CN1709944A - Method for raising heat-resistance property of organic silicon resin adopting polyheadral oligo-sesqui silione - Google Patents
Method for raising heat-resistance property of organic silicon resin adopting polyheadral oligo-sesqui silione Download PDFInfo
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Abstract
This is the method of improving the thermal stability of organosilicon resin adopting polyhedral oligomeric silsesquioxane (POSS). It relates to a kind of method of improving the thermal stability of organosilicon resin. The invention solves the problem of reducing the wave-transmissivity of the organosilicon resin by all the methods that changes the structure of the pendent groups of polysiloxane or changes the structure of main chain or adds thermostable padding to improve the thermal stability of the organosilicon resin. It includes following steps: a. adopt methyl methoxy silane monomer as raw material, prepare organosilicon resin through hydrolyzation and polyesterification reaction; b. add alcohol solvent into the prepared organosilicon resin to prepare the organosilicon resin with alcohol as solvent; besides it also includes Step c.: add 0.5 -10% POSS of the weight of the organosilicon resin into the organosilicon resin produced in Step b., the reaction temperature is 60 -90 Deg. C, the reaction time is 4 -8 hours, and vacuum membrane distillation. The modified organosilicon resin produced by the method has high heat-resisting performance.
Description
Technical field:
The present invention relates to a kind of method that improves heat resistance of organic silicon resin, be specifically related to a kind of method that adopts polyhedral oligomeric silsesquioxane to improve heat resistance of organic silicon resin.
Background technology:
Needs along with development of aviation and aerospace technology and modernized war, the flight Mach number of aerospace flight vehicle improves constantly, it is more and more higher to be in temperature and thermal shocking that the radome of the pneumatic heating maximum position of aircraft need bear, resistance to elevated temperatures for the space flight electromagnetic wave transparent material has proposed higher, more urgent requirement, and this more closely depends on the research and development of high temperature resistant wave-permeable resin matrix.Therefore, the resistance toheat of raising resin matrix has become the direction of first developing of space flight electromagnetic wave transparent material.The resin matrix of early stage space flight wave-penetrating composite material mainly contains resol, Resins, epoxy, unsaturated polyester, Vinylite, polybutadiene, butadiene styrene resin, allyl ester resin etc.The use temperature of above resin all is no more than 200 ℃, is applicable to the situation that aircraft speed is not high, and is just inapplicable to these materials of hypersonic missile radome.It is several that the fire resistant resin matrix that uses as radome material mainly contains polyimide (PI), polybenzimidazole (PBI), polytetrafluoroethylene (PTFE) and silicone resin etc. at present.Wherein, silicone resin is a kind of extremely attractive space flight electromagnetic wave transparent material resin matrix, its the most outstanding performance is excellent thermo-oxidative stability, this mainly is because silicone resin is to be skeleton with Si-O-Si, the bond energy of its C-C key is 307kJ/mol, and the bond energy of Si-O key is 450kJ/mol, so the thermostability of silicone resin is very high, can not decompose at 200~250 ℃ of following life-time service, nondiscoloration, the short period of time can anti-300 ℃ high temperature.Three kinds of approach of main at present employing improve the resistance toheat of silicone resins, promptly change the structure of polysiloxane side group; Change the structure of main chain; Add high temperature resistant filler etc.The structure that changes the polysiloxane side group mainly is to introduce the thermotolerance group on the side chain of polysiloxane, as make the side group etc. that additive, linking agent or introducing contain condensed ring with the silicoorganic compound that contain many phenyl; The method that changes backbone structure has: introduce heat-stable large volume segment or aromatic ring in main chain, synthesize the silicon double-strand polymer or introduce heteroatoms in main chain, as Ti, B, N etc.; Adding high temperature resistant filler mainly is to adopt some metal oxides to improve the high-temperature stability of silicone resin.These methods can both improve the resistance toheat of silicone resin to a certain extent, but because contain phenyl compound or the metal oxide introduced have all reduced the saturating ripple rate of silicone resin (in frequency have been 10GHz, when temperature was 20 ℃, the specific inductivity of silicone resin was 2.8~2.9).
Summary of the invention:
The objective of the invention is for solving existing for improving the heat resistance of organic silicon resin energy, adopt the structure that changes polysiloxane side group structure or change main chain or add high temperature resistant filler, but the problem that these methods can make the saturating ripple rate of silicone resin reduce, a kind of employing polyhedral oligomeric silsesquioxane (Polyhedral Oligomeric Silsesquioxane is provided now, abbreviation POSS) method of raising heat resistance of organic silicon resin, the silicone resin of being made by this method has the advantage that does not reduce saturating ripple rate.It may further comprise the steps: a, employing methyl alkoxy silane monomer are raw material, make silicone resin by hydrolysis and polycondensation; Add alcoholic solvent in b, the silicone resin made in a step, making with the alcohols is that the mass percent of solvent is 30~50% silicone resin; It also comprises the c step: add polyhedral oligomeric silsesquioxane in the silicone resin that the b step makes, the add-on of polyhedral oligomeric silsesquioxane is occupied 0.5~10% of machine silicone resin quality, temperature of reaction is 60~90 ℃, reaction times is 4~8h, carries out underpressure distillation after reaction finishes.
The present invention has following beneficial effect: one, the present invention adopts the polyhedral oligomeric silsesquioxane modification to prepare silicone resin.Polyhedral oligomeric silsesquioxane is a kind of polymkeric substance strongthener that is subjected to extensive concern in recent years in the world.Poss monomers is that a class is the ring-type nano level cage type molecule that skeleton is connected into Si-O, its structure mainly has following two characteristics: (1) includes the inorganic supporting structure of being made up of Si and O, gives the polyhedral oligomeric silsesquioxane good heat-resistant; (2) outside alkane substituting group or the active reactive group of connecting, organic group can improve the consistency between polyhedral oligomeric silsesquioxane and the polymkeric substance, and reactive group can be realized the chemical bonding effect between polyhedral oligomeric silsesquioxane and the polymkeric substance.Polyhedral oligomeric silsesquioxane can be used as additive and combines with ordinary resin by polymerization or crosslinked action, thereby significantly improves the resistance toheat of resin.In addition, this material structure contains uniform nano level hole, (in frequency is 10GHz to have good low-k, when temperature is 20 ℃, the specific inductivity of polyhedral oligomeric silsesquioxane is 2.1~2.7), poss monomers is incorporated in other polymkeric substance, can effectively reduces the specific inductivity of polymkeric substance.Therefore, (silicone resin before the modification does not decompose at 250 ℃ of following life-time service, nondiscoloration, and the short period of time can anti-350 ℃ high temperature to adopt the resin matrix of poss monomers modification space flight wave-penetrating composite material can effectively improve the resistance to elevated temperatures of silicone resin matrix under the prerequisite that does not influence its saturating ripple rate; Silicone resin after modification life-time service under 250~350 ℃ temperature does not decompose, nondiscoloration, and the short period of time can anti-450~550 ℃ high temperature, can improve 240.4~328.3 ℃ through the initial heat decomposition temperature of silicone resin in air atmosphere of modification).Two, adopt polyhedral oligomeric silsesquioxane that silicone resin is carried out modification, can obviously reduce the thermal weight loss (rate of weight loss of silicone resin in the time of 400 ℃ 11.5% before 1~5.5% after reducing to modification of silicone resin by modification; After modification is reduced in 21.5% before by the modification of the rate of weight loss of silicone resin in the time of 900 ℃ 6.5~15.5%).Three, polyhedral oligomeric sesquialter stone siloxanes of the present invention can be the polyhedral oligomeric silsesquioxane that has hydroxy functional group, as: three silanol phenyl silsesquioxanes (TriSilanolPhenyl-POSS), three silanol isobutyl-silsesquioxanes (TriSilanolIsobutyl-POSS), three silanol suberane base silsesquioxanes (TriSilanolCyclohexyl-POSS), three silanol pentamethylene base silsesquioxanes (TriSilanolICyclopentyl-POSS), one silanol isobutyl-silsesquioxane (MonoSilanolIsobutyl-POSS), one silanol suberane base silsesquioxane (MonoSilanolCyclohexyl-POSS), one silanol pentamethylene base silsesquioxane (MonoSilanolICyclopentyl-POSS) or eight hydroxypropyl dimethyl silanyl silsesquioxanes (OctaHydroxypropyldimethylsilyl-POSS); Also can be the polyhedral oligomeric silsesquioxane that does not have hydroxy functional group, as: methacryloxy silsesquioxane (Methacryl-POSSCage Mixture), prestox silsesquioxane (OctaMethyl-POSS) or octaphenyl silsesquioxane (OctaMethyl-POSS).Employing has the prepared silicone resin of polyhedral oligomeric silsesquioxane modification of hydroxy functional group, can make and carry out the condensation dehydration reaction between the hydroxyl of polyhedral oligomeric silsesquioxane and silicone resin and make polyhedral oligomeric silsesquioxane be connected the side chain or the two ends of silicone resin, form a successive macromolecular chain, and in whole system, form reticulated structure; If selected poss monomers does not have hydroxy functional group, it can directly be blended in the silicone resin.After solidifying, the polyhedral oligomeric silsesquioxane modified organic silicone resin that adopts these two kinds of methods to prepare all has outstanding high temperature resistance.Four, this method has simple, the maneuverable advantage of technology.
Embodiment:
Embodiment one: the employing polyhedral oligomeric silsesquioxane of present embodiment improves the method for heat resistance of organic silicon resin, it is finished by following steps: a, employing methyl alkoxy silane monomer are raw material, make silicone resin by hydrolysis and polycondensation; Add alcoholic solvent in b, the silicone resin made in a step, making with the alcohols is that the mass percent of solvent is 30~50% silicone resin; C, polyhedral oligomeric silsesquioxane is joined in the silicone resin that the b step makes, the add-on of polyhedral oligomeric silsesquioxane is occupied 0.5~10% of machine silicone resin quality, temperature of reaction is 60~90 ℃, reaction times is 4~8h, carry out underpressure distillation under the condition that in temperature be between 50~80 ℃ then, system vacuum tightness is 9~11mmHg, steam alcoholic solvent and water, make silicone resin.
Embodiment two: the difference of present embodiment and embodiment one is: the add-on of the polyhedral oligomeric silsesquioxane in the c step of present embodiment is occupied 0.6% of machine silicone resin quality, temperature of reaction is 65 ℃, reaction times is 4.5h, carry out underpressure distillation under the condition that after reaction finishes, be between 50~80 ℃, system vacuum tightness is 9mmHg in temperature.Adopt above-mentioned technical parameter to can be made into silicone resin with resistance to elevated temperatures.
Embodiment three: the difference of present embodiment and embodiment one is: the add-on of the polyhedral oligomeric silsesquioxane in the c step of present embodiment is occupied 9.5% of machine silicone resin quality, temperature of reaction is 85 ℃, reaction times is 7.5h, carry out underpressure distillation under the condition that after reaction finishes, be between 50~80 ℃, system vacuum tightness is 11mmHg in temperature.Adopt above-mentioned technical parameter can be made into and have the silicone resin of resistance to elevated temperatures preferably.
Embodiment four: the difference of present embodiment and embodiment one is: the add-on of the polyhedral oligomeric silsesquioxane in the c step of present embodiment is occupied 9.5% of machine silicone resin quality, temperature of reaction is 75 ℃, reaction times is 6h, carry out underpressure distillation under the condition that after reaction finishes, be between 50~80 ℃, system vacuum tightness is 10mmHg in temperature.Adopt above-mentioned technical parameter to can be made into silicone resin with good resistance to elevated temperatures.
Embodiment five: the difference of present embodiment and embodiment one is: in a step of present embodiment, with methyl alkoxy silane monomer and alcoholic solvent is that 1: 1~1: 3 ratio joins in the four-hole bottle and mixes in molar ratio, when again mixing solutions being warming up to 50~80 ℃, adopt dropping funnel to splash into aqueous solution of hydrochloric acid, be hydrolyzed and polycondensation, the amount of splashing into of hydrochloric acid accounts for 0.01~2% of methyl alkoxy silane monomer quality, in the mixing solutions that reaction finishes, add and splash into suitable sodium hydroxide of weight or ammoniacal liquor with hydrochloric acid, mixing solutions is neutralized to pH=7, obtain the silicone resin prepolymer, be between 50~80 ℃ in temperature then, system vacuum tightness is to carry out underpressure distillation under the condition of 9~11mmHg, steam alcoholic solvent and water, make silicone resin.Select above-mentioned technical parameter for use, can improve the percent hydrolysis and the hydrolysis rate of methyl alkoxy silane monomer.
Embodiment six: the difference of present embodiment and embodiment five is: in a step of present embodiment, methyl alkoxy silane monomer and 1: 2 in molar ratio ratio of alcoholic solvent joined in the four-hole bottle mix, when again mixing solutions being warming up to 65 ℃, adopt dropping funnel to splash into aqueous solution of hydrochloric acid, be hydrolyzed and polycondensation, the amount of splashing into of hydrochloric acid accounts for 1% of methyl alkoxy silane monomer quality, in the mixing solutions that reaction finishes, add and splash into suitable sodium hydroxide of weight or ammoniacal liquor with hydrochloric acid, mixing solutions is neutralized to pH=7, obtain the silicone resin prepolymer, it is 65 ℃ in temperature then, system vacuum tightness is to carry out underpressure distillation under the condition of 10mmHg, steam alcoholic solvent and water, make silicone resin.Select above-mentioned technical parameter for use, can effectively improve the percent hydrolysis and the hydrolysis rate of methyl alkoxy silane monomer.
Embodiment seven: the difference of present embodiment and embodiment one is: in the b step of present embodiment, add alcoholic solvent in the silicone resin of making in a step, making with the alcohols is that the mass percent of solvent is 40% silicone resin.Made silicone resin stable performance is beneficial to keeping and storage.
Embodiment eight: the difference of present embodiment and embodiment one, embodiment five is: the methyl alkoxy silane of present embodiment is methyltrimethoxy silane or Union carbide A-162.Because the price of methyltrimethoxy silane or Union carbide A-162 is lower, select methyltrimethoxy silane or Union carbide A-162 raw material for use as the preparation silicone resin, can reduce production costs.
Embodiment nine: the difference of present embodiment and embodiment five, embodiment seven is: the present embodiment alcoholic solvent is methyl alcohol or ethanol or Virahol or butanols.Adopt alcoholic solvent commonly used, its price is low, buys easily.
The specific embodiment ten: the difference of present embodiment and the specific embodiment one is: the polyhedral oligomeric silsesquioxane of present embodiment is for the polyhedral oligomeric silsesquioxane of hydroxy functional group or without the polyhedral oligomeric silsesquioxane of hydroxy functional group, described polyhedral oligomeric silsesquioxane with hydroxy functional group is three silanol phenyl silsesquioxanes or three silanol isobutyl group silsesquioxanes or three silanol cycloheptane base silsesquioxanes or three silanol pentamethylene base silsesquioxanes or a silanol isobutyl group silsesquioxane or a silanol cycloheptane base silsesquioxane or a silanol pentamethylene base silsesquioxane or eight hydroxypropyl dimethyl silanyl silsesquioxanes; The described polyhedral oligomeric silsesquioxane that does not have hydroxy functional group is methacryloxy silsesquioxane or prestox silsesquioxane or octaphenyl silsesquioxane.Adopt above-mentioned polyhedral oligomeric silsesquioxane to prepare to have superior heat resistance can silicone resin.
Embodiment 11: present embodiment is an example with the preparation silicone resin, its preparation method is finished by following steps: a, agitator will be housed, dropping funnel, the four-hole bottle of the 500ml of reflux condensing tube and thermometer places water-bath, adding 1mol Union carbide A-162 and 2mol ethanol stir in four-hole bottle, adding 3mol water and 0.04ml concentrated hydrochloric acid mix in dropping funnel then, warming-in-water to 50 ℃, the aqueous solution of beginning dripping hydrochloric acid, time with 20min dropwises, controlled temperature is between 50~70 ℃, reaction 3~5hr, add 0.04ml ammoniacal liquor then mixing solutions is neutralized to pH=7, obtain the silicone resin prepolymer, be between 50~80 ℃ in temperature then, system vacuum tightness is to carry out underpressure distillation under the condition of 10mmHg, steam alcoholic solvent and water, obtain the water white silicone resin that contains terminal hydroxy group; It is 50% silicone resin that b, the ethanol that adds 2~10ml in the silicone resin that contains terminal hydroxy group that a step is made are made mass percent.
Prepared silicone resin Si-OH matrix amount mark is 5~15%, and weight-average molar mass is 2396g/mol, and the initial heat decomposition temperature in air atmosphere is 246.6 ℃; Rate of weight loss in the time of 400 ℃ is 11.5%; Rate of weight loss in the time of 900 ℃ is 21.5%; Do not decompose at 200~250 ℃ of following life-time service, nondiscoloration, the short period of time can anti-300 ℃ high temperature.
Embodiment 12: present embodiment is an example to prepare three silanol phenyl silsesquioxane modified organic silicone resins: its preparation method is finished by following steps: get the silicone resin 20g that is made by the b step in the embodiment 11, the three silanol phenyl silsesquioxanes that add 0.5g, control reaction temperature is in 60~90 ℃ of scopes, reaction times is 5~8h, carry out underpressure distillation under the condition that after reaction finishes, be between 50~80 ℃, system vacuum tightness is 10mmHg in temperature.
The weight-average molar mass of three prepared silanol phenyl silsesquioxane modified organic silicone resins is 2463g/mol, and the initial heat decomposition temperature in air atmosphere is 550 ℃; Rate of weight loss in the time of 400 ℃ is 2.5%; Rate of weight loss in the time of 900 ℃ is 11.7%; Under 250~300 ℃ temperature life-time service do not decompose, nondiscoloration, the short period of time can anti-500 ℃ high temperature.
Embodiment 13: present embodiment is an example to prepare three silanol isobutyl-silsesquioxane modified organic silicone resins: its preparation method is finished by following steps: get the silicone resin 20g that is made by the b step in the embodiment 11, the three silanol isobutyl-silsesquioxanes that add 0.5g, control reaction temperature is in 60~80 ℃ of scopes, reaction times is 4~6h, carry out underpressure distillation under the condition that after reaction finishes, be between 50~80 ℃, system vacuum tightness is 9mmHg in temperature.
The weight-average molar mass of three prepared silanol isobutyl-silsesquioxane modified organic silicone resins is 2653g/mol, and the initial heat decomposition temperature in air atmosphere is 574.9 ℃; Rate of weight loss in the time of 400 ℃ is 1%; Rate of weight loss in the time of 900 ℃ is 6.5%; Under 300~350 ℃ temperature life-time service do not decompose, nondiscoloration, the short period of time can anti-550 ℃ high temperature.
Embodiment 14: present embodiment is an example to prepare a silanol isobutyl-silsesquioxane modified organic silicone resin: its preparation method is finished by following steps: get the silicone resin 20g that is made by the b step in the embodiment 11, a silanol isobutyl-silsesquioxane that adds 0.5g, control reaction temperature is in 60~80 ℃ of scopes, reaction times is 4~6h, carry out underpressure distillation under the condition that after reaction finishes, be between 50~80 ℃, system vacuum tightness is 11mmHg in temperature.
The weight-average molar mass of a prepared silanol isobutyl-silsesquioxane modified organic silicone resin is 2735g/mol, and the initial heat decomposition temperature in air atmosphere is 487 ℃; Rate of weight loss in the time of 400 ℃ is 5.5%; Rate of weight loss in the time of 900 ℃ is 15.5%; Under 250~300 ℃ temperature life-time service do not decompose, nondiscoloration, the short period of time can anti-450 ℃ high temperature.
Embodiment 15: present embodiment is an example with preparation methacryloxy silsesquioxane modified organic silicone resin: its preparation method is finished by following steps: get the silicone resin 20g that is made by the b step in the embodiment 11, add the methacryloxy silsesquioxane of 0.5g, stirring gets final product.
The prepared initial heat decomposition temperature of methacryloxy silsesquioxane modified organic silicone resin in air atmosphere is 500.7 ℃; Rate of weight loss in the time of 400 ℃ is 4%; Rate of weight loss in the time of 900 ℃ is 13%; Under 250~300 ℃ temperature life-time service do not decompose, nondiscoloration, the short period of time can anti-550 ℃ high temperature.
Claims (10)
1, a kind of method that adopts polyhedral oligomeric silsesquioxane to improve heat resistance of organic silicon resin, it may further comprise the steps: a, employing methyl alkoxy silane monomer are raw material, make silicone resin by hydrolysis and polycondensation; Add alcoholic solvent in b, the silicone resin made in a step, making with the alcohols is that the mass percent of solvent is 30~50% silicone resin; It is characterized in that it also comprises the c step: in the silicone resin that the b step makes, add polyhedral oligomeric silsesquioxane, the add-on of polyhedral oligomeric silsesquioxane is occupied 0.5~10% of machine silicone resin quality, temperature of reaction is 60~90 ℃, reaction times is 4~8h, and reaction finishes and carries out underpressure distillation under the condition that the back in temperature is between 50~80 ℃, system vacuum tightness is 9~11mmHg.
2, employing polyhedral oligomeric silsesquioxane according to claim 1 improves the method for heat resistance of organic silicon resin, the add-on that it is characterized in that the polyhedral oligomeric silsesquioxane in the c step is occupied 0.6% of machine silicone resin quality, temperature of reaction is 65 ℃, reaction times is 4.5h, and reaction finishes and carries out underpressure distillation under the condition that the back in temperature is between 50~80 ℃, system vacuum tightness is 9mmHg.
3, employing polyhedral oligomeric silsesquioxane according to claim 1 improves the method for heat resistance of organic silicon resin, the add-on that it is characterized in that the polyhedral oligomeric silsesquioxane in the c step is occupied 9.5% of machine silicone resin quality, temperature of reaction is 85 ℃, reaction times is 7.5h, carry out underpressure distillation under the condition that after reaction finishes, be between 50~80 ℃, system vacuum tightness is 11mmHg in temperature.
4, employing polyhedral oligomeric silsesquioxane according to claim 1 improves the method for heat resistance of organic silicon resin, the add-on that it is characterized in that the polyhedral oligomeric silsesquioxane in the c step is occupied 9.5% of machine silicone resin quality, temperature of reaction is 75 ℃, reaction times is 6h, carry out underpressure distillation under the condition that after reaction finishes, be between 50~80 ℃, system vacuum tightness is 10mmHg in temperature.
5, employing polyhedral oligomeric silsesquioxane according to claim 1 improves the method for heat resistance of organic silicon resin, it is characterized in that in a step, with methyl alkoxy silane monomer and alcoholic solvent is that 1: 1~1: 3 ratio joins in the four-hole bottle and mixes in molar ratio, when again mixing solutions being warming up to 50~80 ℃, adopt dropping funnel to splash into aqueous solution of hydrochloric acid, be hydrolyzed and polycondensation, the amount of splashing into of hydrochloric acid accounts for 0.01~2% of methyl alkoxy silane monomer quality, in the mixing solutions that reaction finishes, add and splash into suitable sodium hydroxide of weight or ammoniacal liquor with hydrochloric acid, mixing solutions is neutralized to pH=7, obtain the silicone resin prepolymer, be between 50~80 ℃ in temperature then, system vacuum tightness is to carry out underpressure distillation under the condition of 9~11mmHg, steam alcoholic solvent and water, make silicone resin.
6, employing polyhedral oligomeric silsesquioxane according to claim 5 improves the method for heat resistance of organic silicon resin, it is characterized in that in a step, methyl alkoxy silane monomer and 1: 2 in molar ratio ratio of alcoholic solvent joined in the four-hole bottle mix, when again mixing solutions being warming up to 65 ℃, adopt dropping funnel to splash into aqueous solution of hydrochloric acid, be hydrolyzed and polycondensation, the amount of splashing into of hydrochloric acid accounts for 1% of methyl alkoxy silane monomer quality, in the mixing solutions that reaction finishes, add and splash into suitable sodium hydroxide of weight or ammoniacal liquor with hydrochloric acid, mixing solutions is neutralized to pH=7, obtain the silicone resin prepolymer, be between 50~80 ℃ in temperature then, system vacuum tightness is to carry out underpressure distillation under the condition of 10mmHg, steam alcoholic solvent and water, make silicone resin.
7, employing polyhedral oligomeric silsesquioxane according to claim 1 improves the method for heat resistance of organic silicon resin, it is characterized in that in the b step, add alcoholic solvent in the silicone resin of making in a step, making with the alcohols is that the mass percent of solvent is 40% silicone resin.
8, adopt polyhedral oligomeric silsesquioxane to improve the method for heat resistance of organic silicon resin according to claim 1 or 5, it is characterized in that described methyl alkoxy silane is methyltrimethoxy silane or Union carbide A-162.
9, according to the method for claim 5 or 7 described employing polyhedral oligomeric silsesquioxanes raising heat resistance of organic silicon resin, it is characterized in that described alcoholic solvent is methyl alcohol or ethanol or Virahol or butanols.
10, employing polyhedral oligomeric silsesquioxane according to claim 1 improves the method for heat resistance of organic silicon resin, it is characterized in that described polyhedral oligomeric silsesquioxane is the polyhedral oligomeric silsesquioxane that has the polyhedral oligomeric silsesquioxane of hydroxy functional group or do not have hydroxy functional group.
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Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
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CN101544763B (en) * | 2008-03-24 | 2011-08-31 | 中国科学院化学研究所 | Modified silicone resin and preparation method thereof |
CN104211965A (en) * | 2013-06-03 | 2014-12-17 | 北京化工大学 | Preparation method for net-like methyl phenyl vinyl polysiloxane for LED packaging |
CN108395668A (en) * | 2018-02-11 | 2018-08-14 | 航天材料及工艺研究所 | A kind of hybrid phenol-formaldehyde resin and the preparation method and application thereof that silsesquioxane is modified |
CN109206751A (en) * | 2018-07-18 | 2019-01-15 | 上海阿莱德实业股份有限公司 | Antenna house weather-resistance flame-retardant polypropylene modified material and preparation method thereof |
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2005
- 2005-06-07 CN CN 200510010068 patent/CN1283695C/en active Active
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
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CN101544763B (en) * | 2008-03-24 | 2011-08-31 | 中国科学院化学研究所 | Modified silicone resin and preparation method thereof |
CN104211965A (en) * | 2013-06-03 | 2014-12-17 | 北京化工大学 | Preparation method for net-like methyl phenyl vinyl polysiloxane for LED packaging |
CN108395668A (en) * | 2018-02-11 | 2018-08-14 | 航天材料及工艺研究所 | A kind of hybrid phenol-formaldehyde resin and the preparation method and application thereof that silsesquioxane is modified |
CN109206751A (en) * | 2018-07-18 | 2019-01-15 | 上海阿莱德实业股份有限公司 | Antenna house weather-resistance flame-retardant polypropylene modified material and preparation method thereof |
CN114874509A (en) * | 2022-05-06 | 2022-08-09 | 青岛双星轮胎工业有限公司 | Rubber composition and preparation method thereof |
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