the following method:
adding vinyltriethoxysilane, graphene, deionized water and polyethylene pyrrolidone into a reaction bottle, stirring, heating to 30 ℃, adjusting the pH value to 4.5 by using a hydrochloric acid aqueous solution, stirring for reacting for 2.5 hours, adjusting the pH value to 7.0 by adding ammonia water, centrifuging, filtering, and obtaining a filter cake which is polysiloxane nanospheres;
wherein the mass ratio of the vinyltriethoxysilane to the graphene to the deionized water to the polyvinyl pyrrolidone is 110: 14: 700: 1.8;
the polyvinyl pyrrolidone is polyvinyl pyrrolidone K90;
the molar concentration of the hydrochloric acid aqueous solution is 3.5 mol/L;
the mass concentration of the ammonia water is 27%.
Example 5
A two-component polysiloxane modified phenolic resin is composed of the following raw materials: 115kg of phenol, 75kg of formaldehyde aqueous solution, 30kg of cross-linked polysiloxane, 25kg of polysiloxane nano-microspheres, 10kg of benzoxazine and 0.3kg of organic acid;
the mass concentration of the formaldehyde aqueous solution is 30 percent;
the organic acid is dodecyl benzene sulfonic acid;
wherein the cross-linked polysiloxane is prepared according to the following method:
taking phenyl tri (dimethylsiloxy) silane and tetramethylammonium hydroxide, heating to 70 ℃ under the protection of nitrogen, dropwise adding 1, 2-bis (trimethoxysilylethane) and 3-mercaptopropyl methyldimethoxysilane to obtain a mixed solution, ensuring that the temperature of the mixed solution is 80 ℃ in the dropwise adding process, heating to 115 ℃ after the dropwise adding is finished, and stirring for reacting for 2 hours to obtain crosslinked polysiloxane;
wherein the mass ratio of phenyltri (dimethylsiloxy) silane to tetramethylammonium hydroxide to 1, 2-bistrimethoxysilyl ethane to 3-mercaptopropylmethyldimethoxysilane is 108: 0.05: 45: 35;
the polysiloxane nano-microsphere is prepared by the following method:
adding vinyltriethoxysilane, graphene, deionized water and polyethylene pyrrolidone into a reaction bottle, stirring, heating to 30 ℃, adjusting the pH value to 5.0 by using a hydrochloric acid aqueous solution, stirring for reacting for 2 hours, adjusting the pH value to 7.0 by adding ammonia water, centrifuging, filtering, and obtaining a filter cake which is polysiloxane nanospheres;
wherein the mass ratio of the vinyltriethoxysilane to the graphene to the deionized water to the polyvinyl pyrrolidone is 110: 12: 600: 1.0;
the polyvinyl pyrrolidone is polyvinyl pyrrolidone K90;
the molar concentration of the hydrochloric acid aqueous solution is 3 mol/L;
the mass concentration of the ammonia water is 26%.
Example 6
The preparation method of the two-component polysiloxane modified phenolic resin disclosed in the embodiment 1 comprises the following steps:
adding 110kg of phenol, 70kg of formaldehyde aqueous solution and 8kg of benzoxazine into a reaction kettle, heating to 50 ℃, adding 0.05kg of organic acid, stirring for reacting for 1.5 hours, adding 24kg of cross-linked polysiloxane and 15kg of polysiloxane nano microspheres, heating to 120 ℃, stirring for reacting for 1 hour, reducing the vacuum degree in the reaction kettle to 0-0.05 MPa, stirring for reacting until the temperature of the reaction liquid reaches 150 ℃, and stopping the reaction to obtain the two-component polysiloxane modified phenolic resin;
the mass concentration of the formaldehyde aqueous solution is 20%;
the organic acid is formic acid.
Example 7
The preparation method of the two-component polysiloxane modified phenolic resin, which is described in the embodiment 2, comprises the following steps:
adding 120kg of phenol, 80kg of formaldehyde aqueous solution and 15kg of benzoxazine into a reaction kettle, heating to 90 ℃, adding 0.4kg of organic acid, stirring for reacting for 1.5 hours, adding 33kg of cross-linked polysiloxane and 28kg of polysiloxane nano microspheres, heating to 140 ℃, stirring for reacting for 2 hours, reducing the vacuum degree in the reaction kettle to 0-0.05 MPa, stirring for reacting until the temperature of the reaction liquid reaches 150 ℃, and stopping the reaction to obtain the two-component polysiloxane modified phenolic resin;
the mass concentration of the formaldehyde aqueous solution is 35%;
the organic acid is dodecyl benzene sulfonic acid.
Example 8
The preparation method of the two-component polysiloxane modified phenolic resin, which is described in the embodiment 3, comprises the following steps:
adding 112kg of phenol, 78kg of formaldehyde aqueous solution and 12kg of benzoxazine into a reaction kettle, heating to 60 ℃, adding 0.2kg of organic acid, stirring for reacting for 1 hour, adding 20kg of cross-linked polysiloxane and 20kg of polysiloxane nano microspheres, heating to 130 ℃, stirring for reacting for 1.5 hours, reducing the vacuum degree in the reaction kettle to 0-0.05 MPa, stirring for reacting until the temperature of the reaction liquid reaches 150 ℃, and stopping the reaction to obtain the double-component polysiloxane modified phenolic resin;
the mass concentration of the formaldehyde aqueous solution is 25%;
the organic acid is formic acid.
Example 9
The preparation method of the two-component polysiloxane modified phenolic resin disclosed by the embodiment 4 comprises the following steps of:
adding 115kg of phenol, 76kg of formaldehyde aqueous solution and 10kg of benzoxazine into a reaction kettle, heating to 70 ℃, adding 0.2kg of organic acid, stirring for reacting for 1.2 hours, adding 30kg of cross-linked polysiloxane and 25kg of polysiloxane nano microspheres, heating to 120-140 ℃, stirring for reacting for 1.5 hours, reducing the vacuum degree in the reaction kettle to 0-0.05 MPa, stirring for reacting until the temperature of the reaction liquid reaches 150 ℃, and stopping the reaction to obtain the two-component polysiloxane modified phenolic resin;
the mass concentration of the formaldehyde aqueous solution is 30 percent;
the organic acid is formic acid.
Example 10
The preparation method of the two-component polysiloxane modified phenolic resin disclosed by the embodiment 5 comprises the following steps of:
adding 115kg of phenol, 75kg of formaldehyde aqueous solution and 10kg of benzoxazine into a reaction kettle, heating to 80 ℃, adding 0.3kg of organic acid, stirring for reacting for 1.5 hours, adding 30kg of cross-linked polysiloxane and 25kg of polysiloxane nano microspheres, heating to 130 ℃, stirring for reacting for 1.5 hours, reducing the vacuum degree in the reaction kettle to 0-0.05 MPa, stirring for reacting until the temperature of the reaction liquid reaches 150 ℃, and stopping the reaction to obtain the double-component polysiloxane modified phenolic resin;
the mass concentration of the formaldehyde aqueous solution is 30 percent;
the organic acid is dodecyl benzene sulfonic acid.
Test example
The hardness of the phenolic resin in the invention embodiment is tested according to the method described in the national standard GB/T531.1-2008; the mechanical properties were tested according to the method described in GB/T528-2009. The test results are shown in Table 1. Comparative phenolic resin was prepared according to the method of patent CN 109422857A.
TABLE 1 mechanical properties of the phenolic resins prepared in the examples
From the results in table 1, it can be seen that the phenolic resins prepared in the examples of the present invention have better hardness, better tensile properties at 50%, 100% and 300%, and higher tensile strength at break, compared with the phenolic resins prepared in patent CN 109422857A.
Claims (6)
1. A two-component polysiloxane modified phenolic resin is characterized in that: the composite material comprises the following raw materials in parts by weight: 110-120 parts of phenol, 70-80 parts of formaldehyde aqueous solution, 24-33 parts of cross-linked polysiloxane, 15-28 parts of polysiloxane nano microspheres, 8-15 parts of benzoxazine and 0.05-0.4 part of organic acid;
the mass concentration of the formaldehyde aqueous solution is 20-35%;
the organic acid is formic acid or dodecyl benzene sulfonic acid;
wherein the cross-linked polysiloxane is prepared according to the following method:
heating phenyl tri (dimethylsiloxy) silane and tetramethylammonium hydroxide to 70 ℃ under the protection of nitrogen, dropwise adding 1, 2-bis-trimethoxysilylethane and 3-mercaptopropyl methyldimethoxysilane to obtain a mixed solution, ensuring the temperature of the mixed solution to be 70-90 ℃ in the dropwise adding process, heating to 110-120 ℃ after the dropwise adding is finished, and stirring for reacting for 1-3 hours to obtain crosslinked polysiloxane;
wherein the mass ratio of phenyltri (dimethylsiloxy) silane to tetramethylammonium hydroxide to 1, 2-bistrimethoxysilyl ethane to 3-mercaptopropylmethyldimethoxysilane is 100-110: 0.04-0.12: 42-50: 33 to 38;
the polysiloxane nano-microsphere is prepared by the following method:
adding vinyltriethoxysilane, graphene, deionized water and polyvinylpyrrolidone into a reaction bottle, starting stirring, heating to 25-40 ℃, adjusting the pH value to 3.5-5.5 with a hydrochloric acid aqueous solution, stirring for reaction for 1-3 hours, adding ammonia water to adjust the pH value to 6.5-8.0, centrifuging, filtering, and obtaining a filter cake which is polysiloxane nanospheres;
the mass ratio of the vinyltriethoxysilane to the graphene to the deionized water to the polyvinylpyrrolidone is 80-120: 10-15: 500-800: 0.5 to 2;
the polyvinylpyrrolidone is polyvinylpyrrolidone K30 or polyvinylpyrrolidone K90;
the molar concentration of the hydrochloric acid aqueous solution is 2-4 mol/L;
the mass concentration of the ammonia water is 25-28%.
2. The two-component polysiloxane-modified phenolic resin according to claim 1, wherein: the mass fraction of the formaldehyde aqueous solution is 25-30%.
3. The two-component polysiloxane-modified phenolic resin according to claim 1, wherein: the organic acid is dodecyl benzene sulfonic acid.
4. The two-component polysiloxane-modified phenolic resin according to claim 1, wherein: the polyvinylpyrrolidone is polyvinylpyrrolidone K90.
5. The two-component polysiloxane-modified phenolic resin according to claim 1, which is characterized in that: the mass ratio of phenyltri (dimethylsiloxy) silane to tetramethylammonium hydroxide to 1, 2-bistrimethoxysilyl ethane to 3-mercaptopropylmethyldimethoxysilane is 108: 0.05: 45: 35.
6. the method for preparing the two-component polysiloxane-modified phenolic resin according to claim 1, which is characterized in that: the method comprises the following steps of:
adding 110-120 parts of phenol, 70-80 parts of formaldehyde aqueous solution and 8-15 parts of benzoxazine into a reaction kettle, heating to 50-90 ℃, adding 0.05-0.4 part of organic acid, stirring for reaction for 0.5-1.5 hours, adding 24-33 parts of cross-linked polysiloxane and 15-28 parts of polysiloxane nano microspheres, heating to 120-140 ℃, stirring for reaction for 1-2 hours, reducing the vacuum degree in the reaction kettle to 0-0.05 MPa, and stopping the reaction until the temperature of the reaction liquid reaches 150 ℃ to obtain the two-component polysiloxane modified phenolic resin;
the mass concentration of the formaldehyde aqueous solution is 20-35%;
the organic acid is formic acid or dodecyl benzene sulfonic acid;
wherein the cross-linked polysiloxane is prepared according to the following method:
heating phenyl tri (dimethylsiloxy) silane and tetramethylammonium hydroxide to 70 ℃ under the protection of nitrogen, dropwise adding 1, 2-bis (trimethoxysilylethane) and 3-mercaptopropyl methyldimethoxysilane to obtain a mixed solution, ensuring the temperature of the mixed solution to be 70-90 ℃ in the dropwise adding process, heating to 110-120 ℃ after dropwise adding, and stirring for reacting for 1-3 hours to obtain crosslinked polysiloxane;
wherein the mass ratio of phenyltri (dimethylsiloxy) silane to tetramethylammonium hydroxide to 1, 2-bistrimethoxysilyl ethane to 3-mercaptopropylmethyldimethoxysilane is 100-110: 0.04-0.12: 42-50: 33 to 38;
the polysiloxane nano-microsphere is prepared by the following method:
adding vinyltriethoxysilane, graphene, deionized water and polyvinylpyrrolidone into a reaction bottle, starting stirring, heating to 25-40 ℃, adjusting the pH value to 3.5-5.5 with a hydrochloric acid aqueous solution, stirring for reaction for 1-3 hours, adding ammonia water to adjust the pH value to 6.5-8.0, centrifuging, filtering, and obtaining a filter cake which is polysiloxane nanospheres;
the mass ratio of the vinyltriethoxysilane to the graphene to the deionized water to the polyvinylpyrrolidone is 80-120: 10-15: 500-800: 0.5 to 2;
the polyvinylpyrrolidone is polyvinylpyrrolidone K30 or polyvinylpyrrolidone K90;
the molar concentration of the hydrochloric acid aqueous solution is 2-4 mol/L;
the mass concentration of the ammonia water is 25-28%.
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| CN1187836A (en) * | 1995-04-21 | 1998-07-15 | 阿迈隆国际公司 | Phenolic resin compositions with improved impact resistance |
| TW555808B (en) * | 2000-02-11 | 2003-10-01 | Chung Shan Inst Of Science | Phenolic aldehyde resin modified with polysiloxane amide and polysiloxane amide and manufacturing method thereof |
| ES2240410T3 (en) * | 2000-02-23 | 2005-10-16 | Georgia-Pacific Resins, Inc. | COMPOSITIONS AND COMPOUNDS OF PHENOLIC RESINS MODIFIED WITH AN EPOXIDIC FUNCTIONALITY POLYSYLOXANE. |
| CN106589790A (en) * | 2016-11-30 | 2017-04-26 | 徐电友 | Preparation method of polysiloxane modified phenolic resin high-temperature-resistant insulating material |
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| CN1187836A (en) * | 1995-04-21 | 1998-07-15 | 阿迈隆国际公司 | Phenolic resin compositions with improved impact resistance |
| TW555808B (en) * | 2000-02-11 | 2003-10-01 | Chung Shan Inst Of Science | Phenolic aldehyde resin modified with polysiloxane amide and polysiloxane amide and manufacturing method thereof |
| ES2240410T3 (en) * | 2000-02-23 | 2005-10-16 | Georgia-Pacific Resins, Inc. | COMPOSITIONS AND COMPOUNDS OF PHENOLIC RESINS MODIFIED WITH AN EPOXIDIC FUNCTIONALITY POLYSYLOXANE. |
| CN106589790A (en) * | 2016-11-30 | 2017-04-26 | 徐电友 | Preparation method of polysiloxane modified phenolic resin high-temperature-resistant insulating material |
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