CN103467353B - Containing the bismaleimides and preparation method thereof of fluorenyl and aryl oxide bond structure - Google Patents
Containing the bismaleimides and preparation method thereof of fluorenyl and aryl oxide bond structure Download PDFInfo
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- CN103467353B CN103467353B CN201310437116.7A CN201310437116A CN103467353B CN 103467353 B CN103467353 B CN 103467353B CN 201310437116 A CN201310437116 A CN 201310437116A CN 103467353 B CN103467353 B CN 103467353B
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Abstract
The invention provides a kind of bismaleimides containing fluorenyl and aryl oxide bond structure and preparation method thereof, the bismaleimides containing fluorenyl and aryl oxide bond structure has following structural formula:
substituent R in formula
1, R
2be selected from hydrogen atom, halogen atom, nitro, C independently of one another
1~ C
20aliphatic alkyl or derivatives thereof or C
6~ C
12aromatic hydrocarbon alkyl or derivatives thereof.
Description
Technical field
The invention belongs to technical field of polymer materials, be specifically related to bismaleimides containing fluorenyl and aryl oxide bond structure and preparation method thereof.
Background technology
Bismaleimides is a kind of important thermosetting resin, has good high temperature resistant, radiation hardness, wet-heat resisting, chemical resistance, possesses the performance that high strength, high-modulus and high thermal resistance etc. are excellent.But bismaleimides is insoluble in common solvent, after the higher and solidification of fusing point, the shortcomings such as property is crisp limit its application.The method improving bimaleimide resin toughness has a lot, and the bismaleimides containing flexible chain and aromatic ring structure in the main chain of design and synthesizing new is one of effective ways improving its performance.
Owing to having high second-order transition temperature, excellent heatproof oxidation performance and mechanical property etc. containing the polymkeric substance of fluorenyl structure, therefore polyimide, poly-peptamine, poly quinoline etc. are studied containing the thermally stable polymer of fluorenyl structure and be synthesized in a large number.The INDRA K.VARMA of NASA's Ames Research Center has synthesized in nineteen eighty-two the bismaleimides 9 containing fluorenyl structure first, two (4-maleimidophenyl) fluorenes (see structural formula A) of 9-, Canadian KUMAR ASHWANI applied for the European patent of this structure bismaleimides in 2011.But this monomer fusing point reaches 340 DEG C, namely solidifies after melting, and its solvability in majority of organic solvent is all poor.
Document 1(Journal of Applied Polymer Science, 2008,107) three kinds of chain-prolonged type fluorenyl bimaleimide monomers containing imide bond are reported, its solvability is significantly improved, dissolve in chloroform, methylene dichloride, tetrahydrofuran (THF), N, dinethylformamide equal solvent, but the bismaleimides melt temperature of this class formation is still higher, and melting peak is a broad peak, between 240-300 DEG C, fusing point and solidification value are comparatively close, melting is worked in coordination with solidification and occurs, curing exotherm is concentrated, and causes melt-processed difficulty.And both there is not yet disclosed patent or bibliographical information up to now containing high heatproof oxidation performance fluorenes ring bismaleimides containing rotatable aryl oxide connecting key and preparation method thereof.
Summary of the invention
An object of the present invention is to provide that a kind of favorable solubility, fusing point are low, curing exotherm is steady and the bismaleimides containing fluorenyl and aryl oxide bond structure of cured article fine heat-resisting performance.Two of object of the present invention is to provide the above-mentioned novel preparation method containing the bismaleimides of fluorenyl and aryl oxide bond structure.
It is as follows that the present invention solves the technical scheme that its technical problem takes.
Contain a bismaleimides for fluorenyl and aryl oxide bond structure, it is characterized in that there is following structural formula:
Substituent R in formula
1, R
2be selected from hydrogen atom, halogen atom, nitro, C independently of one another
1~ C
20aliphatic alkyl or derivatives thereof or C
6~ C
12aromatic hydrocarbon alkyl or derivatives thereof.
The preparation method containing the bismaleimides of fluorenyl and aryl oxide bond structure that the present invention relates to comprises the steps:
(1) containing aromatic diamine and maleic anhydride mol ratio 1:2 ~ 2.3 of fluorenyl and aryl oxide bond structure, react 4 ~ 10 hours in polar aprotic solvent at 0 ~ 50 DEG C, filter, filter cake obtains the bismaleimide amino acid containing fluorenyl and aryl oxide bond structure through vacuum-drying, and the consumption of polar aprotic solvent is that 1 mole of aromatic diamine containing fluorenyl and aryl oxide bond structure uses polar aprotic solvent 400 ~ 1000 milliliters;
(2) the bismaleimide amino acid containing fluorenyl and aryl oxide bond structure that generates of upper step is under the effect of dewatering agent and catalyzer, react 5 ~ 10 hours in polar aprotic solvent at 20 ~ 80 DEG C, reaction solution adds water and separates out solid, filtration, filter cake obtains the bismaleimides containing fluorenyl and aryl oxide bond structure through vacuum-drying, and the consumption of polar aprotic solvent is that 1 mole of bismaleimide amino acid containing fluorenyl and aryl oxide bond structure uses polar aprotic solvent 500 ~ 2000 milliliters.
The synthetic route of the above-mentioned bismaleimides containing fluorenyl and aryl oxide bond structure is as follows:
(1) one in the preferred acetone of the polar aprotic solvent, described in (2), DMF, N,N-dimethylacetamide, N-Methyl pyrrolidone, pyridine or tetrahydrofuran (THF).
(2) the preferred diacetyl oxide of the dewatering agent described in, the preferred acetate of catalyzer and/or triethylamine.
One or more mixture in the described preferred sodium-acetate of catalyst acetic acid salt, magnesium acetate and Cobaltous diacetate.
The consumption of dewatering agent diacetyl oxide is preferably 3 ~ 8 times of the bismaleimide amino acid mole number containing fluorenyl and aryl oxide bond structure, the consumption of catalyst of triethylamine is preferably 0.5 ~ 5 times of the bismaleimide amino acid mole number containing fluorenyl and aryl oxide bond structure, and the consumption of catalyst acetic acid salt is preferably 1 mole of bismaleimide amino acid containing fluorenyl and aryl oxide bond structure and uses 0.5 ~ 5g.
The invention has the beneficial effects as follows: bismaleimides of the present invention is the bismaleimides that a class contains fluorenyl and aryl oxide bond structure, its primary structure is the thermotolerance that condensed cyclic structure can keep good, in addition owing to introducing aryl oxide key in molecular structure, molecular chain is made to have certain kindliness, make the increase of its solvability, fusing point reduction, widen its melt-processed window.
Accompanying drawing explanation
Fig. 1 is the infrared spectra of two [4-(4-maleimide phenoxyl) phenyl] fluorenes of the embodiment of the present invention 19,9-.
Fig. 2 is the H nuclear magnetic spectrum of two [4-(4-maleimide phenoxyl) phenyl] fluorenes of the embodiment of the present invention 19,9-.
Fig. 3 is the infrared spectra of two [4-(4-the maleimide phenoxyl)-3-aminomethyl phenyl] fluorenes of the embodiment of the present invention 29,9-.
Fig. 4 is the H nuclear magnetic spectrum of two [4-(4-the maleimide phenoxyl)-3-aminomethyl phenyl] fluorenes of the embodiment of the present invention 29,9-.
Fig. 5 is the hot weightless picture of the embodiment of the present invention 1.
Fig. 6 is the hot weightless picture of the embodiment of the present invention 2.
Embodiment
Set forth the present invention further below in conjunction with specific embodiment, but its object is to understand the present invention better, but not limit the scope of the invention.
Two [4-(4-maleimide phenoxyl) phenyl] fluorenes of embodiment 1:9,9-
(1) maleic anhydride (0.21mol) is dissolved in 20ml acetone, stirring and dissolving.Aromatic diamine I(0.1mol by containing fluorenyl and aryl oxide bond structure) be dissolved in 80ml acetone, be slowly added dropwise in the acetone soln of maleic anhydride, react 8 hours under room temperature.After reaction terminates, filtered by the yellow solid generated, filter cake obtains the bismaleimide amino acid II containing fluorenyl and aryl oxide bond structure through vacuum-drying, and it is 99.5% that productive rate 92.7%, HPLC measures purity.FT-IR（KBr，cm
-1）：3288，1543（-NH），1712（-C=O）。
(2) the bismaleimide amino acid II(0.1mol upper step generated) be suspended in 200ml acetone, add 0.15g sodium-acetate, be heated to 50 DEG C, drip 18ml triethylamine and 40ml diacetyl oxide, question response liquid to become after homogeneous phase isothermal reaction 10 hours.After reaction terminates, reaction solution is slowly added dropwise in water, the crystal generated is filtered, vacuum-drying, obtain 9,9-yellow two [4-(4-maleimide phenoxyl) phenyl] fluorenes III, productive rate 88%, fusing point: 129.2 DEG C.FT-IR(KBr, cm
-1): [seeing Fig. 1] 3089(-C=CH), 1717(C=O), 1395,1148(C-N-C).
1hNMR(400MHz, CDCl
3): [seeing Fig. 2] δ 7.77(2H, d, ArH), 7.41(2H, t, ArH) and, 7.36(2H, d, ArH), 7.30(2H, t, ArH), 7.26(4H, d, ArH) and, 7.18(4H, d, ArH), 7.04(4H, t, ArH), 6.89(4H, d, ArH) and, 6.82(4H, s ,-C=CH).TG(thermal weight loss): [seeing Fig. 5].Solubility experiment: [in table 1].
Two [4-(4-the maleimide phenoxyl)-3-aminomethyl phenyl] fluorenes of embodiment 2:9,9-
(1) maleic anhydride (0.21mol) is dissolved in 20ml acetone, stirring and dissolving.Aromatic diamine I ' (0.1mol) containing methyl fluorenes and aryl oxide bond structure is dissolved in 80ml acetone, is slowly added dropwise in the acetone soln of maleic anhydride, react 8 hours under room temperature.After reaction terminates, filtered by the yellow solid generated, filter cake obtains the bismaleimide amino acid II ' containing methyl fluorenes and aryl oxide bond structure through vacuum-drying, and it is 99.5% that productive rate 91.2%, HPLC measures purity.FT-IR（KBr，cm
-1）：3282，1550（-NH），2958，2916（-CH
3），1707（-C=O）。
(2) the bismaleimide amino acid II ' (0.1mol) upper step generated is suspended in 200ml acetone, adds 0.15g sodium-acetate, is heated to 50 DEG C, drips 18ml triethylamine and 40ml diacetyl oxide, and question response liquid to become after homogeneous phase isothermal reaction 10 hours.After reaction terminates, reaction solution is slowly added dropwise in water, the crystal generated is filtered, vacuum-drying, obtain 9,9-yellow two [4-(4-maleimide phenoxyl)-3-aminomethyl phenyl] fluorenes III ', productive rate 85%, fusing point: 126.0 DEG C.FT-IR(KBr, cm
-1): [seeing Fig. 3] 3105(-C=CH), 2924,2856(-CH
3), 1716(C=O), 1394,1151(C-N-C).
1hNMR(400MHz, CDCl
3): [seeing Fig. 4] δ 7.78(2H, d, ArH), 7.44(2H, d, ArH), 7.39(2H, t, ArH), 7.31(2H, t, ArH), 7.21(4H, d, ArH), 7.04(4H, m, ArH), 6.95(4H, d, ArH), 6.82(4H, s ,-C=CH), 6.80(2H, d, ArH), 2.11(6H, s ,-CH
3).TG(thermal weight loss): [seeing Fig. 6].Solubility experiment: [in table 1].
Table 1. contains the solvability of the bismaleimide monomer of fluorenyl and aryl oxide bond structure
-: insoluble; ++: Yi Rong.
Claims (6)
1. contain a bismaleimides for fluorenyl and aryl oxide bond structure, it is characterized in that there is following structural formula:
2. the preparation method containing the bismaleimides of fluorenyl and aryl oxide bond structure according to claim 1, is characterized in that, comprise the steps:
(1) containing aromatic diamine and maleic anhydride mol ratio 1:2 ~ 2.3 of fluorenyl and aryl oxide bond structure, react 4 ~ 10 hours in polar aprotic solvent at 0 ~ 50 DEG C, filter, filter cake obtains the bismaleimide amino acid containing fluorenyl and aryl oxide bond structure through vacuum-drying, and the consumption of polar aprotic solvent is that 1 mole of aromatic diamine containing fluorenyl and aryl oxide bond structure uses polar aprotic solvent 400 ~ 1000 milliliters;
(2) the bismaleimide amino acid containing fluorenyl and aryl oxide bond structure that generates of upper step is under the effect of dewatering agent and catalyzer, react 5 ~ 10 hours in polar aprotic solvent at 20 ~ 80 DEG C, reaction solution adds water and separates out solid, filtration, filter cake obtains the bismaleimides containing fluorenyl and aryl oxide bond structure through vacuum-drying, and the consumption of polar aprotic solvent is that 1 mole of bismaleimide amino acid containing fluorenyl and aryl oxide bond structure uses polar aprotic solvent 500 ~ 2000 milliliters.
3. preparation method according to claim 2, it is characterized in that, (1), the polar aprotic solvent described in (2) is the one in acetone, DMF, N,N-dimethylacetamide, N-Methyl pyrrolidone, pyridine or tetrahydrofuran (THF).
4. preparation method according to claim 2, is characterized in that, the dewatering agent described in (2) is diacetyl oxide, and catalyzer is acetate and/or triethylamine.
5. preparation method according to claim 4, is characterized in that, described catalyst acetic acid salt is one or more the mixture in sodium-acetate, magnesium acetate and Cobaltous diacetate.
6. preparation method according to claim 4, it is characterized in that, the consumption of dewatering agent diacetyl oxide is 3 ~ 8 times of the bismaleimide amino acid mole number containing fluorenyl and aryl oxide bond structure, the consumption of catalyst of triethylamine is 0.5 ~ 5 times of the bismaleimide amino acid mole number containing fluorenyl and aryl oxide bond structure, and the consumption of catalyst acetic acid salt is that 1 mole of bismaleimide amino acid containing fluorenyl and aryl oxide bond structure uses 0.5 ~ 5g.
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| CN102604043A (en) * | 2012-02-29 | 2012-07-25 | 株洲时代新材料科技股份有限公司 | Double-component imine modified epoxy solvent-free impregnated resin and preparation and use methods |
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| N-(4-羟基苯基) 马来酰亚胺的合成及其光谱分析;洪伟，等;《化学分析计量》;20111120;第20卷(第6期);全文 * |
| 新颖含酞侧基双马来酰亚胺及其改性树脂体系的研究;熊需海;《中国博士学位论文全文数据库工程科技Ⅰ辑》;20120915(第09期);正文第4-5、29、31-32、38-39页 * |
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Inventor after: Chen Ping Inventor after: Zhang Liying Inventor after: Zhao Xiaojing Inventor after: Xia Lianlian Inventor after: Xiong Xuhai Inventor after: Fan Shengdi Inventor before: Zhang Liying Inventor before: Chen Ping Inventor before: Zhao Xiaojing Inventor before: Xia Lianlian Inventor before: Xiong Xuhai Inventor before: Fan Shengdi |
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Effective date of registration: 20170405 Address after: 116024 Liaoning, Dalian, Ganjingzi Ling Road, No. 2 Patentee after: DALIAN University OF TECHNOLOGY Address before: 518131 Shenzhen, Longhua, New District, the people on the streets of the village of Tong Tong Tau Village, building 69 Patentee before: SHENZHEN BAOLIMO TECHNOLOGY Co.,Ltd. Patentee before: Dalian University of Technology Effective date of registration: 20170405 Address after: 518131 Shenzhen, Longhua, New District, the people on the streets of the village of Tong Tong Tau Village, building 69 Patentee after: SHENZHEN BAOLIMO TECHNOLOGY Co.,Ltd. Patentee after: DALIAN University OF TECHNOLOGY Address before: 116600 Liaoning, Jinzhou New District, Liaohe West Road, No. 18 Patentee before: DALIAN NATIONALITIES University Patentee before: Dalian University of Technology |
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Application publication date: 20131225 Assignee: JIANGSU XINYANG NEW MATERIAL CO.,LTD. Assignor: DALIAN UNIVERSITY OF TECHNOLOGY Contract record no.: X2020980000359 Denomination of invention: Bismaleimide containing fluorenyl and aromatic ether bond structure, and preparation method thereof Granted publication date: 20151028 License type: Exclusive License Record date: 20200227 |