CN105218811B - 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
- Publication number
- CN105218811B CN105218811B CN201510600243.3A CN201510600243A CN105218811B CN 105218811 B CN105218811 B CN 105218811B CN 201510600243 A CN201510600243 A CN 201510600243A CN 105218811 B CN105218811 B CN 105218811B
- Authority
- CN
- China
- Prior art keywords
- phenyl
- phosphonic acid
- hydroxyphenyls
- cyanate ester
- chloropropyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 0 C=*c(cc1)ccc1OP(c1ccccc1)(Oc(cc1)ccc1O*C1OCC1)=O Chemical compound C=*c(cc1)ccc1OP(c1ccccc1)(Oc(cc1)ccc1O*C1OCC1)=O 0.000 description 1
Landscapes
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
The present invention relates to a kind of phosphorus silicon flame retardant type cyanate ester resin and preparation method thereof, resin components include dicyclopentadiene type ethylene rhodanate or bisphenol A cyanate ester monomer and more (4 hydroxyphenyls (4 (methoxyl group of oxirane 2) phenyl) phenyl-phosphonic acid fat) substitution chloropropyl silsesquioxane.More (4 hydroxyphenyls (4 (methoxyl group of oxirane 2) phenyl) phenyl-phosphonic acid fat) substitution chloropropyl silsesquioxane may participate in cyanate curing reaction as reactive flame retardant, its compatibility with resin is improved, while may also function as toughness reinforcing, reduce the effect of dielectric constant.Therefore, solidfied material has excellent dielectric properties, good mechanical property and fire resistance, can be used as high performance electronic packaging material.
Description
Technical field
The invention belongs to advanced compound materials science domain, more particularly to a kind of phosphorus-silicon flame retardant type cyanate ester resin
And preparation method thereof.
Background technology
Cyanate ester resin is widely used in Aero-Space, printed circuit board (PCB), resistance to height as a kind of high-performance composite materials matrix
The fields such as warm adhesive.But in the application of high performance material, the anti-flammability of cyanate ester resin is difficult to meet to require, therefore this
A kind of phosphorous POSS based flameproofings of response type of Patent exploitation, the phosphorus-silicon type fire retardant contain epoxy-functional, can remove cyanate
Condensation reaction occurs for resin, so as to improve the compatibility of phosphorous POSS based flameproofings and cyanate ester resin.Due to phosphorus and silicon member
The synergy of element, resin surface can be promoted to form fine and close layer of charcoal during burning, so as to greatly improve the anti-flammability of cyanate ester resin
Energy.Simultaneously because the presence of cage type POSS structures, the dielectric properties of resin matrix also obtain larger raising.Solidfied material has good
Mechanical property, excellent dielectric properties and fire resistance, to widen cyanate ester resin its in high-performance engineering field should
With having great importance.
The content of the invention
Technical problems to be solved
In order to avoid the shortcomings of the prior art, the present invention proposes a kind of phosphorus-silicon flame retardant type cyanate ester resin and its system
Preparation Method, the resin cured matter have excellent dielectric properties, good mechanical property and fire resistance, can be used as high-performance electric
Sub- encapsulating material uses.
Technical scheme
A kind of phosphorus-silicon flame retardant type cyanate ester resin, it is characterised in that including 100 parts of dicyclopentadiene type ethylene rhodanates or bis-phenol
A type cyanate resins alicyclic monomer, 0.1~20 part more (4- hydroxyphenyls (4- (oxirane -2- methoxyl groups) phenyl) phenyl-phosphonic acids
Fat) substitution chloropropyl silsesquioxane；More (4- hydroxyphenyls (4- (oxirane -2- methoxyl groups) phenyl) the phenyl-phosphonic acid fat)
Substitution chloropropyl silsesquioxane structural formula be：
The number of above-mentioned chemical substance is mass fraction.
A kind of method for preparing the phosphorus-silicon flame retardant type cyanate ester resin, it is characterised in that step is as follows：
Step 1：By more (4- hydroxyphenyls (4- (oxirane -2- methoxyl groups) phenyl) phenyl-phosphonic acids of 0.1~20 mass parts
Fat) substitute chloropropyl silsesquioxane and 100 parts of dicyclopentadiene type ethylene rhodanates or bisphenol A cyanate ester monomer at 110 DEG C
10~30min of pre-polymerization；
Step 2：Pour into mould, be put into air dry oven and solidified after 130 DEG C of lower pumpings steep, curing process：
160℃/1h+180℃/1h+200℃/2h+220℃/2h；Then cool down, after the demoulding, post-process 2h at 240 DEG C, obtain phosphorus-silicon
Flame retardant type cyanate ester resin.
The pumping bubble of the step 2 is to steep 60min in 130 DEG C of lower pumpings.
The mould preheats more than 30min in 120 DEG C of baking oven.
More (4- hydroxyphenyls (4- (oxirane -2- methoxyl groups) phenyl) the phenyl-phosphonic acid fat) substitutes chloropropyl sesquialter silicon
The preparation process of oxygen alkane is：
Step 1：Based on molal quantity, by 1 part of chloropropyl POSS, 4~10 parts of O, O- bis- (4- (hydroxyl) phenyl) phenyl-phosphonic acid
Ester, 10ml~400ml DMF mixed dissolution, add 1~50ml triethylamines, 1~5 part of KI, in water
React 6~12 hours at 60~80 DEG C of bath, after completion of the reaction solvent evaporated, with dilute hydrochloric acid solution and distill water washing two respectively
It is secondary, after recrystallization, obtain white crystal more (two (4- hydroxyphenyls) phenyl phosphonic acid esters) substitution chloropropyl silsesquioxane；
Step 2：Based on molal quantity, (two (4- hydroxyphenyls) phenyl phosphonic acid esters) more than 1 part are substituted into chloropropyl silsesquioxane,
After 50ml~500ml DMF mixed dissolutions, 4~16 parts of Na are added2CO3, 1~20 part of KI, at 30~60 DEG C
After stirring 1~3h, 8~20 parts of epoxychloropropane are added, 60~100 DEG C of 6~12h of reaction, distillation, solvent is removed, obtains more
(4- hydroxyphenyls (4- (oxirane -2- methoxyl groups) phenyl) phenyl-phosphonic acid fat) substitutes chloropropyl silsesquioxane.
Beneficial effect
A kind of phosphorus proposed by the present invention-silicon flame retardant type cyanate ester resin and preparation method thereof, resin components include bicyclic penta
Diene type cyanate or bisphenol A cyanate ester monomer and more (4- hydroxyphenyls (4- (oxirane -2- methoxyl groups) phenyl) Phenylphosphines
Sour fat) substitution chloropropyl silsesquioxane.More (4- hydroxyphenyls (4- (oxirane -2- methoxyl groups) phenyl) phenyl-phosphonic acid fat) take
Cyanate curing reaction is may participate in as reactive flame retardant for chloropropyl silsesquioxane, it is compatible with resin to improve it
Property, while may also function as toughness reinforcing, reduce the effect of dielectric constant.Therefore, solidfied material has excellent dielectric properties, good power
Performance and fire resistance are learned, can be used as high performance electronic packaging material.
More (4- hydroxyphenyls (4- (oxirane -2- methoxies in phosphorus-silicon flame retardant type cyanate ester resin system of the present invention
Base) phenyl) phenyl-phosphonic acid fat) substitute chloropropyl silsesquioxane and cyanate ester resin system that there is good compatibility, phosphorus member
Element acts synergistically with element silicon, larger raising resins fire retardant.Also, more (4- hydroxyphenyls (4- (oxirane -2- methoxyl groups)
Phenyl) phenyl-phosphonic acid fat) substitution chloropropyl silsesquioxane may participate in the solidification of resin, the crosslink density of resin is reduced, so as to
Improve its toughness.It can thus be stated that phosphorus-silicon flame retardant type cyanate ester resin that the present invention is developed can both improve common cyanate
The defects of resin toughness and anti-flammability deficiency, the problem of additive flame retardant is with its poor compatibility can be overcome again.Simultaneously as
The dielectric properties for causing resin matrix are also obtained larger raising by the presence of cage type POSS structures.
Brief description of the drawings
Fig. 1：Phosphorus-silicon flame retardant type ethylene rhodanate resin curing reaction mechanism
Embodiment
In conjunction with embodiment, accompanying drawing, the invention will be further described：
The present invention program：A kind of phosphorous POSS of response type that can be reacted with resin containing epoxy-functional is synthesized first
Based flameproofing, i.e., more (4- hydroxyphenyls (4- (oxirane -2- methoxyl groups) phenyl) phenyl-phosphonic acid fat) substitution chloropropyl sesquialter silicon
Oxygen alkane, it is then added into cyanate resin alicyclic monomer or performed polymer, because it contains epoxy-functional, may participate in cyanate resin
The solidification of fat so that more (4- hydroxyphenyls (4- (oxirane -2- methoxyl groups) phenyl) phenyl-phosphonic acid fat) substitutes chloropropyl sesquialter
Siloxanes is connected in cyanate ester resin network, so as to improve its toughness, anti-flammability and dielectric properties.Its curing kinetics
Such as Fig. 1.
The structural formula of the dicyclopentadiene type ethylene rhodanate is as follows：
The structural formula of the bisphenol A-type cyanate resin monomer is as follows：
More (4- hydroxyphenyls (4- (oxirane -2- methoxyl groups) phenyl) the phenyl-phosphonic acid fat) substitutes chloropropyl sesquialter silicon
The structural formula of oxygen alkane is as follows：
Specific embodiment：
Embodiment 1：
Step 1：Based on molal quantity, by 0.001mol chloropropyls POSS, 0.008mol O, O- bis- (4- (hydroxyl) phenyl) benzene
Base phosphonate ester, 100ml DMF is added in three-necked flask, after dissolving, adds 2ml triethylamines, 0.008mol
KI, 12 hours are reacted at 60 DEG C of water-bath, after completion of the reaction solvent evaporated, respectively with dilute hydrochloric acid solution and distillation water washing two
It is secondary, after recrystallization, obtain white crystal more (two (4- hydroxyphenyls) phenyl phosphonic acid esters) substitution chloropropyl silsesquioxane.
Step 2：Based on molal quantity, 0.001mol more (two (4- hydroxyphenyls) phenyl phosphonic acid esters) is substituted into chloropropyl sesquialter silicon
Oxygen alkane, 100ml DMFs add three-necked flask, after dissolving, add 0.012mol Na2CO3, 0.004mol
KI, after stirring 3h at 30~60 DEG C, 0.012mol epoxychloropropane is added, 60~100 DEG C of 6~12h of reaction, distills, removes
Solvent, obtain more (4- hydroxyphenyls (4- (oxirane -2- methoxyl groups) phenyl) phenyl-phosphonic acid fat) substitution chloropropyl silsesquioxane
Alkane.
Step 3：By mass, by (4- hydroxyphenyls (4- (oxirane -2- methoxyl groups) phenyl) phenyl-phosphonic acid fat) more than 2 parts
Substitute the pre-polymerization at 110 DEG C of chloropropyl silsesquioxane and 100 parts of dicyclopentadiene type ethylene rhodanates or bisphenol A cyanate ester monomer
10~30min, pour into the mould that more than 30min is preheated in 120 DEG C of baking oven, steep about 60min in 130 DEG C of lower pumpings, so
After be put into air dry oven and solidified, curing process：160℃/1h+180℃/1h+200℃/2h+220℃/2h.Cooling,
After the demoulding, 2h is post-processed at 240 DEG C, that is, obtains phosphorus-silicon flame retardant type cyanate ester resin.
Embodiment 2：
Step 1：By 0.001mol chloropropyls POSS, 0.0012mol O, O- bis- (4- (hydroxyl) phenyl) phenyl phosphonic acid esters,
150ml DMF is added in three-necked flask, after dissolving, adds 5ml triethylamines, 0.008mol KI, water-bath
Reacted 8 hours at 80 DEG C, solvent evaporated, is washed twice with dilute hydrochloric acid solution and distilled water respectively after completion of the reaction, after recrystallization,
Obtain white crystal more (two (4- hydroxyphenyls) phenyl phosphonic acid esters) substitution chloropropyl silsesquioxane.
Step 2：0.001mol more (two (4- hydroxyphenyls) phenyl phosphonic acid esters) is substituted into chloropropyl silsesquioxane, 150ml
DMF adds three-necked flask, after dissolving, adds 0.010mol Na2CO3, 0.004mol KI, stir at 60 DEG C
After 1h, 0.016mol epoxychloropropane is added, 60~100 DEG C of reaction 12h, solvent evaporated, is extracted with ethyl acetate after washing,
Washing, dry, distillation, remove solvent, obtain more (4- hydroxyphenyls (4- (oxirane -2- methoxyl groups) phenyl) phenyl-phosphonic acid fat)
Substitute chloropropyl silsesquioxane.
Step 3：By mass, by 4 parts more (4- hydroxyphenyls (4- (oxirane -2- methoxyl groups) phenyl) phenyl-phosphonic acids
Fat) substitute chloropropyl silsesquioxane and 100 parts of dicyclopentadiene type ethylene rhodanates or bisphenol A cyanate ester monomer at 110 DEG C
10~30min of pre-polymerization, pour into the mould that more than 30min is preheated in 120 DEG C of baking oven, in 130 DEG C of lower pumping bubbles about
60min, it is then placed in air dry oven and is solidified, curing process：160℃/1h+180℃/1h+200℃/2h+220℃/
2h.Cooling, after the demoulding, 2h is post-processed at 240 DEG C, that is, obtains phosphorus-silicon flame retardant type cyanate ester resin.
Embodiment 3：
Step 1：Based on molal quantity, by 0.001mol chloropropyls POSS, 0.008mol O, O- bis- (4- (hydroxyl) phenyl) benzene
Base phosphonate ester, 100ml DMF is added in three-necked flask, after dissolving, adds 2ml triethylamines, 0.008mol
KI, 12 hours are reacted at 60 DEG C of water-bath, after completion of the reaction solvent evaporated, respectively with dilute hydrochloric acid solution and distillation water washing two
It is secondary, after recrystallization, obtain white crystal more (two (4- hydroxyphenyls) phenyl phosphonic acid esters) substitution chloropropyl silsesquioxane.
Step 2：Based on molal quantity, 0.001mol more (two (4- hydroxyphenyls) phenyl phosphonic acid esters) is substituted into chloropropyl sesquialter silicon
Oxygen alkane, 100ml DMFs add three-necked flask, after dissolving, add 0.012mol Na2CO3, 0.004mol
KI, after stirring 3h at 30~60 DEG C, 0.012mol epoxychloropropane is added, 60~100 DEG C of 6~12h of reaction, distills, removes
Solvent, obtain more (4- hydroxyphenyls (4- (oxirane -2- methoxyl groups) phenyl) phenyl-phosphonic acid fat) substitution chloropropyl silsesquioxane
Alkane.
Step 3：By mass, by 6 parts more (4- hydroxyphenyls (4- (oxirane -2- methoxyl groups) phenyl) phenyl-phosphonic acids
Fat) substitute chloropropyl silsesquioxane and 100 parts of dicyclopentadiene type ethylene rhodanates or bisphenol A cyanate ester monomer at 110 DEG C
10~30min of pre-polymerization, pour into the mould that more than 30min is preheated in 120 DEG C of baking oven, in 130 DEG C of lower pumping bubbles about
60min, it is then placed in air dry oven and is solidified, curing process：160℃/1h+180℃/1h+200℃/2h+220℃/
2h.Cooling, after the demoulding, 2h is post-processed at 240 DEG C, that is, obtains phosphorus-silicon flame retardant type cyanate ester resin.
Embodiment 4：
Step 1：By 0.001mol chloropropyls POSS, 0.0012mol O, O- bis- (4- (hydroxyl) phenyl) phenyl phosphonic acid esters,
150ml DMF is added in three-necked flask, after dissolving, adds 5ml triethylamines, 0.008mol KI, water-bath
Reacted 8 hours at 80 DEG C, solvent evaporated, is washed twice with dilute hydrochloric acid solution and distilled water respectively after completion of the reaction, after recrystallization,
Obtain white crystal more (two (4- hydroxyphenyls) phenyl phosphonic acid esters) substitution chloropropyl silsesquioxane.
Step 2：0.001mol more (two (4- hydroxyphenyls) phenyl phosphonic acid esters) is substituted into chloropropyl silsesquioxane, 150ml
DMF adds three-necked flask, after dissolving, adds 0.010mol Na2CO3, 0.004mol KI, stir at 60 DEG C
After 1h, 0.016mol epoxychloropropane is added, 60~100 DEG C of reaction 12h, solvent evaporated, is extracted with ethyl acetate after washing,
Washing, dry, distillation, remove solvent, obtain more (4- hydroxyphenyls (4- (oxirane -2- methoxyl groups) phenyl) phenyl-phosphonic acid fat)
Substitute chloropropyl silsesquioxane.
Step 3：By mass, by 10 parts more (4- hydroxyphenyls (4- (oxirane -2- methoxyl groups) phenyl) phenyl-phosphonic acids
Fat) substitute chloropropyl silsesquioxane and 100 parts of dicyclopentadiene type ethylene rhodanates or bisphenol A cyanate ester monomer at 110 DEG C
10~30min of pre-polymerization, pour into the mould that more than 30min is preheated in 120 DEG C of baking oven, in 130 DEG C of lower pumping bubbles about
60min, it is then placed in air dry oven and is solidified, curing process：160℃/1h+180℃/1h+200℃/2h+220℃/
2h.Cooling, after the demoulding, 2h is post-processed at 240 DEG C, that is, obtains phosphorus-silicon flame retardant type cyanate ester resin.
Embodiment 5：
Step 1：By 0.001mol chloropropyls POSS, 0.0012mol O, O- bis- (4- (hydroxyl) phenyl) phenyl phosphonic acid esters,
150ml DMF is added in three-necked flask, after dissolving, adds 5ml triethylamines, 0.008mol KI, water-bath
Reacted 8 hours at 80 DEG C, solvent evaporated, is washed twice with dilute hydrochloric acid solution and distilled water respectively after completion of the reaction, after recrystallization,
Obtain white crystal more (two (4- hydroxyphenyls) phenyl phosphonic acid esters) substitution chloropropyl silsesquioxane.
Step 2：0.001mol more (two (4- hydroxyphenyls) phenyl phosphonic acid esters) is substituted into chloropropyl silsesquioxane, 150ml
DMF adds three-necked flask, after dissolving, adds 0.010mol Na2CO3, 0.004mol KI, stir at 60 DEG C
After 1h, 0.016mol epoxychloropropane is added, 60~100 DEG C of reaction 12h, solvent evaporated, is extracted with ethyl acetate after washing,
Washing, dry, distillation, remove solvent, obtain more (4- hydroxyphenyls (4- (oxirane -2- methoxyl groups) phenyl) phenyl-phosphonic acid fat)
Substitute chloropropyl silsesquioxane.
Step 3：By mass, by 5 parts more (4- hydroxyphenyls (4- (oxirane -2- methoxyl groups) phenyl) phenyl-phosphonic acids
Fat) substitute chloropropyl silsesquioxane and 100 parts of dicyclopentadiene type ethylene rhodanates or bisphenol A cyanate ester monomer at 110 DEG C
10~30min of pre-polymerization, pour into the mould that more than 30min is preheated in 120 DEG C of baking oven, in 130 DEG C of lower pumping bubbles about
60min, it is then placed in air dry oven and is solidified, curing process：160℃/1h+180℃/1h+200℃/2h+220℃/
2h.Cooling, after the demoulding, 2h is post-processed at 240 DEG C, that is, obtains phosphorus-silicon flame retardant type cyanate ester resin.
Claims (1)
1. a kind of method for preparing phosphorus-silicon flame retardant type cyanate ester resin, described phosphorus-silicon flame retardant type cyanate ester resin, including 100
Part dicyclopentadiene type ethylene rhodanate or bisphenol A cyanate ester resin monomer, 0.1~20 part of more (4- hydroxyphenyls (4- (epoxy second
Alkane -2- methoxyl groups) phenyl) phenyl phosphonic acid esters) substitution chloropropyl silsesquioxane；More (4- hydroxyphenyls (4- (epoxy second
Alkane -2- methoxyl groups) phenyl) phenyl phosphonic acid esters) and substitution chloropropyl silsesquioxane structural formula be：
The number of above-mentioned chemical substance is mass fraction；It is characterized in that step is as follows：
Step 1：By more (4- hydroxyphenyls (4- (oxirane -2- methoxyl groups) phenyl) phenyl phosphonic acid esters) of 0.1~20 mass parts
Substitute the pre-polymerization at 110 DEG C of chloropropyl silsesquioxane and 100 parts of dicyclopentadiene type ethylene rhodanates or bisphenol A cyanate ester monomer
10~30min；
Step 2：Pour into mould, be put into air dry oven and solidified after 130 DEG C of lower pumpings steep, curing process：160
℃/1h+180℃/1h+200℃/2h+220℃/2h；Then cool down, after the demoulding, 2h is post-processed at 240 DEG C, obtain phosphorus-silicon resistance
Combustion type cyanate ester resin；
The pumping bubble of the step 2 is to steep 60min in 130 DEG C of lower pumpings；
The mould preheats more than 30min in 120 DEG C of baking oven；
More (4- hydroxyphenyls (4- (oxirane -2- methoxyl groups) phenyl) phenyl phosphonic acid esters) substitute chloropropyl silsesquioxane
The preparation process of alkane is：
Step 1：Based on molal quantity, by 1 part of chloropropyl POSS, 4~10 parts of O, O- bis- (4- (hydroxyl) phenyl) phenyl phosphonic acid esters,
10ml~400ml DMF mixed dissolution, add 1~50ml triethylamines, 1~5 part of KI, in water-bath 60
Reacted 6~12 hours at~80 DEG C, solvent evaporated, is washed twice with dilute hydrochloric acid solution and distilled water respectively after completion of the reaction, weight
After crystallization, white crystal more (two (4- hydroxyphenyls) phenyl phosphonic acid esters) substitution chloropropyl silsesquioxane is obtained；
Step 2：Based on molal quantity, (two (4- hydroxyphenyls) phenyl phosphonic acid esters) more than 1 part are substituted into chloropropyl silsesquioxane, 50ml
After~500ml DMF mixed dissolutions, 4~16 parts of Na are added2CO3, 1~20 part of KI, 1 is stirred at 30~60 DEG C
After~3h, 8~20 parts of epoxychloropropane are added, 60~100 DEG C of 6~12h of reaction, distillation, solvent is removed, obtains more (4- hydroxyls
Phenyl (4- (oxirane -2- methoxyl groups) phenyl) phenyl phosphonic acid esters) substitution chloropropyl silsesquioxane.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510600243.3A CN105218811B (en) | 2015-09-18 | 2015-09-18 | A kind of phosphorus silicon flame retardant type cyanate ester resin and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510600243.3A CN105218811B (en) | 2015-09-18 | 2015-09-18 | A kind of phosphorus silicon flame retardant type cyanate ester resin and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105218811A CN105218811A (en) | 2016-01-06 |
| CN105218811B true CN105218811B (en) | 2017-11-17 |
Family
ID=54988128
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510600243.3A Expired - Fee Related CN105218811B (en) | 2015-09-18 | 2015-09-18 | A kind of phosphorus silicon flame retardant type cyanate ester resin and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105218811B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| 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 |
| 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 |
| 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 |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101565545B (en) * | 2009-04-01 | 2011-05-11 | 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 |
| CN104650583B (en) * | 2013-11-20 | 2018-06-08 | 深圳光启创新技术有限公司 | Modified cyanic acid ester resin composite material, metamaterial substrate, their preparation method and Meta Materials |
| CN104558601B (en) * | 2015-01-09 | 2016-10-05 | 西北工业大学 | A kind of phosphor-containing flame-proof type cyanate ester resin and preparation method thereof |
-
2015
- 2015-09-18 CN CN201510600243.3A patent/CN105218811B/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN105218811A (en) | 2016-01-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| TWI555754B (en) | Manufacture of advanced epoxy resins and their high tg thermosets for electronic applications | |
| CN105218811B (en) | A kind of phosphorus silicon flame retardant type cyanate ester resin and preparation method thereof | |
| CN103834168B (en) | A kind of halogen-free flame resistance resin composite | |
| JP6318191B2 (en) | Flame retardant compounds, curing agents and polyphenolic epoxy resins | |
| CN106366128B (en) | Phosphine phenanthrene class compound and its preparation method and application | |
| JP6461170B2 (en) | Thermosetting resin composition | |
| CN108250675A (en) | A kind of phosphorous active ester and its halogen-free composition and copper clad foil substrate | |
| CN102964777B (en) | Phosphorus-containing and halogen-free flame retardant resin adhesive as well as preparation method and application thereof | |
| CN105348742B (en) | Compositions of thermosetting resin, prepreg and the laminate of the benzoxazine colophony containing melamine-type | |
| JP2008533236A (en) | Non-halogen flame retardant highly heat-resistant phosphorus-modified epoxy resin composition | |
| JP2012522100A (en) | Phosphorus-modified phenol novolac resin, curing agent containing the same, and epoxy resin composition | |
| CN106166874A (en) | Halogen-free copper-clad plate and preparation method thereof | |
| CN105086449B (en) | Phosphorus-containing POSS (polyhedral oligomeric silsesquioxane) flame-retardant bismaleimide resin and preparation method thereof | |
| CN105331053A (en) | Halogen-free resin composition, and prepreg and laminated board for printed circuit prepared from the resin composition | |
| JP2014516973A (en) | Phosphorus-containing compounds useful for the production of halogen-free ignition resistant polymers | |
| KR20140009029A (en) | Novolac-based epoxy compound, preparing method thereof, composition, cured product thereof, and use thereof | |
| CN103013046A (en) | Halogen-free flame retardant resin composition and use thereof | |
| TWI466913B (en) | A kind of halogenated flame retardant and high glass transition temperature of phenolic resin hardener and its preparation method | |
| TWI426122B (en) | Low dielectric dielectric flame retardant bifunctional Benzoxazine resin and its manufacturing method | |
| TW200410997A (en) | Curing agents for epoxy resins, use thereof and epoxy resin cured therewith | |
| JP5158739B2 (en) | Thermosetting polymer composition and cured product thereof | |
| TW593527B (en) | Halogen-free, phosphorus-free flame-retardant advanced epoxy resin and an epoxy composition containing the same | |
| CN104558601B (en) | A kind of phosphor-containing flame-proof type cyanate ester resin and preparation method thereof | |
| CN105801814A (en) | Halogen-free thermosetting resin composition and prepreg and printed circuit laminated board using the same | |
| JP2005255813A (en) | Epoxy resin composition and its cured product |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20190612 Address after: 523808 Zhongsheng silver building, No. three road, Songshan Lake headquarters, Dongguan, Guangdong, 20 Patentee after: Dongguan Sanhang civil Military Integration Innovation Institute Address before: 710072 No. 127 Youyi West Road, Shaanxi, Xi'an Patentee before: Northwestern Polytechnical University |
|
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20171117 Termination date: 20180918 |