CN102675594A - High-elasticity-modulus cyanate ester/bismaleimide resin compound - Google Patents
High-elasticity-modulus cyanate ester/bismaleimide resin compound Download PDFInfo
- Publication number
- CN102675594A CN102675594A CN2012101694400A CN201210169440A CN102675594A CN 102675594 A CN102675594 A CN 102675594A CN 2012101694400 A CN2012101694400 A CN 2012101694400A CN 201210169440 A CN201210169440 A CN 201210169440A CN 102675594 A CN102675594 A CN 102675594A
- Authority
- CN
- China
- Prior art keywords
- cyanate
- phenylene
- bisoxazolines
- functionality
- resin
- 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
Abstract
The invention relates to a high-elasticity-modulus cyanate ester/bismaleimide resin compound. The raw materials of the resin consist of a cyanate ester monomer, a bismaleimide monomer, a bioxazoline compound and a tri-functional or tetra-functional glycidyl amine epoxy compound. The tri-functional or tetra-functional glycidyl amine epoxy compound is introduced into cyanate ester/bismaleimide/bioxazoline, and is subjected to a co-curing reaction, so that a thermosetting resin material with high glass transition temperature and high elasticity modulus is obtained. Due to the adoption of the high-elasticity-modulus cyanate ester/bismaleimide resin compound, the curing reaction of resin can be promoted, and properties such as elasticity modulus, glass transition temperature and the like of cured resin can be improved.
Description
Technical field
The present invention relates to a kind of cyanate/bimaleimide resin compsn of high elastic coefficient.
Background technology
Thermosetting resin is one type of important polymer materials, usually as the matrix for preparing matrix material.
A performance shortcomings of matrix material is that its Young's modulus is low, generally than low about 10 times of metallic substance.This is that the modulus of matrix (thermosetting resin) is much smaller than strongthener (like fiber, particle etc.) because in matrix material, and this is when matrix material is stressed, often owing to rigidity produces bigger distortion inadequately.When matrix material received bigger stress (like compression, shearing), matrix reached surrender prior to strongthener, produces tiny crack, effectively carrier of strand and transmission stress.If stress continues to increase, matrix will destroy prior to strongthener, cause the mechanical property of matrix material sharply to descend until destruction.Therefore, keep or improve performance of composites, key is to improve the modulus of matrix resin.
The approaches and methods that improves the thermosetting resin modulus has: (1) increases the molecule chain rigidity, mainly is in the chemical structure of monomer resin, to introduce aromatic ring, heterocyclic group; (2) increasing polarity of chain, mainly is in the chemical structure of monomer resin, to introduce polar group, like carboxamido-group, ester group etc.; (3) appropriateness improves degree of crosslinking, weakens the relative slippage of molecular chain; (4) add nanoparticle.Wherein the first three mode is to improve the modulus of thermosetting resin through chemical means, and a kind of mode in back then belongs to physical means.
The contriver is in the research in early stage; A kind of " cyanate/bismaleimide co-cured resin " (cyanate/bismaleimide co-cured resin and preparation method thereof ZL200910052207.2) proposed; That this resin belongs to is high temperature resistant, the high-performance thermosetting resin of HS, low-k and low-dielectric loss, and the modulus in flexure of cured resin is 4.5 ~ 4.7.For some harsh environment for use, still exist the big inadequately problem of modulus, be further improved.
The contriver finds, polyfunctional group Racemic glycidol amine epoxy can be as a kind of linking agent, through with component generation curing reaction such as cyanate, improve the cross-linking density of cured resin, thereby improve macro physical performances such as its Young's modulus and second-order transition temperature.
Summary of the invention
The objective of the invention is to propose a kind of cyanate/bimaleimide resin compsn of high elastic coefficient.
The cyanate that the contriver proposes in the ZL200910052207.2 patent/bismaleimides/bisoxazoline co-cured resin is one type of high-performance thermosetting matrix resin with high glass-transition temperature, HS, low-k and low-dielectric loss.The contriver finds, on the basis that this matrix resin is formed, through introducing the epoxy component of 3 functionality and 4 functionality, can put forward macro physical performance, particularly Young's modulus and the resistance toheat of cured resin effectively.
Epoxy compounds self can with cyanate or bismaleimides generation curing reaction, form thermoset resin material with co-curing structure.The contriver finds; In cyanate/bismaleimides/bisoxazoline resin system; When adding Racemic glycidol amine epoxy compounds; Tertiary amine chemical structure in the glycidyl amine epoxy will play certain katalysis to the curing reaction of cyanate, helps improving monomeric transformation efficiency in the solidification process, promotes the completion of curing reaction.Simultaneously, the Racemic glycidol amine epoxy of polyfunctionality is a kind of high efficiency linking agent, can increase the cross-linking density of cured resin, performances such as the Young's modulus of raising resin, second-order transition temperature.
Cyanate/bimaleimide resin the compsn of the high elastic coefficient that the present invention proposes; The raw material of said resin is made up of the Racemic glycidol amine epoxy compounds of cyanate ester monomer, bismaleimide amine monomers, bisoxazoline compounds, 3 functionality or 4 functionality, and the weight percent of its component is:
Cyanate ester monomer 5-45%
Bismaleimide amine monomers 5-30%
Bisoxazoline compounds 1-15%
All the other are 3 functionality or 4 functionality glycidyl amine epoxy compoundss, and its gross weight satisfies 100%.
Among the present invention, said cyanate ester monomer comprises: bisphenol A cyanate ester (4,4 '-two cyanate ester based phenyl-propane; BADCy), bis-phenol L type cyanate (4; 4 '-two cyanate ester based phenyl-ethane, BEDCy), (4,4'-[1 for bis-phenol M type cyanate; 3-phenyl two (1-methyl-ethylidene)] two phenyl cyanide acid esters) or phenolic cyanate (PT) etc. in any, also can be in its prepolymer etc. any.
Among the present invention, said bismaleimide amine monomers comprises: 4,4 '-diphenyl methane dimaleimide (BDM), N, penylene bismaleimides, 4 between N-, 4 '-phenyl ether bismaleimides or 4, in 4 '-sulfobenzide bismaleimides etc. any.
Among the present invention, said 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-oxazolines), 2,2 '-octylene two (2-oxazoline), 2,2 '-ethylene two (in 4-methyl-2-oxazoline) Huo Duan oxazoline polyethers etc. any.
Among the present invention, described 3 functionality or 4 functionality Racemic glycidol amine epoxy compoundss comprise: triglycidyl group PARA AMINOPHENOL (like AFG-90 etc.), 4,4'-MDA epoxy resin (like AG-80, SKE-3 etc.), four glycidyl group-4; 4'-diaminodiphenyl oxide (4; 4'-TGDDE, trade names SKE-1) or four glycidyl group-3,4'-diaminodiphenyl oxide (3; 4'-TGDDE, trade names SKE-2) etc. in more than one.
The compositions of thermosetting resin of the high elastic coefficient that the present invention proposes can prepare through the method for 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 is with usual vehicles such as DMF, butanone or acetone dissolvings, and is mixed with certain density glue, just can lay-up, like woven fiber glass, carbon cloth etc., be used for forming composite.
The invention has the advantages that: the Racemic glycidol amine epoxy compounds of 3 functionality or 4 functionality is incorporated in cyanate/bismaleimides/bisoxazoline modified resin; The curing reaction of resin not only can be promoted, the performance such as Young's modulus and second-order transition temperature of cured resin can also be improved.
Embodiment
Further specify the present invention through embodiment below.
Embodiment 1
Take by weighing 40.0g bisphenol A cyanate ester (BADCy) and 6.5g four glycidyl group-4, and the 4'-diaminodiphenyl oxide (4,4'-TGDDE) in beaker; Be heated to fusion, add 15.0 g 4 then, 4 '-diphenyl methane dimaleimide; 8.5g 2,2 '-(1, the 3-phenylene)-bisoxazolines; Under 80 ~ 120 ℃ temperature, fuse, stir, obtain uncured modified resin.
Uncured resin outgased 15 minutes in 80 ℃ of vacuum drying ovens, poured into then in the mould that scribbles the estersil releasing agent, and the curing process by 150 ℃/1h+180 ℃/1h+200 ℃/2h in the electronics baking oven is cured, and the after fixing condition is 240 ℃/3h.The cured resin that obtains is the dark brown red solid, 294 ℃ of second-order transition temperatures (DMA method), flexural strength 142.3MPa, modulus in flexure 5.7GPa.
Embodiment 2
Take by weighing 25g bisphenol A cyanate ester (BADCy), 15 g 4,4 '-diphenyl methane dimaleimide, 10 g 2,2 '-(1, the 3-phenylene)-bisoxazolines, 20g four glycidyl group-4, (4,4'-TGDDE), all the other and embodiment 1 are together for the 4'-diaminodiphenyl oxide.
288.4 ℃ of the second-order transition temperatures of cured resin (DMA method), flexural strength 134.3MPa, modulus in flexure 5.6GPa.
Embodiment 3
Take by weighing 35g phenolic cyanate (PT), 25 g 4,4 '-diphenyl methane dimaleimide, 6 g 2,2 '-(1, the 3-phenylene)-bisoxazolines, 35g4,4'-MDA epoxy resin, all the other and embodiment 1 are together.
335.5 ℃ of the second-order transition temperatures of cured resin (DMA method), flexural strength 100.6MPa, modulus in flexure 6.2GPa.
Embodiment 4
Take by weighing 35g 4,4 '-two cyanate ester based phenyl-ethane (BEDCy), 25g N, penylene bismaleimides between N-, 9 g 2,2 '-(1, the 3-phenylene)-bisoxazoline, 21g triglycidyl group PARA AMINOPHENOL, all the other and embodiment 1 are together.
263.4 ℃ of the second-order transition temperatures of cured resin (DMA method), flexural strength 146.4MPa, modulus in flexure 4.9GPa.
Comparative Examples:
Take by weighing 90g bisphenol A cyanate ester (BADCy) in beaker, be heated to fusion, add 10 g 4 then, 4 '-diphenyl methane dimaleimide, 9g 2,2 '-(1, the 3-phenylene)-bisoxazolines, the preparation process of resin is with embodiment 1.286 ℃ of the cured resin second-order transition temperatures that obtains (DMA method), flexural strength 111.8MPa, modulus in flexure 4.5GPa.
Comparison by embodiment and Comparative Examples; Cyanate of the present invention/bismaleimides/bisoxazoline/epihydric alcohol amine resin solidifies the cured resin that obtains high glass-transition temperature, and the cured resin that its bending elastic modulus does not more add the glycidyl amine epoxy crosslinking agent has had raising by a relatively large margin.
Claims (5)
1. the cyanate of a high elastic coefficient/bimaleimide resin compsn; The raw material that it is characterized in that said resin is made up of the Racemic glycidol amine epoxy compounds of cyanate ester monomer, bismaleimide amine monomers, bisoxazoline compounds, 3 functionality or 4 functionality, and the weight percent of its component is:
Cyanate ester monomer 5-45%
Bismaleimide amine monomers 5-30%
Bisoxazoline compounds 1-15%
All the other are 3 functionality or 4 functionality glycidyl amine epoxy compoundss, and its gross weight satisfies 100%.
2. the cyanate of high elastic coefficient according to claim 1/bimaleimide resin compsn; It is characterized in that said cyanate ester monomer comprises: in bisphenol A cyanate ester, bis-phenol L type cyanate, bis-phenol M type cyanate or the phenolic cyanate any, or in its prepolymer any.
3. the cyanate of high elastic coefficient according to claim 1/bimaleimide resin compsn; It is characterized in that said bismaleimide amine monomers comprises: 4; 4 '-diphenyl methane dimaleimide, N; Penylene bismaleimides, 4 between N-, 4 '-phenyl ether bismaleimides or 4, in 4 '-sulfobenzide bismaleimides any.
4. the cyanate of high elastic coefficient according to claim 1/bimaleimide resin compsn is characterized in that said 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-oxazolines), 2,2 '-octylene two (2-oxazoline), 2,2 '-ethylene two (in 4-methyl-2-oxazoline) Huo Duan oxazoline polyethers any.
5. the cyanate of high elastic coefficient according to claim 1/bimaleimide resin compsn; It is characterized in that described 3 functionality or 4 functionality Racemic glycidol amine epoxy compoundss comprise: triglycidyl group PARA AMINOPHENOL, 4; 4'-MDA epoxy resin, four glycidyl group-4; 4'-diaminodiphenyl oxide or four glycidyl group-3, in the 4'-diaminodiphenyl oxide more than one.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012101694400A CN102675594A (en) | 2012-05-29 | 2012-05-29 | High-elasticity-modulus cyanate ester/bismaleimide resin compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012101694400A CN102675594A (en) | 2012-05-29 | 2012-05-29 | High-elasticity-modulus cyanate ester/bismaleimide resin compound |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102675594A true CN102675594A (en) | 2012-09-19 |
Family
ID=46808189
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2012101694400A Pending CN102675594A (en) | 2012-05-29 | 2012-05-29 | High-elasticity-modulus cyanate ester/bismaleimide resin compound |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102675594A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103665326A (en) * | 2013-09-26 | 2014-03-26 | 同济大学 | Thermosetting cyanate/bismaleimide resin composition |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101481490A (en) * | 2009-01-19 | 2009-07-15 | 东莞联茂电子科技有限公司 | Thermosetting resin composition and use |
| CN101597371A (en) * | 2009-05-26 | 2009-12-09 | 同济大学 | High-ductility co-cured resin of cyanate and preparation method thereof, application |
| CN102336892A (en) * | 2011-06-29 | 2012-02-01 | 同济大学 | Modified cyanate ester resin system for package substrate, and preparation method and application thereof |
-
2012
- 2012-05-29 CN CN2012101694400A patent/CN102675594A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101481490A (en) * | 2009-01-19 | 2009-07-15 | 东莞联茂电子科技有限公司 | Thermosetting resin composition and use |
| CN101597371A (en) * | 2009-05-26 | 2009-12-09 | 同济大学 | High-ductility co-cured resin of cyanate and preparation method thereof, application |
| CN102336892A (en) * | 2011-06-29 | 2012-02-01 | 同济大学 | Modified cyanate ester resin system for package substrate, and preparation method and application thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103665326A (en) * | 2013-09-26 | 2014-03-26 | 同济大学 | Thermosetting cyanate/bismaleimide resin composition |
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 | |
| CN104974346A (en) | Preparation method of liquid-crystal allyl-compound-modified bismaleimide resin | |
| CN111100455A (en) | PBO fiber reinforced resin matrix composite material and preparation method thereof | |
| CN1884376A (en) | Thermostable benzoxazine resin compound and its preparation method and uses | |
| CN101570598B (en) | Cyanate/bismaleimide co-cured resin and preparation method and application thereof | |
| CN103665326A (en) | Thermosetting cyanate/bismaleimide resin composition | |
| CN101735573A (en) | Modified epoxy resin film for RFI molding process and preparation method thereof | |
| CN110818932A (en) | Norbornene-based end-capped benzoxazine oligomer prepreg composition, and preparation method and application method thereof | |
| CN102286151B (en) | Thermosetting modified cyanate ester resin and preparation method thereof | |
| CN101570599B (en) | Cyanate/bisoxazoline co-cured resin and preparation method and application thereof | |
| JP2011174045A5 (en) | ||
| CN102675594A (en) | High-elasticity-modulus cyanate ester/bismaleimide resin compound | |
| CN102702482A (en) | High-strength and high-modulus thermosetting resin composition | |
| CN113004690B (en) | Bismaleimide resin composition, preparation method and application thereof | |
| CN111875793A (en) | Phthalonitrile resin for composite material and preparation method thereof | |
| CN103756314B (en) | For the preparation method of the bimaleimide resin of matrix material liquid condition shaping | |
| CN109096753B (en) | Nitrile resin composite material and preparation method thereof | |
| CN113583276B (en) | Benzoxazine toughening modification method | |
| CN105694033B (en) | A kind of o-phthalonitrile resin composition and preparation method thereof and application method | |
| CN110041702A (en) | Hot melt prepreg lower shrinkage cyanate ester resin system and preparation method thereof | |
| CN102702519B (en) | Cyanate ester/bisoxazoline/glycidyl amine epoxy resin composition | |
| CN102675632A (en) | Cyanate/bismaleimide/bisoxazoline/polyethylene glycol resin composition | |
| CN103497332B (en) | Cyanate/bismaleimide/bis(oxazoline)/ polyethylene glycol/epoxy/anhydride resin composition | |
| CN109096488B (en) | Phthalonitrile resin composition and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C12 | Rejection of a patent application after its publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20120919 |