CN102020846B - Furfurylamine type benzoxazine resin/maleimide compound composition - Google Patents
Furfurylamine type benzoxazine resin/maleimide compound composition Download PDFInfo
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- CN102020846B CN102020846B CN201010296176.8A CN201010296176A CN102020846B CN 102020846 B CN102020846 B CN 102020846B CN 201010296176 A CN201010296176 A CN 201010296176A CN 102020846 B CN102020846 B CN 102020846B
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- benzoxazine colophony
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Abstract
The invention relates to a furfurylamine type benzoxazine resin/maleimide compound composition, which is prepared from furfurylamine type benzoxazine resin and a series of maleimide group-containing compounds. The composition can be cured at lower temperature and used in a plurality of fields of coatings, thermosetting plastics, substrate resin of composite materials, and the like.
Description
Technical field
The present invention relates to chaff amine type benzoxazine colophony/maleimide compound composition.Specifically, the present invention relates to the composition that chaff amine type benzoxazine colophony and maleimide compound obtain through blend, and use said composition and the composition of other thermosetting resins through being mixed with.
Background technology
Benzoxazine is to take the intermediate of the 6-membered heterocyclic compound that phenolic compound, aldehydes and primary amine compounds consist of nitrogen and Sauerstoffatom as the synthetic class of raw material, heating and/or adding the reticulation that the nitrogenous similar resol of ring-opening polymerization generation occurs under catalyst action, be called benzoxazine colophony.Benzoxazine colophony is except having the excellent properties that comprises traditional resol such as high heat resistance, flame retardant resistance, good electricity, chemical property, low water absorbable, low cost, it does not have small molecules to emit in solidification process, goods zero shrink or have a slight expansion, polymkeric substance has low thermal expansivity, good resistance to elevated temperatures and mechanical property, the special benefits such as moisture resistance is good.
You closes benzoxazine and mainly the background technology of synthetic method can be with reference to the inventor in " containing the allylic benzoxazine intermediate of N-and composition and method of making the same " (Chinese Patent Application No.: 03146797.0), " phenolphthalein type benzoxazine intermediate and composition and method of making the same " (Chinese Patent Application No.: 200510087724.5), " containing silsesquioxane and its composition and the preparation method of benzoxazinyl group " (Chinese Patent Application No.: 200610114117.8), " benzoxazine colophony based on renewable resources and composition and preparation method " (Chinese Patent Application No.: 200910143891.5), 200910163123.6) and " benzoxazine resin/ionic liquid compositions " (Chinese Patent Application No.: the content 201010178500.6) " cage type silsesquioxane salt and the compositions of thermosetting resin with latent katalysis " (Chinese Patent Application No.:.
Although benzoxazine has excellent performance, higher solidification value is a large bottleneck that is restricting its industrial applications.For reducing the solidification value of benzoxazine, the whole bag of tricks has been proposed.Catalysis benzoxazine ring-opening polymerization (the Y X Wang and H Ishida such as phosphorus pentachloride, phosphorus trichloride, phosphorus oxychloride, titanium tetrachloride, aluminum chloride, p-methyl benzenesulfonic acid methyl esters such as Y XWang, in 1999, have been reported, Polymer, 1999,40,4563); Within 1999, J Dunkers adopts the catalysis benzoxazine ring-opening polymerizations (J Dunkers and H Ishida, J.Polym.Sci.Part A.Polym.Chem., 1999,37,1913) such as acetic acid, hexanodioic acid, trifluoroacetic acid, p-cresol; Calendar year 2001 Ishida is used for benzoxazine ring-opening polymerization or curing reaction by above-mentioned positively charged ion ring-opening polymerization catalyst in United States Patent (USP) 6225440.Hajime Kimura etc. has studied tosic acid and has reacted the salt that obtains with organic amine for the impact of the solidification process of benzoxazine/bisoxazoline resin, benzoxazine/epoxy resin, result shows that these organic ammonium salts of tosic acid can reduce the solidification value of resin system, shortens set time.The carbon residue amount of Dan oxazine resin has no raising.(specifically referring to Hajime Kimura, akihiro Matsumoto, Keiko Ohtsuka, Journal of Applied Polymer Science, 2008,107:710-718)
The inventor is also doing a large amount of work aspect research benzoxazine resin curing agent, we have reported a kind of cage-type silsesquioxane salt (Chinese Patent Application No.: 200910163123.6), research shows that this compound can significantly reduce initial solidification value and the peak value solidification value of dihydroxyphenyl propane aniline type benzoxazine with potential katalysis.In " benzoxazine resin/ionic liquid compositions " (Chinese Patent Application No.: 201010178500.6), we are applied to ionic liquid in dihydroxyphenyl propane aniline type benzoxazine colophony, even if research finds to add a small amount of ionic liquid, peak value solidification value still can obviously reduce.
Maleimide compound is that a class is easily prepared and applies industrial chemicals very widely, is widely used in vulcanization crosslinking agent, heat-proof modifier and resin intermediate etc.Maleimide compound and benzoxazine copolymerization are obviously reduced to solidification value, have no report.
Summary of the invention
The object of the invention is to propose chaff amine type benzoxazine colophony/maleimide compound composition and method of making the same.
Benzoxazine colophony/maleimide compound composition that the present invention proposes, wherein the mass ratio of maleimide compound and benzoxazine colophony is 0.5～50: 99.5～50.
Benzoxazine colophony/maleimide compound composition that the present invention proposes, wherein the mass ratio of maleimide compound and benzoxazine colophony is preferably 1～50: 99～50.
Chaff amine type benzoxazine colophony/composition that the present invention proposes, wherein chaff amine type benzoxazine colophony refers to compound or the polymkeric substance that contains chaff amine benzoxazinyl group.
Chaff amine type benzoxazine colophony/composition that the present invention proposes, wherein chaff amine type benzoxazine colophony refers to compound or the polymkeric substance that contains chaff amine benzoxazinyl group, the compound that the benzoxazinyl group compound relating to comprises following four class formation unit with and composition thereof:
1)
Wherein: R5 is chaff amine groups, R1～R4 is H, alkyl, aryl, alicyclic radical or other organic groups [as unsaturated group (vinyl, allyl group), trialkyl silyl, itrile group, hydroxyl, carboxyl etc.], the halogen atom (as chlorine, fluorine, bromine etc.) that contains 1～20 carbon atom; And R1～R4 can be identical, also can be different.
2)
N=2,3 or 4 wherein; X is alkylidene group (as methylene radical, ethylidene, 2,2-propylidene, 2, the fluoro-propylidene of 2-6), arylidene, sub-alicyclic radical, ether, thioether group, carbonyl, sulfuryl, also can there is no X (being xenyl benzoxazine intermediate); R4 is chaff amine groups, and R1～R3 is H, alkyl, aryl, alicyclic radical, unsaturated group (vinyl, allyl group), trialkyl silyl, itrile group, hydroxyl, carboxyl, halogen band alkyl or the halogen atom (as chlorine, fluorine, bromine) etc. that contain 1～20 carbon atom; And R1～R3 can be identical, also can be different.
3)
Polymkeric substance, multipolymer containing this structural unit; Wherein R1～R3 is H, alkyl (as methyl etc.), aryl, alicyclic radical etc.; R4 is chaff amine groups;
4)
Polymkeric substance, multipolymer containing this structural unit; Wherein R1, R2 are the organic groups such as alkylidene group (as methylene radical), arylidene, sub-alicyclic radical, ether, thioether group, carbonyl, sulfuryl; R3 is chaff amine groups.
The embodiment being specifically related in the present invention be take following three kinds be representative, dihydroxyphenyl propane chaff amine type benzoxazine, Eugenol chaff amine type benzoxazine and methyl catechol chaff amine type benzoxazine, but be not limited in this three kinds of oxazine compounds and composition thereof.
Dihydroxyphenyl propane chaff amine type benzoxazine
Eugenol chaff amine type benzoxazine methyl catechol chaff amine type benzoxazine
Chaff amine type benzoxazine colophony/composition that the present invention proposes, wherein maleimide compound is the organic compound that contains maleimide amine functional group, the maleimide compound of hybrid inorganic-organic cage-type silsesquioxane (POSS) structure and the polymkeric substance that contains maleimide base group, and their mixture.
Chaff amine type benzoxazine colophony/composition that the present invention proposes, wherein maleimide compound is the organic compound that contains maleimide amine functional group and their mixture, N-phenylmaleimide for example, N, N '-(4,4 '-methylenediphenyl) bismaleimides.
N-phenylmaleimide
N, N '-(4,4 '-methylenediphenyl) bismaleimides
Chaff amine type benzoxazine colophony/maleimide compound composition that the present invention proposes, wherein maleimide compound can be the maleimide compound that contains hybrid inorganic-organic cage-type silsesquioxane (POSS) structure.
Chaff amine type benzoxazine colophony/maleimide compound composition that the present invention proposes, wherein maleimide compound can be eight maleimide amination POSS (OMPS) and single maleimide amination POSS and their mixture.
The single maleimide amination of eight maleimide amination POSS (OMPS) POSS
Benzoxazine colophony/maleimide compound composition that the present invention proposes adopts solution blending process to be prepared, be that chaff amine type benzoxazine colophony and maleimide compound are dissolved in solvent specifically, then solvent evaporates obtained completely to chaff amine type benzoxazine colophony/maleimide compound composition of mixing.
The various strongtheners that benzoxazine colophony/maleimide compound composition that the present invention proposes can be familiar with those skilled in the art, comprise inorganic reinforcement, such as silicon-dioxide, calcium carbonate, carbon nanotube, carbon fiber etc., organic reinforcing comprises aramid fiber etc., hybrid reinforcement material such as polyhedral oligomeric silsesquioxane etc., prepare various compositions, to obtain thermosetting resin and the goods thereof of different purposes.
Benzoxazine colophony/maleimide compound composition that the present invention proposes, applicable to the various contour machining procedures of the familiar thermosetting resin of those skilled in the art and matrix material thereof, as sprayup process, resin transfer molding technology (RTM technology), die press technology for forming, casting molding process, impregnation technology, winding process, pultrusion molding process etc.; The strongthener of preparing matrix material use can be that various fibers or nanometer strengthen particle; The porosity of resulting product or matrix material is low, shrinks little; Can be used as high-performance adhesive and coating, as the matrix resin of high performance composite, and can replace traditional resol, epoxy resin for electronic industry.
Embodiment
Benzoxazine colophony/maleimide compound composition adopts the method for solution blending to be prepared, be that chaff amine type benzoxazine colophony and maleimide compound are dissolved in solvent specifically, then solvent evaporates obtained completely to chaff amine type benzoxazine colophony/maleimide compound composition of mixing.Following examples all adopt the method for solution blending to prepare chaff amine type benzoxazine colophony/maleimide compound composition.The peak value solidification value of compositions of thermosetting resin adopts differential scanning calorimeter (DSC) method to measure.
Comparative example 1
Dihydroxyphenyl propane chaff amine type benzoxazine colophony is carried out to DSC test, and recording its cure peak temperature is 237 ℃.
Comparative example 2
Methyl catechol chaff amine type benzoxazine colophony is ground, obtain pale yellow powder, pale yellow powder is carried out to DSC test, record it and near 170 ℃, start to decompose, decomposition rate is greater than curing speed, and curing reaction can not occur.
Comparative example 3
Eugenol chaff amine type benzoxazine colophony is ground, obtain pale yellow powder, pale yellow powder is carried out to DSC test, record it and near 200 ℃, start to decompose, decomposition rate is greater than curing speed, and curing reaction can not occur.
Embodiment 1
With the ratio of 0.5: 99.5 (mass ratio) configuration eight maleimide amination POSS (OMPS) and dihydroxyphenyl propane chaff amine type benzoxazine colophony composition, composition carries out DSC test, and recording cure peak temperature is 231 ℃.
Embodiment 2
With the ratio of 1: 99 (mass ratio) configuration eight maleimide amination POSS (OMPS) and dihydroxyphenyl propane chaff amine type benzoxazine colophony composition, composition carries out DSC test, and recording cure peak temperature is 230 ℃.
Embodiment 3
With the ratios of 2: 98 (mass ratio) configuration eight maleimide amination POSS (OMPS) and dihydroxyphenyl propane chaff amine type benzoxazine colophony composition, composition carries out DSC test, and recording cure peak temperature is 226 ℃.
Embodiment 4
With the ratios of 3: 97 (mass ratio) configuration eight maleimide amination POSS (OMPS) and dihydroxyphenyl propane chaff amine type benzoxazine colophony composition, composition carries out DSC test, and recording cure peak temperature is 224 ℃.
Embodiment 5
With the ratios of 5: 95 (mass ratio) configuration eight maleimide amination POSS (OMPS) and dihydroxyphenyl propane chaff amine type benzoxazine colophony composition, composition carries out DSC test, and recording cure peak temperature is 219 ℃.
Embodiment 6
With the ratios of 11: 89 (mass ratio) configuration eight maleimide amination POSS (OMPS) and dihydroxyphenyl propane chaff amine type benzoxazine colophony composition, composition carries out DSC test, and recording cure peak temperature is 209 ℃.
Embodiment 7
With the ratios of 20: 80 (mass ratio) configuration eight maleimide amination POSS (OMPS) and dihydroxyphenyl propane chaff amine type benzoxazine colophony composition, composition carries out DSC test, and recording cure peak temperature is 196 ℃.
Embodiment 8
With the ratios of 32: 68 (mass ratio) configuration eight maleimide amination POSS (OMPS) and dihydroxyphenyl propane chaff amine type benzoxazine colophony composition, composition carries out DSC test, and recording cure peak temperature is 191 ℃.
Embodiment 9
With the ratios of 50: 50 (mass ratio) configuration eight maleimide amination POSS (OMPS) and dihydroxyphenyl propane chaff amine type benzoxazine colophony composition, composition carries out DSC test, and recording cure peak temperature is 187 ℃.
Embodiment 10
With the ratios of 5: 95 (mass ratio) configuration N-phenylmaleimide and dihydroxyphenyl propane chaff amine type benzoxazine colophony composition, composition carries out DSC test, and recording cure peak temperature is 220 ℃.
Embodiment 11
With the ratios of 20: 80 (mass ratio) configuration N-phenylmaleimide and dihydroxyphenyl propane chaff amine type benzoxazine colophony composition, composition carries out DSC test, and recording cure peak temperature is 214 ℃.
Embodiment 12
With the ratios of 42: 58 (mass ratio) configuration N-phenylmaleimide and dihydroxyphenyl propane chaff amine type benzoxazine colophony composition, composition carries out DSC test, and recording cure peak temperature is 202 ℃.
Embodiment 13
With the ratios of 5: 95 (mass ratio) configuration bismaleimides and dihydroxyphenyl propane chaff amine type benzoxazine colophony composition, composition carries out DSC test, and recording cure peak temperature is 218 ℃.
Embodiment 14
With the ratios of 20: 80 (mass ratio) configuration bismaleimides and dihydroxyphenyl propane chaff amine type benzoxazine colophony composition, composition carries out DSC test, and recording cure peak temperature is 219 ℃.
Embodiment 15
With the ratios of 50: 50 (mass ratio) configuration bismaleimides and dihydroxyphenyl propane chaff amine type benzoxazine colophony composition, composition carries out DSC test, and recording cure peak temperature is 208 ℃.
Embodiment 16
With the ratios of 10: 10: 80 (mass ratio) configuration bismaleimides, N-phenylmaleimide and dihydroxyphenyl propane chaff amine type benzoxazine colophony composition, composition carries out DSC test, and recording cure peak temperature is 210 ℃.
Embodiment 17
With the ratios of 5: 95 (mass ratio), configure single maleimide amination POSS and dihydroxyphenyl propane chaff amine type benzoxazine colophony composition, composition carries out DSC test, and recording cure peak temperature is 205 ℃.
Embodiment 18
With the ratios of 50: 50 (mass ratio), configure single maleimide amination POSS and dihydroxyphenyl propane chaff amine type benzoxazine colophony composition, composition carries out DSC test, and recording cure peak temperature is 148 ℃.
Embodiment 19
With the ratios of 6: 94 (mass ratio) configuration eight maleimide amination POSS (OMPS) and methyl catechol chaff amine type benzoxazine colophony composition, composition carries out DSC test, said composition thermolysis in solidification process obviously weakens, and recording cure peak temperature is 248 ℃.
Embodiment 20
With the ratios of 3: 97 (mass ratio) configuration eight maleimide amination POSS (OMPS) and Eugenol chaff amine type benzoxazine colophony composition, composition carries out DSC test, said composition is without thermolysis in solidification process, and recording cure peak temperature is 248 ℃.
Claims (8)
1. benzoxazine colophony/maleimide compound composition, the mass ratio that it is characterized in that maleimide compound and benzoxazine colophony is 0.1～50: 99.9～50, described benzoxazine colophony refers to compound or polymkeric substance and their mixture of the benzoxazinyl group that contains chaff amine groups, the compound that comprises following four class formation unit with and composition thereof:
1)
Wherein: R5 is furfuryl, R1～R4 is selected from H, a kind of containing in alkyl, aryl, alicyclic radical, vinyl, allyl group, trialkyl silyl, itrile group, hydroxyl, carboxyl and the halogen atom of 1～20 carbon atom;
2)
N=2 wherein; X is a kind of in alkylidene group, arylidene, sub-alicyclic radical, ether, thioether group, carbonyl, sulfuryl and singly-bound; R4 is furfuryl, and R1～R3 is H, a kind of containing in alkyl, aryl, alicyclic radical, vinyl, allyl group, trialkyl silyl, itrile group, hydroxyl, carboxyl, haloalkyl and the halogen atom of 1～20 carbon atom;
3)
Polymkeric substance, multipolymer containing this structural unit; Wherein R1～R3 is selected from a kind of in H, alkyl, aryl and alicyclic radical; R4 is furfuryl;
4)
Polymkeric substance, multipolymer containing this structural unit; Wherein R1, R2 are selected from a kind of in alkylidene group, arylidene, sub-alicyclic radical, ether, thioether group, carbonyl and sulfuryl; R3 is furfuryl.
2. benzoxazine colophony/maleimide compound composition according to claim 1, the mass ratio that it is characterized in that maleimide compound and benzoxazine colophony preferably 1～50: 99～50.
3. benzoxazine colophony/maleimide compound composition according to claim 1, is characterized in that described halogen atom is selected from a kind of in chlorine, fluorine and bromine.
4. benzoxazine colophony/maleimide compound composition according to claim 1, is characterized in that alkylidene group in described X group is selected from a kind of in methylene radical, ethylidene and 2,2-propylidene.
5. benzoxazine colophony/maleimide compound composition according to claim 1, it is characterized in that maleimide compound is the organic compound that contains maleimide amine functional group, the polymkeric substance that contains maleimide base group and their mixture.
6. benzoxazine colophony/maleimide compound composition according to claim 1, it is characterized in that maleimide compound is N-phenylmaleimide, N, N '-(4,4 '-methylenediphenyl) bismaleimides and their mixture.
7. benzoxazine colophony/maleimide compound composition according to claim 1, is characterized in that maleimide compound is the maleimide compound that contains hybrid inorganic-organic cage silsesquioxane structure.
8. benzoxazine colophony/maleimide compound composition according to claim 1, is characterized in that maleimide compound is eight maleimide amination cage-type silsesquioxanes and single maleimide amination cage-type silsesquioxane and their mixture.
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| CN102020846B true CN102020846B (en) | 2014-03-19 |
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Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| JP5607091B2 (en) * | 2012-02-27 | 2014-10-15 | 信越化学工業株式会社 | Fluorine-containing maleimide compound and method for producing the same |
| CN104230837B (en) * | 2013-06-24 | 2016-04-06 | 北京化工大学 | pyrene amine type benzoxazine compound and preparation method thereof |
| CN108485182B (en) * | 2018-03-26 | 2020-04-28 | 常熟生益科技有限公司 | High-frequency resin composition and prepreg and laminated board manufactured by using same |
| CN108440901B (en) * | 2018-03-26 | 2020-07-14 | 常熟生益科技有限公司 | High-frequency resin composition, and prepreg, interlayer insulating film and laminated board prepared from high-frequency resin composition |
| CN109679048B (en) * | 2019-01-16 | 2021-06-22 | 江苏大学 | Main chain type benzoxazine resin and preparation method thereof |
| CN110872281B (en) * | 2019-11-29 | 2024-02-27 | 淮北绿洲新材料有限责任公司 | Preparation methods of tertiary phenol-furfuryl amine type benzoxazine monomer, cured resin and copolymer resin thereof |
| CN114836034B (en) * | 2022-06-01 | 2023-02-17 | 江南大学 | Bismaleimide resin composition and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6482946B1 (en) * | 1999-11-05 | 2002-11-19 | Dow Global Technologies Inc. | High char yield benzoxazine compositions |
| CN1451679A (en) * | 2003-04-30 | 2003-10-29 | 四川大学 | Modified benzoxazine resin capable of using for RTM and process for preparing same |
| CN1944429A (en) * | 2006-10-30 | 2007-04-11 | 北京化工大学 | 2-oxazolinyl-benzo oxazinyl compound and its composition and preparing method |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6482946B1 (en) * | 1999-11-05 | 2002-11-19 | Dow Global Technologies Inc. | High char yield benzoxazine compositions |
| CN1451679A (en) * | 2003-04-30 | 2003-10-29 | 四川大学 | Modified benzoxazine resin capable of using for RTM and process for preparing same |
| CN1944429A (en) * | 2006-10-30 | 2007-04-11 | 北京化工大学 | 2-oxazolinyl-benzo oxazinyl compound and its composition and preparing method |
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