CN101570598A - Cyanate/bismaleimide co-cured resin and preparation method and application thereof - Google Patents
Cyanate/bismaleimide co-cured resin and preparation method and application thereof Download PDFInfo
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- CN101570598A CN101570598A CNA2009100522072A CN200910052207A CN101570598A CN 101570598 A CN101570598 A CN 101570598A CN A2009100522072 A CNA2009100522072 A CN A2009100522072A CN 200910052207 A CN200910052207 A CN 200910052207A CN 101570598 A CN101570598 A CN 101570598A
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- cyanate
- bismaleimide
- cured resin
- bisoxazolines
- phenylene
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Abstract
The invention relates to cyanate/bismaleimide co-cured resin and a preparation method and application thereof. The cyanate/bismaleimide co-cured resin consists of the following components by mass percentage: 10 to 90 percent of cyanate monomer, 9 to 60 percent of bismaleimide monomer, and 1 to 30 percent of bisoxazoline compound. The resin can be prepared by adopting a melting mixing method or a solution mixing method. The resin can perform co-curing reaction during heat curing to obtain a resin material with a co-cured structure, and has excellent mechanical property, heat resistance, dielectric property and the like. The cyanate/bismaleimide co-cured resin can be widely applied to high-performance printed circuit boards, wave-transmitting structural materials and high-tenacity structural materials.
Description
Technical field
The present invention relates to a kind of cyanate/bismaleimide co-cured resin and preparation method thereof, use.
Background technology
Cyanate is the thermosetting resin that a class has good dielectric properties, mechanical property, thermotolerance, low water absorption, having a wide range of applications in fields such as high-performance circuit board, transparent structure material and high tenacity structure materials, also is that high-tech sector develops one of requisite material.Bimaleimide resin is the good thermosetting resin of a class thermotolerance (230～340 ℃ of a second-order transition temperature), with cyanate and the bismaleimides formation modified resin that combines, expection is both advantages comprehensively, the resin material that obtains having superior heat resistance and mechanical property.
US 4110364 has proposed cyanate/bimaleimide modified resin system the earliest, this system mainly is made of bisphenol A cyanate ester and ditane type bismaleimides, developed a kind of " BT resin " on this basis, be applied in the manufacturing of electronic package substrate.US 5886134 adopts the bismaleimides of ether-containing key structure and cyanate to constitute modified resin system.
Yet, show that by the result of multiple analysis means research in the solidification process of cyanate/bismaleimides, the co-curing reaction can not take place two kinds of resins, can only distinguish separately and solidify, and finally form a kind of interpenetrating net polymer (IPN) in the above-mentioned patent.(reference: Hamerton I., Herman H, Mudhar A K, Chaplin A, Shaw S J, Multivariate analysis of spectra of cyanate ester/bismaleimide blends andcorrelations with properties, Polymer, 2002,43 (11): 3381-3386).This IPN structural polymer has the double glass transition temperature, and the use temperature of material is subjected to lower glass transition temperatures one side's restriction, makes that the thermotolerance of modified resin is not high.
In order to improve the thermotolerance of cyanate/bimaleimide modified resin, chemical copolymerization is effective ways, by introduce cross-linking set between the IPN network, introduces the thermotolerance that crosslinking structure improves resin between two kinds of curing network.For cyanate/Bismaleimide Resin, a kind of feasible method is to contain simultaneously in the synthetic molecules structure-OCN, the reactive monomer of allyl group or maleimide (maleimide) group, it is joined in cyanate/bimaleimide modified resin system, when solidifying,-OCN and cyanate ester monomer reaction, allyl group or maleimide group then with the bismaleimides monomer reaction, reactive monomer has been played the part of role's (reference: 1 of linking agent, Chaplin A, Hamerton I, Howlin B J, Barton J M, Development of Novel Functionalized Aryl Cyanate Ester Oligomers.1.Synthesis and Thermal Characterization of the Monomers, Macromolecules, 1994,27 (18): 4927-4935; 2, Hamerton I, Barton J M, Chaplin A, Howlin B J, Shaw S J, The development of novel functionalized aryl cyanate esters.Part 2.Mechanicalproperties of the polymers and composites, Polymer, 2001,42:2307-2319), it causes crosslinked between two kinds of curing network, promptly forms crosslinked interpenetrating net polymer (LIPN).Thereby this method is the co-curing reaction of a kind of " indirectly ".
US4,683,276, US4,731,426, US4,769,440, US4,820,798 have announced the modified resin system that is made of cyanic acid esterification bismaleimides monomer and cyanate (or bismaleimides, epoxy etc.), mainly are to realize cyanate and bismaleimides co-curing by the monomer that contains cyanate functional group and maleimide amine functional group in the molecular structure simultaneously.
US6,616,984 have announced in the inferior imide system of cyanate/span, add in the molecular structure and contain the linking agent that key and epoxy-functional are closed in insatiable hunger simultaneously, and realize the co-curing reaction of two components by photocuring.
Summary of the invention
The purpose of this invention is to provide a kind of
Cyanate/bismaleimide co-cured resin and preparation method thereof, application.
Cyanate/bismaleimide co-cured resin that the present invention proposes is made up of cyanate ester monomer, bismaleimide amine monomers and bisoxazoline compounds, and the mass percent of its component is:
Cyanate ester monomer 10-90%
Bismaleimide amine monomers 9-60%
Bisoxazoline compounds 1-30%.
Among the present invention, described 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), bis-phenol M type cyanate (4,4 '-[1,3-phenyl two (1-methyl-ethylidene)] two phenyl cyanide acid esters) or phenol aldehyde type cyanate (PT) etc. in any, also can be in its prepolymer etc. any.
Among the present invention, described bismaleimide amine monomers comprises: 4,4 '-diphenyl methane dimaleimide (BDM), N, penylene bismaleimides of N, 4,4 '-phenyl ether bismaleimides or 4, in 4 '-sulfobenzide bismaleimides etc. any.
Among 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.
The preparation method of cyanate/bismaleimide co-cured resin that the present invention proposes, adopt the melting mixing method, promptly under 80-150 ℃ temperature, heating makes cyanate ester monomer, bismaleimide amine monomers and bisoxazoline compounds melting mixing even, cooling obtains uncured modified resin.
Among the present invention, uncured modified resin can be successively by heating 1h under 180 ℃ of temperature, and 200 ℃ are heated 2h down, heat 2h down at 240 ℃ at last.Obtain red-brown printing opacity solid resin after the curing, have performances such as good mechanical, heat-resisting, dielectric.The glue that solution obtains after mixing can be used for flooding fortifying fibre, the preparation matrix material.The present invention can be widely used in high-performance printed circuit board (PCB), transparent structure material and the high tenacity structure material.
The contriver sends out existing oxazoline compound and can react with cyanate and bismaleimides generation co-curing in research work, and has produced the new chemical modification system of a class thus: cyanate/bismaleimides/bisoxazoline resin system.This system not only can improve the mechanical property of cured resin, and less to thermotolerance, dielectricity loss of energy, also helps the process industrial art performance that improves uncured resin simultaneously.
The invention has the advantages that: bisoxazoline compounds and cyanate ester monomer, the monomeric consistency of bismaleimides are good, cyanate/bismaleimides/bisoxazoline co-curing system has good manufacturability; Co-cured resin is when improving the cyanate ester resin mechanical property, and is less to the loss influence of its thermotolerance, dielectric properties etc.This resin material has a wide range of applications at aspects such as high-performance circuit board, transparent structure material and high tenacity structure materials.
Embodiment
Further specify the present invention below by embodiment.
Embodiment 1
Take by weighing 90g bisphenol A cyanate ester (BADCy) in beaker, be heated to fusion, add 10g 4 then, 4 '-diphenyl methane dimaleimide, 9g 2,2 '-(1, the 3-phenylene)-bisoxazolines, fusion evenly obtains 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 180 ℃/1h+200 ℃/2h in the electronics baking oven is cured, and the after fixing condition is 240 ℃/2h.The cured resin that obtains is a red-brown printing opacity solid, 286 ℃ of second-order transition temperatures (DMA method), flexural strength 111.8MPa, specific inductivity 3.06, dielectric loss 0.0081 (test frequency 1GHz).
Embodiment 2
Take by weighing 60g bisphenol A cyanate ester (BADCy), 40g 4,4 '-diphenyl methane dimaleimide, and 10g2,2 '-(1, the 3-phenylene)-bisoxazolines, all the other and embodiment 1 are together.
297.4 ℃ of the second-order transition temperatures of cured resin (DMA method), flexural strength 141.6MPa, specific inductivity 3.09, dielectric loss 0.0091 (test frequency 1GHz).
Embodiment 3
Take by weighing 45g bisphenol A cyanate ester (BADCy), 55g 4,4 '-diphenyl methane dimaleimide, and 12g2,2 '-(1, the 3-phenylene)-bisoxazolines, all the other and embodiment 1 are together.
309.7 ℃ of the second-order transition temperatures of cured resin (DMA method), flexural strength 138.8MPa, specific inductivity 3.13, dielectric loss 0.0097 (test frequency 1GHz).
Embodiment 4
Take by weighing 60g bis-phenol L type cyanate (4,4 '-two cyanate ester based phenyl-ethane, BEDCy), 55g 4,4 '-diphenyl methane dimaleimide, 20g N, penylene bismaleimides between N-, 14g g 2,2 '-(1, the 3-phenylene)-bisoxazolines, all the other and embodiment 1 obtain at room temperature being the uncured resin of thick liquid together.
292.4 ℃ of the second-order transition temperatures of cured resin (DMA method), flexural strength 141.4MPa, specific inductivity 3.11, dielectric loss 0.0099 (test frequency 1GHz).
Comparative Examples:
Take by weighing 50g bisphenol A cyanate ester (BADCy), 70g 4, and 4 '-diphenyl methane dimaleimide is put into 80 ℃ of vacuum drying oven degassings 15 minutes behind the heating and melting, pour into then in the mould that scribbles the estersil releasing agent, is cured processing in the electronics baking oven.Cured resin is the dark brown red solid, has double glass transition temperature (224 ℃, 252 ℃, DMA method), flexural strength 128.3MPa,
By the comparison of embodiment and Comparative Examples, cyanate/bismaleimides of the present invention/bisoxazoline resin solidification has obtained the cured resin of single glass transition temperature, the resin that promptly has the co-curing structure, and all than Comparative Examples height.In addition, the flexural strength of co-cured resin also improves than Comparative Examples.
Claims (7)
1, a kind of cyanate/bismaleimide co-cured resin is characterized in that being made up of cyanate ester monomer, bismaleimide amine monomers and bisoxazoline compounds, and the mass percent of its component is:
Cyanate ester monomer 10-90%
Bismaleimide amine monomers 9-60%
Bisoxazoline compounds 1-30%.
2, cyanate/bismaleimide co-cured resin according to claim 1, it is characterized in that described cyanate ester monomer be in bisphenol A cyanate ester, bis-phenol L type cyanate, bis-phenol M type cyanate or the phenol aldehyde type cyanate any, or in its prepolymer any.
3, cyanate/bismaleimide co-cured resin according to claim 1, it is characterized in that described 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.
4, cyanate/bismaleimide co-cured resin according to claim 1, 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 the 4-methyl-2 oxazoline) Huo Duan oxazoline polyethers etc. any.
5, a kind of preparation method of cyanate/bismaleimide co-cured resin as claimed in claim 1, it is characterized in that adopting the melting mixing method, promptly under 80-150 ℃ temperature, heating makes cyanate ester monomer, bismaleimide amine monomers and bisoxazoline compounds melting mixing even, cooling obtains uncured modified resin.
6, the preparation method of cyanate/bismaleimide co-cured resin as claimed in claim 5 is characterized in that adopting the curing process of described uncured modified resin under 180 ℃ of temperature and heat 1h, and 200 ℃ of heating 2h down are at last at 240 ℃ of heating 2h down.
7, a kind of cyanate/bismaleimide co-cured resin as claimed in claim 1 is used in high-performance printed circuit board (PCB), transparent structure material and high tenacity structure material.
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| Application Number | Priority Date | Filing Date | Title |
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| CN2009100522072A CN101570598B (en) | 2009-05-26 | 2009-05-26 | Cyanate/bismaleimide co-cured resin and preparation method and application thereof |
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| CN2009100522072A CN101570598B (en) | 2009-05-26 | 2009-05-26 | Cyanate/bismaleimide co-cured resin and preparation method and application thereof |
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| CN101570598A true CN101570598A (en) | 2009-11-04 |
| CN101570598B CN101570598B (en) | 2011-07-27 |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102675632A (en) * | 2012-05-29 | 2012-09-19 | 同济大学 | Cyanate/bismaleimide/bisoxazoline/polyethylene glycol resin composition |
| CN102675638A (en) * | 2012-05-29 | 2012-09-19 | 同济大学 | Cyanate ester, bis-oxazoline or polyethylene glycol resin composite |
| CN102675828A (en) * | 2012-05-29 | 2012-09-19 | 同济大学 | Cyanate ester/ bismaleimide/ epoxy/ bis-oxazoline/ polyethylene glycol resin composite |
| CN103724931A (en) * | 2013-12-09 | 2014-04-16 | 航天特种材料及工艺技术研究所 | Improved phenolic resin, wave penetrating composite and preparation methods for both |
| CN112048247A (en) * | 2020-09-14 | 2020-12-08 | 黑龙江省科学院石油化学研究院 | Bismaleimide/cyanate ester foamed adhesive film, and preparation method and application thereof |
| CN114685988A (en) * | 2020-12-29 | 2022-07-01 | 洛阳尖端技术研究院 | Modified bismaleimide resin and preparation method and application thereof |
-
2009
- 2009-05-26 CN CN2009100522072A patent/CN101570598B/en not_active Expired - Fee Related
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102675632A (en) * | 2012-05-29 | 2012-09-19 | 同济大学 | Cyanate/bismaleimide/bisoxazoline/polyethylene glycol resin composition |
| CN102675638A (en) * | 2012-05-29 | 2012-09-19 | 同济大学 | Cyanate ester, bis-oxazoline or polyethylene glycol resin composite |
| CN102675828A (en) * | 2012-05-29 | 2012-09-19 | 同济大学 | Cyanate ester/ bismaleimide/ epoxy/ bis-oxazoline/ polyethylene glycol resin composite |
| CN102675638B (en) * | 2012-05-29 | 2013-10-30 | 同济大学 | Cyanate ester/bis-oxazoline/polyethylene glycol resin composite |
| CN103724931A (en) * | 2013-12-09 | 2014-04-16 | 航天特种材料及工艺技术研究所 | Improved phenolic resin, wave penetrating composite and preparation methods for both |
| CN112048247A (en) * | 2020-09-14 | 2020-12-08 | 黑龙江省科学院石油化学研究院 | Bismaleimide/cyanate ester foamed adhesive film, and preparation method and application thereof |
| CN114685988A (en) * | 2020-12-29 | 2022-07-01 | 洛阳尖端技术研究院 | Modified bismaleimide resin and preparation method and application thereof |
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| CN101570598B (en) | 2011-07-27 |
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Granted publication date: 20110727 Termination date: 20140526 |