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CN103467353B - Containing the bismaleimides and preparation method thereof of fluorenyl and aryl oxide bond structure - Google Patents

️Wed Oct 28 2015

Containing the bismaleimides and preparation method thereof of fluorenyl and aryl oxide bond structure Download PDF

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Publication number

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 Authority

China

Prior art keywords

ether bond

aryl ether

bismaleimide

bond structure

containing fluorenyl

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2013-09-22

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CN201310437116.7A

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CN103467353A (en

Inventor

张丽影

陈平

赵小菁

夏连连

熊需海

范圣第

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Shenzhen Baolimo Technology Co ltd

Dalian University of Technology

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Dalian University of Technology

Dalian Nationalities University

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2013-09-22

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2013-09-22

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2015-10-28

2013-09-22 Application filed by Dalian University of Technology, Dalian Nationalities University filed Critical Dalian University of Technology

2013-09-22 Priority to CN201310437116.7A priority Critical patent/CN103467353B/en

2013-12-25 Publication of CN103467353A publication Critical patent/CN103467353A/en

2015-10-28 Application granted granted Critical

2015-10-28 Publication of CN103467353B publication Critical patent/CN103467353B/en

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229920003192 poly(bis maleimide) Polymers 0.000 title claims abstract description 41
125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 title claims abstract description 37
238000002360 preparation method Methods 0.000 title claims abstract description 9
125000003118 aryl group Chemical group 0.000 title description 2
XQUPVDVFXZDTLT-UHFFFAOYSA-N 1-[4-[[4-(2,5-dioxopyrrol-1-yl)phenyl]methyl]phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C(C=C1)=CC=C1CC1=CC=C(N2C(C=CC2=O)=O)C=C1 XQUPVDVFXZDTLT-UHFFFAOYSA-N 0.000 claims abstract description 38
CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 21
WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims description 18
239000002253 acid Substances 0.000 claims description 18
ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 15
ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 12
239000003880 polar aprotic solvent Substances 0.000 claims description 12
239000003054 catalyst Substances 0.000 claims description 9
238000006243 chemical reaction Methods 0.000 claims description 9
QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical group CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 6
WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
150000004984 aromatic diamines Chemical class 0.000 claims description 6
239000012024 dehydrating agents‎ Substances 0.000 claims description 6
FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 6
JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 4
239000012065 filter cake Substances 0.000 claims description 4
238000000034 method Methods 0.000 claims description 4
235000017281 sodium acetate Nutrition 0.000 claims description 4
239000001632 sodium acetate Substances 0.000 claims description 4
239000007787 solid Substances 0.000 claims description 4
XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 claims description 3
YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 2
229940011182 cobalt acetate Drugs 0.000 claims description 2
QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 2
UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 claims description 2
229940069446 magnesium acetate Drugs 0.000 claims description 2
235000011285 magnesium acetate Nutrition 0.000 claims description 2
239000011654 magnesium acetate Substances 0.000 claims description 2
239000000203 mixture Substances 0.000 claims description 2
239000003586 protic polar solvent Substances 0.000 claims description 2
UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
229960004249 sodium acetate Drugs 0.000 claims description 2
OHLUUHNLEMFGTQ-UHFFFAOYSA-N N-methylacetamide Chemical compound CNC(C)=O OHLUUHNLEMFGTQ-UHFFFAOYSA-N 0.000 claims 1
150000001412 amines Chemical class 0.000 claims 1
125000001931 aliphatic group Chemical group 0.000 abstract description 2
125000000217 alkyl group Chemical group 0.000 abstract description 2
125000005843 halogen group Chemical group 0.000 abstract description 2
125000004435 hydrogen atom Chemical group [H]* 0.000 abstract description 2
125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 abstract description 2
125000001424 substituent group Chemical group 0.000 abstract description 2
230000008018 melting Effects 0.000 description 12
238000002844 melting Methods 0.000 description 12
NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 10
238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 4
YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
239000000178 monomer Substances 0.000 description 3
229920000642 polymer Polymers 0.000 description 3
238000007711 solidification Methods 0.000 description 3
230000008023 solidification Effects 0.000 description 3
GKEUODMJRFDLJY-UHFFFAOYSA-N 1-Methylfluorene Chemical compound C12=CC=CC=C2CC2=C1C=CC=C2C GKEUODMJRFDLJY-UHFFFAOYSA-N 0.000 description 2
AAOJYPZTWBWRAD-UHFFFAOYSA-N 1-[4-[4-[9-[4-[4-(2,5-dioxopyrrol-1-yl)phenoxy]phenyl]fluoren-9-yl]phenoxy]phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=C(OC2=CC=C(C=C2)C2(C3=C(C=CC=C3)C3=C2C=CC=C3)C2=CC=C(OC3=CC=C(C=C3)N3C(=O)C=CC3=O)C=C2)C=C1 AAOJYPZTWBWRAD-UHFFFAOYSA-N 0.000 description 2
HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
239000013078 crystal Substances 0.000 description 2
238000010586 diagram Methods 0.000 description 2
238000004128 high performance liquid chromatography Methods 0.000 description 2
238000002329 infrared spectrum Methods 0.000 description 2
238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 2
230000003647 oxidation Effects 0.000 description 2
238000007254 oxidation reaction Methods 0.000 description 2
125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
-1 polypeptidamine Polymers 0.000 description 2
229920005989 resin Polymers 0.000 description 2
239000011347 resin Substances 0.000 description 2
239000002904 solvent Substances 0.000 description 2
238000003756 stirring Methods 0.000 description 2
KLDSXSAQFVJBKK-UHFFFAOYSA-N 1-[4-[4-[9-[4-[4-(2,5-dioxopyrrol-1-yl)phenoxy]-3-methylphenyl]fluoren-9-yl]-2-methylphenoxy]phenyl]pyrrole-2,5-dione Chemical compound C1(C=CC(N1C1=CC=C(OC2=C(C=C(C=C2)C2(C3=CC=CC=C3C=3C=CC=CC2=3)C2=CC(=C(C=C2)OC2=CC=C(C=C2)N2C(C=CC2=O)=O)C)C)C=C1)=O)=O KLDSXSAQFVJBKK-UHFFFAOYSA-N 0.000 description 1
BXPYZSVAHMLJJI-UHFFFAOYSA-N 1-[4-[9-[4-(2,5-dioxopyrrol-1-yl)phenyl]fluoren-9-yl]phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=C(C2(C3=CC=CC=C3C3=CC=CC=C32)C=2C=CC(=CC=2)N2C(C=CC2=O)=O)C=C1 BXPYZSVAHMLJJI-UHFFFAOYSA-N 0.000 description 1
FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
239000004642 Polyimide Substances 0.000 description 1
229920000292 Polyquinoline Polymers 0.000 description 1
150000008378 aryl ethers Chemical class 0.000 description 1
230000009286 beneficial effect Effects 0.000 description 1
239000012295 chemical reaction liquid Substances 0.000 description 1
238000005260 corrosion Methods 0.000 description 1
230000007797 corrosion Effects 0.000 description 1
230000009477 glass transition Effects 0.000 description 1
238000010128 melt processing Methods 0.000 description 1
239000003960 organic solvent Substances 0.000 description 1
229920001721 polyimide Polymers 0.000 description 1
239000002861 polymer material Substances 0.000 description 1
239000000047 product Substances 0.000 description 1
230000005855 radiation Effects 0.000 description 1
239000000126 substance Substances 0.000 description 1
230000002194 synthesizing effect Effects 0.000 description 1
229920001187 thermosetting polymer Polymers 0.000 description 1
230000004580 weight loss Effects 0.000 description 1

Landscapes

Pyrrole Compounds (AREA)
Indole Compounds (AREA)

Abstract

本发明提供一种含芴基及芳醚键结构的双马来酰亚胺及其制备方法，含芴基及芳醚键结构的双马来酰亚胺具有如下结构式：式中的取代基R₁、R₂各自独立地选自氢原子、卤素原子、硝基、C₁～C₂₀的脂肪族烷基或其衍生物、或者C₆～C₁₂的芳香烃烷基或其衍生物。The invention provides a bismaleimide containing a fluorenyl group and an aryl ether bond structure and a preparation method thereof. The bismaleimide containing a fluorenyl group and an aryl ether bond structure has the following structural formula: The substituents R ₁ and R ₂ in the formula are each independently selected from a hydrogen atom, a halogen atom, a nitro group, a C ₁ -C ₂₀ aliphatic alkyl group or its derivatives, or a C ₆ -C ₁₂ aromatic hydrocarbon alkyl group or its derivatives.

Description

含芴基及芳醚键结构的双马来酰亚胺及其制备方法Bismaleimide containing fluorenyl group and aryl ether bond structure and preparation method thereof

技术领域 technical field

本发明属于高分子材料技术领域，具体涉及含芴基及芳醚键结构的双马来酰亚胺及其制备方法。 The invention belongs to the technical field of polymer materials, and in particular relates to a bismaleimide containing a fluorenyl group and an aryl ether bond structure and a preparation method thereof.

背景技术 Background technique

双马来酰亚胺是一种重要的热固性树脂，具有良好的耐高温、耐辐射、耐湿热、耐化学腐蚀性，具备高强度、高模量和耐高温性等优异的性能。但是双马来酰亚胺不溶于普通的溶剂中，熔点较高及固化后性脆等缺点限制了其应用。提高双马来酰亚胺树脂韧性的方法有很多，设计和合成新型的主链中含柔性链和芳环结构的双马来酰亚胺是提高其性能的有效方法之一。 Bismaleimide is an important thermosetting resin with good high temperature resistance, radiation resistance, heat and humidity resistance, chemical corrosion resistance, high strength, high modulus and high temperature resistance and other excellent properties. However, bismaleimide is insoluble in common solvents, its high melting point and brittleness after curing limit its application. There are many ways to improve the toughness of bismaleimide resin, and designing and synthesizing a new type of bismaleimide with flexible chain and aromatic ring structure in the main chain is one of the effective methods to improve its performance.

由于含芴基结构的聚合物具有高的玻璃化转变温度、优异的耐热氧化性和力学性能等，因此聚酰亚胺、聚肽胺、聚喹啉等大量含芴基结构的耐热性聚合物被研究和合成出来。美国航空航天局艾姆斯研究中心的INDRA K.VARMA在1982年首次合成了含芴基结构的双马来酰亚胺9,9-双（4-马来酰亚胺基苯基）芴（见结构式A），加拿大的KUMAR ASHWANI在2011年申请了该结构双马来酰亚胺的欧洲专利。但该单体熔点达到340℃，熔融后即发生固化，并且其在大部分有机溶剂中的溶解性均较差。 Because polymers containing fluorenyl structures have high glass transition temperature, excellent thermal oxidation resistance and mechanical properties, etc., the heat resistance of a large number of fluorenyl-containing structures such as polyimide, polypeptidamine, and polyquinoline Polymers are studied and synthesized. INDRA K.VARMA of NASA Ames Research Center first synthesized bismaleimide 9,9-bis(4-maleimidophenyl)fluorene containing fluorenyl structure in 1982 ( See structural formula A), KUMAR ASHWANI of Canada applied for the European patent of bismaleimide in 2011. However, the monomer has a melting point of 340°C and solidifies after melting, and its solubility in most organic solvents is poor.

文献1（Journal of Applied Polymer Science,2008,107）报道了三种含酰亚胺键的链延长型芴基双马来酰亚胺单体，其溶解性得到了显著的改善，可溶于氯仿、二氯甲烷、四氢呋喃、N,N-二甲基甲酰胺等溶剂，但此类结构的双马来酰亚胺熔融温度仍较高，且熔融峰为一宽峰，在240-300℃之间，熔点和固化温度较为接近，使得熔融与固化协同发生，固化放热集中，造成熔融加工困难。而既含有高耐热氧化性芴环又含有可旋转芳醚连接键的双马来酰亚胺及其制备方法迄今为止尚未见有公开的专利或文献报道。 Document 1 (Journal of Applied Polymer Science, 2008, 107) reported three chain-extended fluorenyl bismaleimide monomers containing imide bonds, their solubility has been significantly improved, and they are soluble in chloroform , dichloromethane, tetrahydrofuran, N,N-dimethylformamide and other solvents, but the melting temperature of bismaleimide with this structure is still high, and the melting peak is a broad peak, which is between 240-300 ° C Between, the melting point and solidification temperature are relatively close, so that melting and solidification occur synergistically, and the exothermic heat of solidification is concentrated, making melting processing difficult. However, bismaleimides containing both high thermal oxidation resistance fluorene rings and rotatable aryl ether linkages and their preparation methods have not been published in patents or literature reports so far.

发明内容 Contents of the invention

本发明的目的之一在于提供一种溶解性良好、熔点低、固化放热平稳、且固化物耐热性能优良的含芴基及芳醚键结构的双马来酰亚胺。本发明的目的之二在于提供上述新型含芴基及芳醚键结构的双马来酰亚胺的制备方法。 One of the objectives of the present invention is to provide a bismaleimide having a fluorenyl group and an aryl ether bond structure with good solubility, low melting point, stable curing exotherm, and excellent heat resistance of the cured product. The second object of the present invention is to provide a method for preparing the above-mentioned novel bismaleimide containing fluorenyl and aryl ether bond structures.

本发明解决其技术问题采取的技术方案如下。 The technical scheme adopted by the present invention to solve its technical problems is as follows.

一种含芴基及芳醚键结构的双马来酰亚胺，其特征在于，具有如下结构式： A bismaleimide containing fluorenyl and aryl ether bond structure is characterized in that it has the following structural formula:

式中的取代基R₁、R₂各自独立地选自氢原子、卤素原子、硝基、C₁～C₂₀的脂肪族烷基或其衍生物、或者C₆～C₁₂的芳香烃烷基或其衍生物。 The substituents R ₁ and R ₂ in the formula are each independently selected from a hydrogen atom, a halogen atom, a nitro group, a C ₁ -C ₂₀ aliphatic alkyl group or its derivatives, or a C ₆ -C ₁₂ aromatic hydrocarbon alkyl group or its derivatives.

本发明涉及的含芴基及芳醚键结构的双马来酰亚胺的制备方法包括如下步骤： The preparation method of the bismaleimide containing fluorenyl and aryl ether bond structure that the present invention relates to comprises the steps:

（1）含芴基及芳醚键结构的芳香族二元胺与马来酸酐摩尔比1:2～2.3， 0～50℃下在极性非质子溶剂中反应4～10小时，过滤，滤饼经真空干燥得到含芴基及芳醚键结构的双马来酰亚胺酸，极性非质子溶剂的用量为1摩尔含芴基及芳醚键结构的芳香族二元胺使用极性非质子溶剂400～1000毫升； (1) The molar ratio of aromatic diamine containing fluorenyl group and aryl ether bond to maleic anhydride is 1:2~2.3, react in a polar aprotic solvent at 0~50°C for 4~10 hours, filter, filter The cake is vacuum-dried to obtain bismaleimide acid containing fluorenyl group and aryl ether bond structure, and the amount of polar aprotic solvent is 1 mole of aromatic diamine containing fluorenyl group and aryl ether bond structure. Protic solvent 400 ~ 1000 ml;

（2）上步生成的含芴基及芳醚键结构的双马来酰亚胺酸在脱水剂及催化剂的作用下，20～80℃下在极性非质子溶剂中反应5～10小时，反应液加水析出固体、过滤，滤饼经真空干燥得到含芴基及芳醚键结构的双马来酰亚胺，极性非质子溶剂的用量为1摩尔含芴基及芳醚键结构的双马来酰亚胺酸使用极性非质子溶剂500～2000毫升。 (2) The bismaleimide acid containing fluorenyl group and aryl ether bond structure generated in the previous step is reacted in a polar aprotic solvent at 20-80°C for 5-10 hours under the action of a dehydrating agent and a catalyst, Add water to the reaction solution to precipitate solids, filter, and vacuum-dry the filter cake to obtain bismaleimide containing fluorenyl and aryl ether bond structures. The amount of polar aprotic solvent is 1 mole of bismaleimide containing fluorenyl groups and aryl ether bond structures. Maleimide acid uses 500-2000 ml of polar aprotic solvent.

上述含芴基及芳醚键结构的双马来酰亚胺的合成路线如下： The synthetic route of the above-mentioned bismaleimide containing fluorenyl and aryl ether bond structure is as follows:

（1）、（2）中所述的极性非质子溶剂优选丙酮、N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、N-甲基吡咯烷酮、吡啶或四氢呋喃中的一种。 The polar aprotic solvents described in (1) and (2) are preferably acetone, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, pyridine or tetrahydrofuran A sort of.

（2）中所述的脱水剂优选乙酸酐，催化剂优选醋酸盐和／或三乙胺。 The dehydrating agent mentioned in (2) is preferably acetic anhydride, and the catalyst is preferably acetate and/or triethylamine.

所述的催化剂醋酸盐优选醋酸钠、醋酸镁和醋酸钴中的一种或两种以上的混合物。 The catalyst acetate is preferably one or a mixture of two or more of sodium acetate, magnesium acetate and cobalt acetate.

脱水剂乙酸酐的用量优选为含芴基及芳醚键结构的双马来酰亚胺酸摩尔数的3～8倍，催化剂三乙胺的用量优选为含芴基及芳醚键结构的双马来酰亚胺酸摩尔数的0.5～5倍，催化剂醋酸盐的用量优选为1摩尔含芴基及芳醚键结构的双马来酰亚胺酸使用0.5～5g。 The amount of dehydrating agent acetic anhydride is preferably 3 to 8 times the number of moles of bismaleimide acid containing fluorenyl and aryl ether bond structure, and the amount of catalyst triethylamine is preferably 3 to 8 times the molar amount of bismaleimide acid containing fluorenyl and aryl ether bond structure. 0.5-5 times the number of moles of maleimide acid, and the dosage of catalyst acetate is preferably 0.5-5 g for 1 mole of bismaleimide acid containing fluorenyl group and aryl ether bond structure.

本发明的有益效果是：本发明所述的双马来酰亚胺是一类含芴基及芳醚键结构的双马来酰亚胺，其主要结构为稠环结构可保持良好的耐热性，另外由于分子结构中引入了芳醚键，使得分子链具有一定的柔顺性，使其溶解性增加、熔点降低，拓宽了其熔融加工窗口。 The beneficial effects of the present invention are: the bismaleimide described in the present invention is a kind of bismaleimide containing fluorenyl and aryl ether bond structure, and its main structure is fused ring structure, which can maintain good heat resistance In addition, due to the introduction of aryl ether bonds in the molecular structure, the molecular chain has a certain degree of flexibility, which increases its solubility and lowers its melting point, which broadens its melt processing window.

附图说明 Description of drawings

图1是本发明实施例19,9-双[4-(4-马来酰亚胺基苯氧基)苯基]芴的红外光谱。 Figure 1 is the infrared spectrum of Example 19,9-bis[4-(4-maleimidophenoxy)phenyl]fluorene of the present invention.

图2是本发明实施例19,9-双[4-(4-马来酰亚胺基苯氧基)苯基]芴的H核磁光谱。 Fig. 2 is the H NMR spectrum of Example 19,9-bis[4-(4-maleimidophenoxy)phenyl]fluorene of the present invention.

图3是本发明实施例29,9-双[4-(4-马来酰亚胺基苯氧基)-3-甲基苯基]芴的红外光谱。 Fig. 3 is the infrared spectrum of Example 29,9-bis[4-(4-maleimidophenoxy)-3-methylphenyl]fluorene of the present invention.

图4是本发明实施例29,9-双[4-(4-马来酰亚胺基苯氧基)-3-甲基苯基]芴的H核磁光谱。 Fig. 4 is the H NMR spectrum of Example 29,9-bis[4-(4-maleimidophenoxy)-3-methylphenyl]fluorene of the present invention.

图5是本发明实施例1的热失重图。 Fig. 5 is the thermal weight loss diagram of Example 1 of the present invention.

图6是本发明实施例2的热失重图。 Fig. 6 is a thermogravimetric diagram of Example 2 of the present invention.

具体实施方式 Detailed ways

下面结合具体实施例进一步阐述本发明，但其目的在于更好地理解本发明，而非限制本发明的保护范围。 The present invention will be further described below in conjunction with specific examples, but the purpose is to better understand the present invention, rather than limit the protection scope of the present invention.

实施例1：9,9-双[4-(4-马来酰亚胺基苯氧基)苯基]芴 Example 1: 9,9-bis[4-(4-maleimidophenoxy)phenyl]fluorene

（1）将马来酸酐（0.21mol）溶于20ml丙酮中，搅拌溶解。将含芴基及芳醚键结构的芳香族二元胺I（0.1mol）溶于80ml丙酮中，缓慢滴加入马来酸酐的丙酮溶液中，室温下反应8小时。反应结束后，将生成的黄色固体过滤，滤饼经真空干燥得到含芴基及芳醚键结构的双马来酰亚胺酸II，产率92.7%，HPLC测定纯度为99.5%。FT-IR（KBr，cm^-1）：3288，1543（-NH），1712（-C=O）。 (1) Dissolve maleic anhydride (0.21mol) in 20ml acetone and stir to dissolve. Dissolve aromatic diamine I (0.1mol) containing fluorenyl group and aryl ether bond structure in 80ml of acetone, slowly drop into the acetone solution of maleic anhydride, and react at room temperature for 8 hours. After the reaction, the resulting yellow solid was filtered, and the filter cake was vacuum-dried to obtain bismaleimide acid II containing a fluorenyl group and an aryl ether bond structure, with a yield of 92.7% and a purity of 99.5% as determined by HPLC. FT-IR (KBr, cm ^-1 ): 3288, 1543 (-NH), 1712 (-C=O).

（2）将上步生成的双马来酰亚胺酸II（0.1mol）悬浮在200ml丙酮中，加入0.15g醋酸钠，加热到50℃，滴加18ml三乙胺和40ml乙酸酐，待反应液变成均相后恒温反应10小时。反应结束后将反应液缓慢滴加入水中，将生成的晶体过滤，真空干燥，得到黄色的9,9-双[4-(4-马来酰亚胺基苯氧基)苯基]芴III，产率88%，熔点：129.2℃。FT-IR（KBr，cm^-1）：[见图1]3089（-C=CH），1717（C=O），1395，1148（C-N-C）。¹HNMR（400MHz，CDCl₃）：[见图2]δ7.77（2H，d，ArH），7.41（2H，t，ArH），7.36（2H，d，ArH），7.30（2H，t，ArH），7.26（4H，d，ArH），7.18（4H，d，ArH），7.04（4H，t，ArH），6.89（4H，d，ArH），6.82（4H，s，-C=CH）。TG（热失重）：[见图5]。溶解性实验：[见表1]。 (2) Suspend bismaleimide acid II (0.1mol) generated in the previous step in 200ml of acetone, add 0.15g of sodium acetate, heat to 50°C, add dropwise 18ml of triethylamine and 40ml of acetic anhydride, and wait for the reaction After the solution became homogeneous, it was reacted at constant temperature for 10 hours. After the reaction, the reaction solution was slowly added dropwise to water, the resulting crystals were filtered and dried in vacuo to obtain yellow 9,9-bis[4-(4-maleimidophenoxy)phenyl]fluorene III, Yield 88%, melting point: 129.2°C. FT-IR (KBr, cm ^-1 ): [See Figure 1] 3089 (-C=CH), 1717 (C=O), 1395, 1148 (CNC). ¹ HNMR (400MHz, CDCl ₃ ): [See Figure 2] δ7.77 (2H, d, ArH), 7.41 (2H, t, ArH), 7.36 (2H, d, ArH), 7.30 (2H, t, ArH ), 7.26 (4H, d, ArH), 7.18 (4H, d, ArH), 7.04 (4H, t, ArH), 6.89 (4H, d, ArH), 6.82 (4H, s, -C=CH). TG (Thermogravimetric): [See Figure 5]. Solubility test: [see Table 1].

实施例2：9,9-双[4-(4-马来酰亚胺基苯氧基)-3-甲基苯基]芴 Example 2: 9,9-bis[4-(4-maleimidophenoxy)-3-methylphenyl]fluorene

（1）将马来酸酐（0.21mol）溶于20ml丙酮中，搅拌溶解。将含甲基芴及芳醚键结构的芳香族二元胺I’（0.1mol）溶于80ml丙酮中，缓慢滴加入马来酸酐的丙酮溶液中，室温下反应8小时。反应结束后，将生成的黄色固体过滤，滤饼经真空干燥得到含甲基芴及芳醚键结构的双马来酰亚胺酸II’，产率91.2%，HPLC测定纯度为99.5%。FT-IR（KBr，cm^-1）：3282，1550（-NH），2958，2916（-CH₃），1707（-C=O）。 (1) Dissolve maleic anhydride (0.21mol) in 20ml acetone and stir to dissolve. Dissolve aromatic diamine I' (0.1mol) containing methylfluorene and aryl ether bond structure in 80ml of acetone, slowly add dropwise to the acetone solution of maleic anhydride, and react at room temperature for 8 hours. After the reaction, the resulting yellow solid was filtered, and the filter cake was vacuum-dried to obtain bismaleimide acid II' containing methylfluorene and aryl ether bond structure, with a yield of 91.2% and a purity of 99.5% as determined by HPLC. FT-IR (KBr, cm ^-1 ): 3282, 1550 (-NH), 2958, 2916 (-CH ₃ ), 1707 (-C=O).

（2）将上步生成的双马来酰亚胺酸II’（0.1mol）悬浮在200ml丙酮中，加入0.15g醋酸钠，加热到50℃，滴加18ml三乙胺和40ml乙酸酐，待反应液变成均相后恒温反应10小时。反应结束后将反应液缓慢滴加入水中，将生成的晶体过滤，真空干燥，得到黄色的9,9-双[4-(4-马来酰亚胺基苯氧基)-3-甲基苯基]芴III’，产率85%，熔点：126.0℃。FT-IR（KBr，cm^-1）：[见图3]3105（-C=CH），2924，2856（-CH₃），1716（C=O），1394，1151（C-N-C）。¹HNMR（400MHz，CDCl₃）：[见图4]δ7.78（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，-CH₃）。TG（热失重）：[见图6]。溶解性实验：[见表1]。 (2) Suspend the bismaleimide acid II' (0.1mol) generated in the previous step in 200ml of acetone, add 0.15g of sodium acetate, heat to 50°C, add dropwise 18ml of triethylamine and 40ml of acetic anhydride, and wait After the reaction liquid became homogeneous, it was reacted at constant temperature for 10 hours. After the reaction, the reaction solution was slowly added dropwise to water, the resulting crystals were filtered and dried in vacuum to obtain yellow 9,9-bis[4-(4-maleimidophenoxy)-3-methylbenzene Base] fluorene III', yield 85%, melting point: 126.0°C. FT-IR (KBr, cm ^-1 ): [See Figure 3] 3105 (-C=CH), 2924, 2856 (-CH ₃ ), 1716 (C=O), 1394, 1151 (CNC). ¹ HNMR (400MHz, CDCl ₃ ): [See Figure 4] δ7.78 (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, _-CH3 ). TG (Thermogravimetric): [See Figure 6]. Solubility test: [see Table 1].

表1.含芴基及芳醚键结构的双马来酰亚胺单体的溶解性 Table 1. Solubility of bismaleimide monomers containing fluorenyl and aryl ether bond structures

-：不溶；++：易溶。 -: insoluble; ++: easily soluble.

Claims (6)

1.一种含芴基及芳醚键结构的双马来酰亚胺，其特征在于，具有如下结构式：1. a bismaleimide containing fluorenyl and aryl ether bond structure, is characterized in that, has following structural formula: 2.制备权利要求1所述的含芴基及芳醚键结构的双马来酰亚胺的方法，其特征在于，包括如下步骤：2. prepare the method for the bismaleimide containing fluorenyl and aryl ether bond structure of claim 1, is characterized in that, comprises the steps: (1)含芴基及芳醚键结构的芳香族二元胺与马来酸酐摩尔比1:2～2.3，0～50℃下在极性非质子溶剂中反应4～10小时，过滤，滤饼经真空干燥得到含芴基及芳醚键结构的双马来酰亚胺酸，极性非质子溶剂的用量为1摩尔含芴基及芳醚键结构的芳香族二元胺使用极性非质子溶剂400～1000毫升；(1) The molar ratio of aromatic diamine containing fluorenyl group and aryl ether bond to maleic anhydride is 1:2~2.3, react in a polar aprotic solvent at 0~50°C for 4~10 hours, filter, filter The cake is vacuum-dried to obtain bismaleimide acid containing fluorenyl group and aryl ether bond structure, and the amount of polar aprotic solvent is 1 mole of aromatic diamine containing fluorenyl group and aryl ether bond structure. Protic solvent 400 ~ 1000 ml; (2)上步生成的含芴基及芳醚键结构的双马来酰亚胺酸在脱水剂及催化剂的作用下，20～80℃下在极性非质子溶剂中反应5～10小时，反应液加水析出固体、过滤，滤饼经真空干燥得到含芴基及芳醚键结构的双马来酰亚胺，极性非质子溶剂的用量为1摩尔含芴基及芳醚键结构的双马来酰亚胺酸使用极性非质子溶剂500～2000毫升。(2) The bismaleimide acid containing fluorenyl group and aryl ether bond structure generated in the previous step is reacted in a polar aprotic solvent at 20-80°C for 5-10 hours under the action of a dehydrating agent and a catalyst, Add water to the reaction solution to precipitate solids, filter, and vacuum-dry the filter cake to obtain bismaleimide containing fluorenyl and aryl ether bond structures. The amount of polar aprotic solvent is 1 mole of bismaleimide containing fluorenyl groups and aryl ether bond structures. Maleimide acid uses 500-2000 ml of polar aprotic solvent. 3.根据权利要求2所述的制备方法，其特征在于，(1)、(2)中所述的极性非质子溶剂为丙酮、N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、N-甲基吡咯烷酮、吡啶或四氢呋喃中的一种。3. the preparation method according to claim 2 is characterized in that, the polar aprotic solvent described in (1), (2) is acetone, N,N-dimethylformamide, N,N-dimethylformamide One of methylacetamide, N-methylpyrrolidone, pyridine or tetrahydrofuran. 4.根据权利要求2所述的制备方法，其特征在于，(2)中所述的脱水剂为乙酸酐，催化剂为醋酸盐和/或三乙胺。4. preparation method according to claim 2 is characterized in that, the dehydrating agent described in (2) is acetic anhydride, and catalyzer is acetate and/or triethylamine. 5.根据权利要求4所述的制备方法，其特征在于，所述的催化剂醋酸盐为醋酸钠、醋酸镁和醋酸钴中的一种或两种以上的混合物。5. preparation method according to claim 4 is characterized in that, described catalyst acetate is the mixture of one or more in sodium acetate, magnesium acetate and cobalt acetate. 6.根据权利要求4所述的制备方法，其特征在于，脱水剂乙酸酐的用量为含芴基及芳醚键结构的双马来酰亚胺酸摩尔数的3～8倍，催化剂三乙胺的用量为含芴基及芳醚键结构的双马来酰亚胺酸摩尔数的0.5～5倍，催化剂醋酸盐的用量为1摩尔含芴基及芳醚键结构的双马来酰亚胺酸使用0.5～5g。6. preparation method according to claim 4 is characterized in that, the consumption of dehydrating agent acetic anhydride is 3～8 times of the bismaleimide acid mole number that contains fluorenyl and aryl ether bond structure, catalyst triethyl The amount of amine used is 0.5 to 5 times the number of moles of bismaleimide acid containing fluorenyl and aryl ether bond structure, and the amount of catalyst acetate used is 1 mole of bismaleimide acid containing fluorenyl group and aryl ether bond structure. Use 0.5-5g of imidic acid.

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