CN105218811A - A kind of phosphorus-silicon flame retardant type cyanate ester resin and preparation method thereof - Google Patents
A kind of phosphorus-silicon flame retardant type cyanate ester resin and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to a kind of phosphorus-silicon flame retardant type cyanate ester resin and preparation method thereof, resin components comprises dicyclopentadiene type ethylene rhodanate or bisphenol A cyanate ester monomer replaces chloropropyl silsesquioxane with many (4-hydroxyphenyl (4-(oxyethane-2-methoxyl group) phenyl) phenyl-phosphonic acid fat).Many (4-hydroxyphenyl (4-(oxyethane-2-methoxyl group) phenyl) phenyl-phosphonic acid fat) replaces chloropropyl silsesquioxane and can participate in cyanate curing reaction as reactive flame retardant, improve the consistency of itself and resin, also can play toughness reinforcing, to reduce specific inductivity effect simultaneously.Therefore, cured article has excellent dielectric properties, good mechanical property and flame retardant properties, can be used as high performance electronic packaging material and uses.
Description
Technical field
The invention belongs to advanced compound materials science domain, particularly relate to a kind of phosphorus-silicon flame retardant type cyanate ester resin and preparation method thereof.
Background technology
Cyanate ester resin, as a kind of high performance composite matrix, is widely used in the fields such as aerospace, printed circuit board (PCB), high-temperature Resistance Adhesives.But in the application of high performance material, the flame retardant resistance of cyanate ester resin is difficult to meet the demands, therefore this patent develops the phosphorous POSS based flameproofing of a kind of response type, this phosphorus-silicon type fire retardant contains epoxy-functional, cyanate ester resin generation condensation reaction can be gone, thus improve the consistency of phosphorous POSS based flameproofing and cyanate ester resin.Due to the synergy of phosphorus and element silicon, can promote during burning that resin surface forms fine and close layer of charcoal, thus greatly improve the flame retardant properties of cyanate ester resin.Simultaneously due to the existence of cage type POSS structure, the dielectric properties of resin matrix also obtain larger raising.Cured article has good mechanical property, excellent dielectric properties and flame retardant properties, has great importance to widening its application in high-performance engineering field of cyanate ester resin.
Summary of the invention
The technical problem solved
In order to avoid the deficiencies in the prior art part, the present invention proposes a kind of phosphorus-silicon flame retardant type cyanate ester resin and preparation method thereof, this resin cured matter has excellent dielectric properties, good mechanical property and flame retardant properties, can be used as high performance electronic packaging material and uses.
Technical scheme
A kind of phosphorus-silicon flame retardant type cyanate ester resin, is characterized in that comprising 100 parts of dicyclopentadiene type ethylene rhodanates or bisphenol A cyanate ester resin monomer, many (4-hydroxyphenyl (4-(oxyethane-2-methoxyl group) phenyl) the phenyl-phosphonic acid fat) of 0.1 ~ 20 part replaces chloropropyl silsesquioxane; The structural formula that described many (4-hydroxyphenyl (4-(oxyethane-2-methoxyl group) phenyl) phenyl-phosphonic acid fat) replaces chloropropyl silsesquioxane is:
The number of above-mentioned chemical substance is mass fraction.
Prepare a method for described phosphorus-silicon flame retardant type cyanate ester resin, it is characterized in that step is as follows:
Step 1: many (4-hydroxyphenyl (4-(oxyethane-2-methoxyl group) phenyl) the phenyl-phosphonic acid fat) of 0.1 ~ 20 mass parts are replaced chloropropyl silsesquioxane and 100 parts of dicyclopentadiene type ethylene rhodanates or bisphenol A cyanate ester monomer pre-polymerization 10 ~ 30min at 110 DEG C;
Step 2: pour in mould, puts into air dry oven and is cured, curing process: 160 DEG C/1h+180 DEG C/1h+200 DEG C/2h+220 DEG C/2h after 130 DEG C of lower pumpings bubble; Then cool, after the demoulding, at 240 DEG C of aftertreatment 2h, obtain phosphorus-silicon flame retardant type cyanate ester resin.
The bubble of bleeding of described step 2 is at 130 DEG C of lower pumping bubble 60min.
Described mould more than preheating 30min in the baking oven of 120 DEG C.
The preparation process that described many (4-hydroxyphenyl (4-(oxyethane-2-methoxyl group) phenyl) phenyl-phosphonic acid fat) replaces chloropropyl silsesquioxane is:
Step 1: by molar basis, by 1 part of chloropropyl POSS, 4 ~ 10 parts of O, O-bis-(4-(hydroxyl) phenyl) phenyl phosphonic acid esters, the N of 10ml ~ 400ml, dinethylformamide mixed dissolution, add 1 ~ 50ml triethylamine again, the KI of 1 ~ 5 part, react 6 ~ 12 hours at water-bath 60 ~ 80 DEG C, solvent evaporated after completion of the reaction, respectively with dilute hydrochloric acid solution and distilled water wash twice, after recrystallization, obtain white crystal many (two (4-hydroxyphenyl) phenyl phosphonic acid esters) and replace chloropropyl silsesquioxane;
Step 2: by molar basis, replaces chloropropyl silsesquioxane, 50ml ~ 500mlN by (two (4-hydroxyphenyl) phenyl phosphonic acid esters) more than 1 part, after dinethylformamide mixed dissolution, adds 4 ~ 16 parts of Na
2cO
31 ~ 20 part of KI, after stirring 1 ~ 3h at 30 ~ 60 DEG C, add 8 ~ 20 parts of epoxy chloropropane again, 60 ~ 100 DEG C of reaction 6 ~ 12h, distillation, removes solvent, obtains many (4-hydroxyphenyl (4-(oxyethane-2-methoxyl group) phenyl) phenyl-phosphonic acid fat) and replace chloropropyl silsesquioxane.
Beneficial effect
A kind of phosphorus-silicon flame retardant type cyanate ester resin that the present invention proposes and preparation method thereof, resin components comprises dicyclopentadiene type ethylene rhodanate or bisphenol A cyanate ester monomer replaces chloropropyl silsesquioxane with many (4-hydroxyphenyl (4-(oxyethane-2-methoxyl group) phenyl) phenyl-phosphonic acid fat).Many (4-hydroxyphenyl (4-(oxyethane-2-methoxyl group) phenyl) phenyl-phosphonic acid fat) replaces chloropropyl silsesquioxane and can participate in cyanate curing reaction as reactive flame retardant, improve the consistency of itself and resin, also can play toughness reinforcing, to reduce specific inductivity effect simultaneously.Therefore, cured article has excellent dielectric properties, good mechanical property and flame retardant properties, can be used as high performance electronic packaging material and uses.
Many (4-hydroxyphenyl (4-(oxyethane-2-methoxyl group) phenyl) phenyl-phosphonic acid fat) in phosphorus of the present invention-silicon flame retardant type cyanate ester resin system replace chloropropyl silsesquioxane and ester cyanate system cording has good consistency, phosphoric and element silicon act synergistically, larger raising resins fire retardant.Further, many (4-hydroxyphenyl (4-(oxyethane-2-methoxyl group) phenyl) phenyl-phosphonic acid fat) replaces the solidification that chloropropyl silsesquioxane can participate in resin, reduces the cross-linking density of resin, thus improves its toughness.Therefore, can say, the phosphorus that the present invention develops-silicon flame retardant type cyanate ester resin both can improve the defect of common cyanate ester resin toughness and flame retardant resistance deficiency, can overcome again the problem of additive flame retardant and its poor compatibility.Meanwhile, due to the existence of cage type POSS structure, also will the dielectric properties of resin matrix be made to obtain larger raising.
Accompanying drawing explanation
Fig. 1: phosphorus-silicon flame retardant type ethylene rhodanate resin curing reaction mechanism
Embodiment
Now in conjunction with the embodiments, the invention will be further described for accompanying drawing:
The present invention program: first synthesize a kind of phosphorous POSS based flameproofing of response type that can carry out reacting with resin containing epoxy-functional, namely many (4-hydroxyphenyl (4-(oxyethane-2-methoxyl group) phenyl) phenyl-phosphonic acid fat) replaces chloropropyl silsesquioxane, then added in cyanate resin alicyclic monomer or performed polymer, because it contains epoxy-functional, the solidification of cyanate ester resin can be participated in, making many (4-hydroxyphenyl (4-(oxyethane-2-methoxyl group) phenyl) phenyl-phosphonic acid fat) replace chloropropyl silsesquioxane is connected in cyanate ester resin network, thus improve its toughness, flame retardant resistance and dielectric properties.Its curing kinetics is as Fig. 1.
The structural formula of described dicyclopentadiene type ethylene rhodanate is as follows:
The structural formula of described bisphenol A-type cyanate resin monomer is as follows:
The structural formula that described many (4-hydroxyphenyl (4-(oxyethane-2-methoxyl group) phenyl) phenyl-phosphonic acid fat) replaces chloropropyl silsesquioxane is as follows:
Specific embodiment:
Embodiment 1:
Step 1: by molar basis, by 0.001mol chloropropyl POSS, 0.008molO, O-bis-(4-(hydroxyl) phenyl) phenyl phosphonic acid esters, the N of 100ml, dinethylformamide adds in there-necked flask, after dissolving, add 2ml triethylamine, the KI of 0.008mol, react 12 hours at water-bath 60 DEG C, solvent evaporated after completion of the reaction, respectively with dilute hydrochloric acid solution and distilled water wash twice, after recrystallization, obtain white crystal many (two (4-hydroxyphenyl) phenyl phosphonic acid esters) and replace chloropropyl silsesquioxane.
Step 2: by molar basis, many for 0.001mol (two (4-hydroxyphenyl) phenyl phosphonic acid esters) is replaced chloropropyl silsesquioxane, 100mlN, and dinethylformamide adds there-necked flask, after dissolving, adds 0.012molNa
2cO
30.004molKI, after stirring 3h at 30 ~ 60 DEG C, add 0.012mol epoxy chloropropane again, 60 ~ 100 DEG C of reaction 6 ~ 12h, distillation, removes solvent, obtains many (4-hydroxyphenyl (4-(oxyethane-2-methoxyl group) phenyl) phenyl-phosphonic acid fat) and replace chloropropyl silsesquioxane.
Step 3: by mass, (4-hydroxyphenyl (4-(oxyethane-2-methoxyl group) phenyl) phenyl-phosphonic acid fat) more than 2 parts is replaced chloropropyl silsesquioxane and 100 parts of dicyclopentadiene type ethylene rhodanates or bisphenol A cyanate ester monomer pre-polymerization 10 ~ 30min at 110 DEG C, pour in the mould of more than preheating 30min in the baking oven of 120 DEG C, about 60min is steeped at 130 DEG C of lower pumpings, then put into air dry oven to be cured, curing process: 160 DEG C/1h+180 DEG C/1h+200 DEG C/2h+220 DEG C/2h.Cooling, after the demoulding, at 240 DEG C of aftertreatment 2h, namely obtains phosphorus-silicon flame retardant type cyanate ester resin.
Embodiment 2:
Step 1: by 0.001mol chloropropyl POSS, 0.0012molO, O-bis-(4-(hydroxyl) phenyl) phenyl phosphonic acid esters, the N of 150ml, dinethylformamide adds in there-necked flask, after dissolving, add 5ml triethylamine, the KI of 0.008mol, react 8 hours at water-bath 80 DEG C, solvent evaporated after completion of the reaction, respectively with dilute hydrochloric acid solution and distilled water wash twice, after recrystallization, obtain white crystal many (two (4-hydroxyphenyl) phenyl phosphonic acid esters) and replace chloropropyl silsesquioxane.
Step 2: many for 0.001mol (two (4-hydroxyphenyl) phenyl phosphonic acid esters) is replaced chloropropyl silsesquioxane, 150mlN, and dinethylformamide adds there-necked flask, after dissolving, adds 0.010molNa
2cO
30.004molKI, after stirring 1h, then adds 0.016mol epoxy chloropropane at 60 DEG C, 60 ~ 100 DEG C of reaction 12h, solvent evaporated, is extracted with ethyl acetate after washing, washing, dry, distillation, removes solvent, obtains many (4-hydroxyphenyl (4-(oxyethane-2-methoxyl group) phenyl) phenyl-phosphonic acid fat) and replace chloropropyl silsesquioxane.
Step 3: by mass, many (4-hydroxyphenyl (4-(oxyethane-2-methoxyl group) phenyl) the phenyl-phosphonic acid fat) of 4 parts are replaced chloropropyl silsesquioxane and 100 parts of dicyclopentadiene type ethylene rhodanates or bisphenol A cyanate ester monomer pre-polymerization 10 ~ 30min at 110 DEG C, pour in the mould of more than preheating 30min in the baking oven of 120 DEG C, about 60min is steeped at 130 DEG C of lower pumpings, then put into air dry oven to be cured, curing process: 160 DEG C/1h+180 DEG C/1h+200 DEG C/2h+220 DEG C/2h.Cooling, after the demoulding, at 240 DEG C of aftertreatment 2h, namely obtains phosphorus-silicon flame retardant type cyanate ester resin.
Embodiment 3:
Step 1: by molar basis, by 0.001mol chloropropyl POSS, 0.008molO, O-bis-(4-(hydroxyl) phenyl) phenyl phosphonic acid esters, the N of 100ml, dinethylformamide adds in there-necked flask, after dissolving, add 2ml triethylamine, the KI of 0.008mol, react 12 hours at water-bath 60 DEG C, solvent evaporated after completion of the reaction, respectively with dilute hydrochloric acid solution and distilled water wash twice, after recrystallization, obtain white crystal many (two (4-hydroxyphenyl) phenyl phosphonic acid esters) and replace chloropropyl silsesquioxane.
Step 2: by molar basis, many for 0.001mol (two (4-hydroxyphenyl) phenyl phosphonic acid esters) is replaced chloropropyl silsesquioxane, 100mlN, and dinethylformamide adds there-necked flask, after dissolving, adds 0.012molNa
2cO
30.004molKI, after stirring 3h at 30 ~ 60 DEG C, add 0.012mol epoxy chloropropane again, 60 ~ 100 DEG C of reaction 6 ~ 12h, distillation, removes solvent, obtains many (4-hydroxyphenyl (4-(oxyethane-2-methoxyl group) phenyl) phenyl-phosphonic acid fat) and replace chloropropyl silsesquioxane.
Step 3: by mass, many (4-hydroxyphenyl (4-(oxyethane-2-methoxyl group) phenyl) the phenyl-phosphonic acid fat) of 6 parts are replaced chloropropyl silsesquioxane and 100 parts of dicyclopentadiene type ethylene rhodanates or bisphenol A cyanate ester monomer pre-polymerization 10 ~ 30min at 110 DEG C, pour in the mould of more than preheating 30min in the baking oven of 120 DEG C, about 60min is steeped at 130 DEG C of lower pumpings, then put into air dry oven to be cured, curing process: 160 DEG C/1h+180 DEG C/1h+200 DEG C/2h+220 DEG C/2h.Cooling, after the demoulding, at 240 DEG C of aftertreatment 2h, namely obtains phosphorus-silicon flame retardant type cyanate ester resin.
Embodiment 4:
Step 1: by 0.001mol chloropropyl POSS, 0.0012molO, O-bis-(4-(hydroxyl) phenyl) phenyl phosphonic acid esters, the N of 150ml, dinethylformamide adds in there-necked flask, after dissolving, add 5ml triethylamine, the KI of 0.008mol, react 8 hours at water-bath 80 DEG C, solvent evaporated after completion of the reaction, respectively with dilute hydrochloric acid solution and distilled water wash twice, after recrystallization, obtain white crystal many (two (4-hydroxyphenyl) phenyl phosphonic acid esters) and replace chloropropyl silsesquioxane.
Step 2: many for 0.001mol (two (4-hydroxyphenyl) phenyl phosphonic acid esters) is replaced chloropropyl silsesquioxane, 150mlN, and dinethylformamide adds there-necked flask, after dissolving, adds 0.010molNa
2cO
30.004molKI, after stirring 1h, then adds 0.016mol epoxy chloropropane at 60 DEG C, 60 ~ 100 DEG C of reaction 12h, solvent evaporated, is extracted with ethyl acetate after washing, washing, dry, distillation, removes solvent, obtains many (4-hydroxyphenyl (4-(oxyethane-2-methoxyl group) phenyl) phenyl-phosphonic acid fat) and replace chloropropyl silsesquioxane.
Step 3: by mass, many (4-hydroxyphenyl (4-(oxyethane-2-methoxyl group) phenyl) the phenyl-phosphonic acid fat) of 10 parts are replaced chloropropyl silsesquioxane and 100 parts of dicyclopentadiene type ethylene rhodanates or bisphenol A cyanate ester monomer pre-polymerization 10 ~ 30min at 110 DEG C, pour in the mould of more than preheating 30min in the baking oven of 120 DEG C, about 60min is steeped at 130 DEG C of lower pumpings, then put into air dry oven to be cured, curing process: 160 DEG C/1h+180 DEG C/1h+200 DEG C/2h+220 DEG C/2h.Cooling, after the demoulding, at 240 DEG C of aftertreatment 2h, namely obtains phosphorus-silicon flame retardant type cyanate ester resin.
Embodiment 5:
Step 1: by 0.001mol chloropropyl POSS, 0.0012molO, O-bis-(4-(hydroxyl) phenyl) phenyl phosphonic acid esters, the N of 150ml, dinethylformamide adds in there-necked flask, after dissolving, add 5ml triethylamine, the KI of 0.008mol, react 8 hours at water-bath 80 DEG C, solvent evaporated after completion of the reaction, respectively with dilute hydrochloric acid solution and distilled water wash twice, after recrystallization, obtain white crystal many (two (4-hydroxyphenyl) phenyl phosphonic acid esters) and replace chloropropyl silsesquioxane.
Step 2: many for 0.001mol (two (4-hydroxyphenyl) phenyl phosphonic acid esters) is replaced chloropropyl silsesquioxane, 150mlN, and dinethylformamide adds there-necked flask, after dissolving, adds 0.010molNa
2cO
30.004molKI, after stirring 1h, then adds 0.016mol epoxy chloropropane at 60 DEG C, 60 ~ 100 DEG C of reaction 12h, solvent evaporated, is extracted with ethyl acetate after washing, washing, dry, distillation, removes solvent, obtains many (4-hydroxyphenyl (4-(oxyethane-2-methoxyl group) phenyl) phenyl-phosphonic acid fat) and replace chloropropyl silsesquioxane.
Step 3: by mass, many (4-hydroxyphenyl (4-(oxyethane-2-methoxyl group) phenyl) the phenyl-phosphonic acid fat) of 5 parts are replaced chloropropyl silsesquioxane and 100 parts of dicyclopentadiene type ethylene rhodanates or bisphenol A cyanate ester monomer pre-polymerization 10 ~ 30min at 110 DEG C, pour in the mould of more than preheating 30min in the baking oven of 120 DEG C, about 60min is steeped at 130 DEG C of lower pumpings, then put into air dry oven to be cured, curing process: 160 DEG C/1h+180 DEG C/1h+200 DEG C/2h+220 DEG C/2h.Cooling, after the demoulding, at 240 DEG C of aftertreatment 2h, namely obtains phosphorus-silicon flame retardant type cyanate ester resin.
Claims (5)
1. phosphorus-silicon flame retardant type cyanate ester resin, is characterized in that comprising 100 parts of dicyclopentadiene type ethylene rhodanates or bisphenol A cyanate ester resin monomer, many (4-hydroxyphenyl (4-(oxyethane-2-methoxyl group) phenyl) the phenyl-phosphonic acid fat) of 0.1 ~ 20 part replaces chloropropyl silsesquioxane; The structural formula that described many (4-hydroxyphenyl (4-(oxyethane-2-methoxyl group) phenyl) phenyl-phosphonic acid fat) replaces chloropropyl silsesquioxane is:
The number of above-mentioned chemical substance is mass fraction.
2. prepare a method for phosphorus described in claim 1-silicon flame retardant type cyanate ester resin, it is characterized in that step is as follows:
Step 1: many (4-hydroxyphenyl (4-(oxyethane-2-methoxyl group) phenyl) the phenyl-phosphonic acid fat) of 0.1 ~ 20 mass parts are replaced chloropropyl silsesquioxane and 100 parts of dicyclopentadiene type ethylene rhodanates or bisphenol A cyanate ester monomer pre-polymerization 10 ~ 30min at 110 DEG C;
Step 2: pour in mould, puts into air dry oven and is cured, curing process: 160 DEG C/1h+180 DEG C/1h+200 DEG C/2h+220 DEG C/2h after 130 DEG C of lower pumpings bubble; Then cool, after the demoulding, at 240 DEG C of aftertreatment 2h, obtain phosphorus-silicon flame retardant type cyanate ester resin.
3. the preparation method of phosphorus according to claim 2-silicon flame retardant type cyanate ester resin, is characterized in that: the bubble of bleeding of described step 2 is at 130 DEG C of lower pumping bubble 60min.
4. the preparation method of phosphorus according to claim 2-silicon flame retardant type cyanate ester resin, is characterized in that: described mould more than preheating 30min in the baking oven of 120 DEG C.
5. the preparation method of phosphorus according to claim 2-silicon flame retardant type cyanate ester resin, is characterized in that: the preparation process that described many (4-hydroxyphenyl (4-(oxyethane-2-methoxyl group) phenyl) phenyl-phosphonic acid fat) replaces chloropropyl silsesquioxane is:
Step 1: by molar basis, by 1 part of chloropropyl POSS, 4 ~ 10 parts of O, O-bis-(4-(hydroxyl) phenyl) phenyl phosphonic acid esters, the N of 10ml ~ 400ml, dinethylformamide mixed dissolution, add 1 ~ 50ml triethylamine again, the KI of 1 ~ 5 part, react 6 ~ 12 hours at water-bath 60 ~ 80 DEG C, solvent evaporated after completion of the reaction, respectively with dilute hydrochloric acid solution and distilled water wash twice, after recrystallization, obtain white crystal many (two (4-hydroxyphenyl) phenyl phosphonic acid esters) and replace chloropropyl silsesquioxane;
Step 2: by molar basis, replaces chloropropyl silsesquioxane, 50ml ~ 500mlN by (two (4-hydroxyphenyl) phenyl phosphonic acid esters) more than 1 part, after dinethylformamide mixed dissolution, adds 4 ~ 16 parts of Na
2cO
31 ~ 20 part of KI, after stirring 1 ~ 3h at 30 ~ 60 DEG C, add 8 ~ 20 parts of epoxy chloropropane again, 60 ~ 100 DEG C of reaction 6 ~ 12h, distillation, removes solvent, obtains many (4-hydroxyphenyl (4-(oxyethane-2-methoxyl group) phenyl) phenyl-phosphonic acid fat) and replace chloropropyl silsesquioxane.
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Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN106750239A (en) * | 2016-11-23 | 2017-05-31 | 厦门大学 | A kind of phosphorus-nitrogen containing fluoropolymer fire retardant and preparation method and application |
CN110372861A (en) * | 2019-06-27 | 2019-10-25 | 扬州天启新材料股份有限公司 | The preparation method of modification dicyclopentadiene type ethylene rhodanate resin with agent of low hygroscopicity |
CN110982264A (en) * | 2019-12-23 | 2020-04-10 | 哈尔滨工业大学 | Preparation method of modified cyanate ester resin with atomic oxygen irradiation resisting characteristic |
CN111004506A (en) * | 2019-12-23 | 2020-04-14 | 哈尔滨工业大学 | Preparation method of modified cyanate ester resin with ultraviolet irradiation resistance |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101565545A (en) * | 2009-04-01 | 2009-10-28 | 北京化工大学 | Method for preparing ethylene rhodanate-epoxy-POSS hybrid resin |
CN102079874A (en) * | 2009-11-27 | 2011-06-01 | 南京理工大学 | Preparation method of cage-type silsesquioxane-containing low-dielectric cyanate hybrid resin |
US8058380B1 (en) * | 2009-06-24 | 2011-11-15 | The United States Of America As Represented By The Secretary Of The Air Force | POSS enhanced compositions |
CN104558601A (en) * | 2015-01-09 | 2015-04-29 | 西北工业大学 | Phosphorus-containing flame-retardant cyanate ester resin and preparation method thereof |
CN104650583A (en) * | 2013-11-20 | 2015-05-27 | 深圳光启创新技术有限公司 | Modified cyanate ester resin composite material, metamaterial base plate, preparation methods thereof and metamaterial |
-
2015
- 2015-09-18 CN CN201510600243.3A patent/CN105218811B/en not_active Expired - Fee Related
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101565545A (en) * | 2009-04-01 | 2009-10-28 | 北京化工大学 | Method for preparing ethylene rhodanate-epoxy-POSS hybrid resin |
US8058380B1 (en) * | 2009-06-24 | 2011-11-15 | The United States Of America As Represented By The Secretary Of The Air Force | POSS enhanced compositions |
CN102079874A (en) * | 2009-11-27 | 2011-06-01 | 南京理工大学 | Preparation method of cage-type silsesquioxane-containing low-dielectric cyanate hybrid resin |
CN104650583A (en) * | 2013-11-20 | 2015-05-27 | 深圳光启创新技术有限公司 | Modified cyanate ester resin composite material, metamaterial base plate, preparation methods thereof and metamaterial |
CN104558601A (en) * | 2015-01-09 | 2015-04-29 | 西北工业大学 | Phosphorus-containing flame-retardant cyanate ester resin and preparation method thereof |
Non-Patent Citations (2)
Title |
---|
HOSOUK CHO, ET AL: "Synthesis, morphology, and viscoelastic properties of polyhedral oligomeric silsesquioxane nanocomposites with epoxy and cyanate ester matrices", 《JOURNAL OF INORGANIC AND ORGANOMETALLIC POLYMERS AND MATERIALS》 * |
赵春宝 等: "氰酸酯树脂/八(γ-氯丙基)多面体低聚倍半硅氧烷复合材料", 《塑料科技》 * |
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CN106750239A (en) * | 2016-11-23 | 2017-05-31 | 厦门大学 | A kind of phosphorus-nitrogen containing fluoropolymer fire retardant and preparation method and application |
CN106750239B (en) * | 2016-11-23 | 2019-02-05 | 厦门大学 | A kind of phosphorus-nitrogen containing silicon polymer fire retardant and the preparation method and application thereof |
CN110372861A (en) * | 2019-06-27 | 2019-10-25 | 扬州天启新材料股份有限公司 | The preparation method of modification dicyclopentadiene type ethylene rhodanate resin with agent of low hygroscopicity |
CN110372861B (en) * | 2019-06-27 | 2020-04-28 | 扬州天启新材料股份有限公司 | Preparation method of modified dicyclopentadiene type cyanate ester resin with low hygroscopicity |
CN110982264A (en) * | 2019-12-23 | 2020-04-10 | 哈尔滨工业大学 | Preparation method of modified cyanate ester resin with atomic oxygen irradiation resisting characteristic |
CN111004506A (en) * | 2019-12-23 | 2020-04-14 | 哈尔滨工业大学 | Preparation method of modified cyanate ester resin with ultraviolet irradiation resistance |
CN111004506B (en) * | 2019-12-23 | 2023-03-10 | 哈尔滨工业大学 | Preparation method of modified cyanate ester resin with ultraviolet irradiation resistance |
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