CN103497310A - High-strength and high-modulus modified cyanate ester resin composition - Google Patents
High-strength and high-modulus modified cyanate ester resin composition Download PDFInfo
- Publication number
- CN103497310A CN103497310A CN201310442784.9A CN201310442784A CN103497310A CN 103497310 A CN103497310 A CN 103497310A CN 201310442784 A CN201310442784 A CN 201310442784A CN 103497310 A CN103497310 A CN 103497310A
- Authority
- CN
- China
- Prior art keywords
- anhydride
- component
- modulus
- cyanate
- resin composition
- 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.)
- Pending
Links
Landscapes
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
The invention relates to a high-strength and high-modulus modified cyanate ester resin composition. The raw material of resin is formed by mixing a component A, a component B and a component C, wherein the raw material of the component A is composed of a cyanate ester monomer, a bismaleimide monomer and a bisoxazoline compound, the component B comprises a bifunctional epoxy compound and a glycidyl amine epoxy compound with three or four degrees of functionality, and the component C is an anhydride compound. The uncured resin has favorable processing property; the cured resin has the characteristics of high strength and high modulus.
Description
Technical field
The present invention relates to a kind of modified cyanic acid ester resin composition with high strength and high-modulus.
Background technology
Cyanate is the thermosetting resin that a class has good dielectric properties, mechanical property, thermotolerance, low water absorption, in fields such as high-performance circuit board, transparent structure material and high tenacity structure materials, has a wide range of applications.Cyanate and other compound are combined according to a specific ratio, carried out chemical modification, can be met the thermoset resin material that the different application field needs.
The contriver, in the research in early stage, has proposed a kind of " high-ductility co-cured resin of cyanate and preparation method thereof, application (ZL 200910052209.1) ".This co-curing modified resin is comprised of cyanate, bismaleimides, epoxy resin He bisoxazoline compounds, by the reaction of the co-curing between different monomers, finally obtains having high tenacity, the heat-resisting and good thermoset resin material of dielectric properties.In order further to improve its modulus, the contriver, in patent CN102702482A, introduces Racemic glycidol amine epoxy as linking agent, improves the modulus of resin material by the method that controllably improves cross-linking density.
Yet in epoxide modified cyanate system, the reactive behavior that exists resin is larger, the problem that under-stream period is short.This has affected the technology stability of resin, and for the high-performance matrix resin, this is a manufacturability defect.The application, in order to improve the manufacturability of modified cyanic acid ester resin, has proposed to introduce the method for anhydride compound in modified resin system.
Summary of the invention
The object of the invention is to propose a kind of cyanate resin composition with high strength and high-modulus.
" high-ductility co-cured resin of cyanate " that the contriver proposes in Chinese patent ZL 200910052209.1, although there is high strength, but still exist the not high enough deficiency of modulus.In order to improve its modulus value, the contriver is in CN102702482A, further use the Racemic glycidol amine epoxy compounds of polyfunctionality (functionality>3) as high efficiency linking agent, increase the cross-linking density of cured resin, thereby improve the modulus of above-mentioned thermosetting resin.And the tertiary amine chemical structure in the glycidyl amine epoxy is reacted with the co-curing of epoxy etc. and will be played certain katalysis curing reaction, the cyanate of cyanate, is conducive to improve the transformation efficiency of monomer in solidification process, promotes completing of curing reaction.
Yet it is larger that this modified resin system exists reactive behavior, the manufacturability issues that under-stream period is short, this meeting of practical application to resin system produces adverse influence.
Anhydride compound is the important epoxy hardener of a class.The anhydride compound cured epoxy has plurality of advantages, and at process aspect: the volatility of acid anhydrides is little, and toxicity is low; Low with the molten mixed rear viscosity of epoxy; The usage period of resin is long.Aspect of performance at cured article: the shrinking percentage of cured article is little, and thermotolerance is high, and mechanical property and dielectric properties are good.These characteristics are very favorable for the processing technology that improves cyanate/bismaleimides/bisoxazoline/epoxy systems (reduce melt viscosity, extend storage period and under-stream period) and the performance of cured resin.
The high strength that the present invention proposes and the modified cyanic acid ester resin composition of high-modulus, described resin raw material is mixed by A component, B component and C component, and wherein: the A component raw material is comprised of cyanate ester monomer, bismaleimide amine monomers and bisoxazoline compounds; The B component is comprised of the Racemic glycidol amine epoxy compounds of bifunctional epoxy compound and 3 functionality or 4 functionality, and the C component is anhydride compound.The weight percent of each component is:
The A component:
Cyanate 30-50%
Bismaleimides 30-50%
Bisoxazoline compounds 10-30%
The B component:
Bifunctional epoxy compound 60-90%
Racemic glycidol amine epoxy compounds 10-40%
The C component:
Anhydride compound 100%
Wherein: the mass ratio of A Zu Fen ﹕ B Zu Fen ﹕ C component is 20 ﹕ 45 ﹕ 35 ~ 70 ﹕ 20 ﹕ 10.
Described anhydride compound comprises: Tetra hydro Phthalic anhydride, trimellitic anhydride, pyromellitic acid anhydride, 3,3 ', 4, any in 4 '-Benzophenone carboxylic acid dianhydride, MALEIC ANHYDRIDE, tung oil acid anhydride, tetrahydrochysene phthalate anhydride, methyl tetrahydrochysene phthalate anhydride, hexahydrophthalic acid anhydride, methyl hexahydrophthalic acid anhydride, carbic anhydride, methyl carbic anhydride, hydrogenation methyl carbic anhydride or tetrahydrotoluene tetracarboxylic dianhydride, or in its mixture any.
In the present invention, described cyanate ester monomer comprises: bisphenol A cyanate ester (4,4 '-dicyanate base phenyl-propane, BADCy), bis-phenol L-type cyanate (4,4 '-dicyanate base phenyl-ethane, BEDCy), bis-phenol M type cyanate (4,4'-[1,3-phenyl two (1-methyl-ethylidene)] two phenyl cyanide acid esters) or Novolac Cyanate Eater Resin (PT) etc. in any, can be maybe in its prepolymer any.
In the present invention, described bismaleimide amine monomers comprises: 4,4 '-diphenyl methane dimaleimide (BDM), 4,4 '-Diphenyl Ether Bismaleimide or 4, in 4 '-sulfobenzide bismaleimides etc. any.
In the present invention, described bisoxazoline compounds comprises: 2, 2 '-(1, the 4-phenylene)-bisoxazolines, 2, 2 '-(1, the 3-phenylene)-bisoxazolines, 2, 2 '-(1, the 4-phenylene)-4-methyl-bisoxazolines, 2, 2 '-(1, the 3-phenylene)-4-methyl-bisoxazolines, 2, 2 '-(1, the 4-phenylene)-4, 4 '-dimethyl ,-bisoxazolines, 2, 2 '-(1, the 3-phenylene)-4, 4 '-dimethyl ,-bisoxazolines, 2, 2 '-ethylene two (2-oxazoline), 2, 2 '-octylene two (2-oxazoline), 2, 2 '-ethylene two (in 4-methyl-2-oxazoline) Huo Duan oxazoline polyethers etc. any.
In the present invention, the commercialization difunctionality epoxy resin that described bifunctional epoxy compound is the various trades mark.
In the present invention, the Racemic glycidol amine epoxy compounds of described 3 functionality or 4 functionality comprises: triglycidyl group p-aminophenol, 4,4'-diaminodiphenylmethane epoxy resin, four glycidyl group-4,4'-diaminodiphenyl oxide (4,4'-TGDDE), four glycidyl group-3, the 4'-diaminodiphenyl oxide (3, any in 4'-TGDDE) etc., can be also in its mixture any.
The high strength that the present invention proposes, the compositions of thermosetting resin of high-modulus, can be by the method preparation of melting mixing.Be about to each component by after the proportioning weighing, at 80 ~ 120 ℃, fully melting mixing is even, obtains uncured resin.Uncured resin can use the usual vehicles such as DMF, butanone, acetone to dissolve, and is mixed with certain density glue, is used for lay-up, as woven fiber glass, carbon cloth etc., for forming composite.
The invention has the advantages that: anhydride compound is incorporated in modified cyanic acid ester resin, can, on the basis of the performances such as the mechanics that does not reduce cured resin, heat-resisting, dielectric, improves the processing performance of uncured resin.
Embodiment
Further illustrate the present invention below by embodiment.
embodiment 1
Take 15.0 g bisphenol A cyanate esters (BADCy), 8.5 g 4,4 '-diphenyl methane dimaleimide, 6.0 g 2,2 '-(1,3-phenylene)-bisoxazolines are in beaker, 80 ~ 120 ℃ of heating, melt evenly, then add 15.0 g epoxy E-44,3.0 g four glycidyl groups-4,4'-diaminodiphenyl oxide (4,4'-TGDDE), 12.0 g methyl carbic anhydride, stir at 80 ~ 100 ℃, obtains sundown, low viscous uncured modified resin.Uncured resin is at room temperature deposited 30 days, and its melt viscosity is without considerable change.
Uncured modified resin in 80 ℃ of vacuum drying ovens degassed 15 minutes, then pour in the mould that scribbles the estersil releasing agent, in the electronics baking oven, is cured processing.Curing process can be undertaken by 150 ℃/1h+180 ℃/1h+200 ℃/2h, and the after fixing condition is 240 ℃/3h, obtains the dark brown red solid resin.Flexural strength 136.7MPa, modulus in flexure 5.3GPa.
embodiment 2
Take 20.0 g bisphenol A cyanate esters (BADCy), 10.0 g 4,4 '-diphenyl methane dimaleimide, 5.0 g 2,2 '-(1, the 3-phenylene)-bisoxazolines, 20.0 g bisphenol type epoxy E-51,6.0 g 4,4'-diaminodiphenylmethane epoxy resin, 15.0 the g carbic anhydride, all the other are identical with embodiment 1.
The flexural strength of cured resin is 145.7 MPa, and modulus in flexure is 5.4 GPa.
embodiment 3
Take 30.0 g bisphenol A cyanate esters (BADCy), 18.0 g 4,4 '-diphenyl methane dimaleimide, 10.0 g 2,2 '-(1,3-phenylene)-bisoxazolines, 20.0 g bisphenol type epoxy E-51,10.0g o-cresol formaldehyde epoxy, 8.0 g four glycidyl group-4, and the 4'-diaminodiphenyl oxide (4,4'-TGDDE), 15.0 g methyl hexahydrophthalic acid anhydride, all the other are identical with embodiment 1.
The flexural strength of cured resin is 148.5MPa, and modulus in flexure is 5. 7GPa.
embodiment 4
Take 20.0 g Novolac Cyanate Eater Resins, 8.0 g 4,4 '-diphenyl methane dimaleimide, 8.0 g N, penylene bismaleimides between N-, 12.0 g 2,2 '-(Isosorbide-5-Nitrae-phenylene)-bisoxazolines, 20.0 g epoxy E-44,8.0 g triglycidyl group p-aminophenol, 24.5 g hexahydrophthalic acid anhydrides, all the other are identical with embodiment 1.
The flexural strength of cured resin is 143.7MPa, and modulus in flexure is 5.7GPa.
comparative Examples:
Take 25g bisphenol type epoxy E-51,20g bisphenol A cyanate ester (BADCy), 13g 4,4 '-diphenyl methane dimaleimide, 4g 2,2 '-(1,3-phenylene)-bisoxazolines, 6g4,4'-diaminodiphenylmethane epoxy resin, preparation method is identical with embodiment 1.Wherein uncured resin is sundown, and after at room temperature depositing 30 days, melt viscosity enlarges markedly.
Uncured resin in 80 ℃ of vacuum drying ovens degassed 15 minutes, then pour in the mould that scribbles the estersil releasing agent, in the electronics baking oven, is cured processing.Curing process can be cured by the curing process of 150 ℃/1h+180 ℃/1h+200 ℃/2h, and the after fixing condition is 220 ℃/4h.The flexural strength of cured resin is 150.1MPa, and modulus in flexure is 5.33GPa.
By the comparison of embodiment and Comparative Examples, used the modified cyanic acid ester resin of anhydride compound, improving the technological while, still kept high flexural strength and Young's modulus.
Claims (6)
1. the modified cyanic acid ester resin composition of a high strength and high-modulus, is characterized in that described resin raw material is mixed by A component, B component and C component, and the A component raw material is comprised of cyanate ester monomer, bismaleimide amine monomers and bisoxazoline compounds; The B component is comprised of the Racemic glycidol amine epoxy compounds of bifunctional epoxy compound and 3 functionality or 4 functionality, and the C component is anhydride compound, and the weight percent of each component is:
The A component:
Cyanate 30-50%
Bismaleimides 30-50%
Bisoxazoline compounds 10-30%
The B component:
Bifunctional epoxy compound 60-90%
Racemic glycidol amine epoxy compounds 10-40%
The C component:
Anhydride compound 100%
Wherein: the mass ratio of A Zu Fen ﹕ B Zu Fen ﹕ C component is 20 ﹕ 45 ﹕ 35 ~ 70 ﹕ 20 ﹕ 10;
Described anhydride compound comprises: Tetra hydro Phthalic anhydride, trimellitic anhydride, pyromellitic acid anhydride, 3,3 ', 4, any in 4 '-Benzophenone carboxylic acid dianhydride, MALEIC ANHYDRIDE, tung oil acid anhydride, tetrahydrochysene phthalate anhydride, methyl tetrahydrochysene phthalate anhydride, hexahydrophthalic acid anhydride, methyl hexahydrophthalic acid anhydride, carbic anhydride, methyl carbic anhydride, hydrogenation methyl carbic anhydride or tetrahydrotoluene tetracarboxylic dianhydride, or in its mixture any.
2. the modified cyanic acid ester resin composition of high strength according to claim 1 and high-modulus, it is characterized in that described cyanate ester monomer comprises: in bisphenol A cyanate ester, bis-phenol L-type cyanate, bis-phenol M type cyanate or Novolac Cyanate Eater Resin any, or in its prepolymer any.
3. the modified cyanic acid ester resin composition of high strength according to claim 1 and high-modulus, it is characterized in that described bismaleimide amine monomers comprises: 4,4 '-diphenyl methane dimaleimide, 4,4 '-Diphenyl Ether Bismaleimide or 4, in 4 '-sulfobenzide bismaleimides any.
4. the modified cyanic acid ester resin composition of high strength according to claim 1 and high-modulus, it is characterized in that described bisoxazoline compounds comprises: 2, 2 '-(1, the 4-phenylene)-bisoxazolines, 2, 2 '-(1, the 3-phenylene)-bisoxazolines, 2, 2 '-(1, the 4-phenylene)-4-methyl-bisoxazolines, 2, 2 '-(1, the 3-phenylene)-4-methyl-bisoxazolines, 2, 2 '-(1, the 4-phenylene)-4, 4 '-dimethyl ,-bisoxazolines, 2, 2 '-(1, the 3-phenylene)-4, 4 '-dimethyl ,-bisoxazolines, 2, 2 '-ethylene two (2-oxazoline), 2, 2 '-octylene two (2-oxazoline), 2, 2 '-ethylene two (in 4-methyl-2-oxazoline) Huo Duan oxazoline polyethers any.
5. the modified cyanic acid ester resin composition of high strength according to claim 1 and high-modulus, is characterized in that described bifunctional epoxy compound is for commercialization difunctionality epoxy resin.
6. the modified cyanic acid ester resin composition of high strength according to claim 1 and high-modulus, the Racemic glycidol amine epoxy compounds that it is characterized in that described 3 functionality or 4 functionality comprises: triglycidyl group p-aminophenol, 4,4'-diaminodiphenylmethane epoxy resin, four glycidyl group-4,4'-diaminodiphenyl oxide, four glycidyl group-3, any in the 4'-diaminodiphenyl oxide, or in its mixture any.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310442784.9A CN103497310A (en) | 2013-09-26 | 2013-09-26 | High-strength and high-modulus modified cyanate ester resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310442784.9A CN103497310A (en) | 2013-09-26 | 2013-09-26 | High-strength and high-modulus modified cyanate ester resin composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103497310A true CN103497310A (en) | 2014-01-08 |
Family
ID=49862581
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310442784.9A Pending CN103497310A (en) | 2013-09-26 | 2013-09-26 | High-strength and high-modulus modified cyanate ester resin composition |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103497310A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105153683A (en) * | 2015-07-28 | 2015-12-16 | 苏州科淼新材料有限公司 | Method for preparing toughened resin composition |
| CN108929519A (en) * | 2017-05-24 | 2018-12-04 | 洛阳尖端技术研究院 | A kind of basalt fiber composite material and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102702482A (en) * | 2012-05-29 | 2012-10-03 | 同济大学 | High-strength and high-modulus thermosetting resin composition |
| CN103265810A (en) * | 2013-05-29 | 2013-08-28 | 苏州生益科技有限公司 | Resin composition for high-frequency high-speed substrate as well as prepreg and laminated board made of resin composition |
-
2013
- 2013-09-26 CN CN201310442784.9A patent/CN103497310A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102702482A (en) * | 2012-05-29 | 2012-10-03 | 同济大学 | High-strength and high-modulus thermosetting resin composition |
| CN103265810A (en) * | 2013-05-29 | 2013-08-28 | 苏州生益科技有限公司 | Resin composition for high-frequency high-speed substrate as well as prepreg and laminated board made of resin composition |
Non-Patent Citations (1)
| Title |
|---|
| 陈平: "《环氧树脂及其应用》", 29 February 2004, 化学工业出版社 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105153683A (en) * | 2015-07-28 | 2015-12-16 | 苏州科淼新材料有限公司 | Method for preparing toughened resin composition |
| CN108929519A (en) * | 2017-05-24 | 2018-12-04 | 洛阳尖端技术研究院 | A kind of basalt fiber composite material and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101597371B (en) | High-ductility co-cured resin of cyanate, preparation method and use thereof | |
| CN101654518B (en) | Thermosetting polyimide resin and preparation method and application thereof | |
| CN107629755B (en) | Preparation method of high-temperature-resistant polyimide adhesive film for bonding polyimide honeycomb and composite material wall plate | |
| CN104233504A (en) | Polyimide/ titanium dioxide hybrid fibers and preparation method thereof | |
| CN106280449B (en) | A kind of high tenacity, benzoxazine/diallyl diphenol/bismaleimide blending resin of low viscosity and preparation method thereof | |
| CN102295740A (en) | Polyamideimide cured epoxy resin composite material and preparation method thereof | |
| CN100457825C (en) | Process of modifying epoxy resin with schiff base type liquid crystal epoxy resin | |
| CN103665326A (en) | Thermosetting cyanate/bismaleimide resin composition | |
| CN101570598B (en) | Cyanate/bismaleimide co-cured resin and preparation method and application thereof | |
| CN107523055B (en) | High-temperature-resistant alkynyl mono-maleimide modified bismaleimide resin and preparation method thereof | |
| CN102702482B (en) | High-strength and high-modulus thermosetting resin composition | |
| CN104628544A (en) | Propenyl phenoxy compounds with three-branch aromatic structure and preparation method thereof, and bismaleimide resin modified by propenyl phenoxy compounds | |
| CN103497310A (en) | High-strength and high-modulus modified cyanate ester resin composition | |
| Ren et al. | Design of the phthalonitrile‐based composite laminates by improving the interfacial compatibility and their enhanced properties | |
| CN102286151B (en) | Thermosetting modified cyanate ester resin and preparation method thereof | |
| CN101570599B (en) | Cyanate/bisoxazoline co-cured resin and preparation method and application thereof | |
| CN103497332B (en) | Cyanate/bismaleimide/bis(oxazoline)/ polyethylene glycol/epoxy/anhydride resin composition | |
| JPS60250026A (en) | Epoxy resin composition | |
| CN102702519B (en) | Cyanate ester/bisoxazoline/glycidyl amine epoxy resin composition | |
| CN103483584A (en) | Cyanate ester/bisoxazoline/glycidyl amine epoxy/anhydride resin composition | |
| CN103497331B (en) | Cyanate/bis(oxazoline)/epoxy/anhydride/polyethylene glycol modified resin composition | |
| CN109162101B (en) | Low-viscosity high-heat-resistance polyimide fiber sizing agent and preparation method thereof | |
| CN102876280A (en) | Cyanate ester/bis-oxazoline thermostable adhesive and preparation method thereof | |
| CN102336892A (en) | Modified cyanate ester resin system for package substrate, and preparation method and application thereof | |
| CN102675632A (en) | Cyanate/bismaleimide/bisoxazoline/polyethylene glycol resin composition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20140108 |