Fabrication and characterization of a novel bismaleimide-benzoxazine resin

doi:10.11949/j.issn.0438-1157.20151496

Abstract

Abstract:

A novel bismaleimide-benzoxazine resin(abbreviated as HPM-BOZ)was synthesized by three steps. Firstly, N-p-hydroxylphenylmaleimide(HPM)was prepared from maleic anhydride and p-aminophenol. Secondly, HPM, 4,4-2 amino diphenyl ether (ODA) and paraformaldehyde were used as raw materials to prepare HPM-BOZ with Mannich reaction. Thirdly, a novel bismaleimide-benzoxazine resin was fabricated by a specific curing process. The chemical structure of HPM and HPM-BOZ was characterized by FTIR, ¹H NMR and ¹³C NMR. Section fracture surface of the resin was analyzed by SEM. The curing behavior of HPM-BOZ was characterized by DSC with two peaks at about 235℃ and 266℃ appeared during its curing, respectively. TGA curves demonstrated that HPM-BOZ had excellent thermal stabilities under the condition of nitrogen, which began to decompose at 410℃ with 5% mass loss temperature of 438℃ and obtained 60.2% char yield at 800℃.

Key words: maleimide, benzoxazine, synthesis, NMR, thermal stability, thermosetting resin

摘要：

首先用马来酸酐、对氨基苯酚为原料合成N-对羟基苯基马来酰亚胺(HPM),然后用合成的HPM、4,4-二氨基二苯醚(ODA)和多聚甲醛为原料进行曼尼希反应合成出含双马来酰亚胺的苯并噁嗪(HPM-BOZ),经高温固化后形成热固性树脂。用FTIR、¹H NMR、¹³C NMR分析了HPM和HPM-BOZ的化学结构,证实了所得的为目标产物;用DSC对HPM-BOZ的固化特性进行研究,用TGA分析了HPM-BOZ的固化物的热稳定性;用SEM分析了树脂的断裂面。结果表明:HPM-BOZ在235℃和266℃出现了两个固化峰;在氮气条件下,热分解温度为410℃,失重5%的温度为438℃,在800℃的残碳率为60.2%。

关键词: 马来酰亚胺, 苯并噁嗪, 合成, 核磁共振, 热稳定性, 热固性树脂

CLC Number:

O631

YUAN Wei, SHI Tiejun, XU Guomei, LI Ming, LIU Jianhua. Fabrication and characterization of a novel bismaleimide-benzoxazine resin[J]. CIESC Journal, 2016, 67(5): 2131-2137.

袁伟, 史铁钧, 徐国梅, 李明, 刘建华. 含双马来酰亚胺的新型双苯并噁嗪的合成及性能[J]. 化工学报, 2016, 67(5): 2131-2137.

References 20

[1]	LIN J, TAREK A, HATSUO I. Bis(benzoxazine-maleimide)s as a novel class of high performance resin: synthesis and properties [J]. Eur. Polym. J., 2010, 46: 354-363.
[2]	GRISHCHUK S, MBHELE Z, SCHMITT S, et al. Structure, thermal and fracture mechanical properties of benzoxazine-modified amine-cured DGEBA epoxy resins [J]. Express Polymer Letters, 2011, 5 (3): 273-282.
[3]	刘建华, 史铁钧. 含双DOPO的双酚A-双苯并噁嗪合成、表征及其固化特性 [J]. 化工学报, 2014, 65 (11): 4607-4613. LIU J H, SHI T J. Synthesis, characterization and curing characteristics of double benzoxazine contained double DOPO based on bisphenol A [J]. CIESC Journal, 2014, 65 (11): 4607-4613.
[4]	LUONG N D, HIPPI U, SOININEN A J, et al. Enhanced mechanical and electrical properties of polyimide film by grapheme sheets via in situ polymerization [J]. Polymer, 2011, 52: 5237-5242.
[5]	SHARMA G R, LIND C, MARIA, R, et al. Preparation and properties of polyimide nanocomposites with negative thermal expansion nanoparticle filler [J]. Materials Chemistry and Physics, 2012, 137: 448-457.
[6]	HSIAO S H, LIN K H. Polyimides derived from novel asymmetric ether diamine [J]. Journal of Polymer Science, 2005, 43: 331-341.
[7]	TAREK A, CARLOS R A, Frans H. Primary amine-functional benzoxazine monomers and their use for amide-containing monomeric benzoxazines [J]. Macromalecules, 2010, 43: 2748-2758.
[8]	CHEN N H, LI H Y, LAI J Y, et al. Synthesis and characterization of benzoxazine-containing, crosslinkable, and sulfonated polymer through Dielse-Alder reaction for direct methanol fuel cells [J]. Polymer, 2013, 54: 2096-2014.
[9]	LIU Y L, CHEN Y G. Novel thermosetting resins based on 4-(N-maleimidophenyl) glycidylether. Preparation and characterization of monomer and cured resins [J]. Polymer, 2003, 44: 6465-6473.
[10]	KE L, HU D, LU Y, et al. Copolymerization of maleimide-based benzoxazine with styrene and the curing kinetics of the resultant copolymer [J]. Polymer Degradation and Stability, 2012, 97: 132-138.
[11]	ISHIDA H, OHBBA S. Synthesis and characterization of maleimide and norbornene functionalized benzoxazines [J]. Polymer, 2005, 46: 5588-5595.
[12]	TAKEICHI T, KAWAUCHI T, AGAG T. High performance polybenzoxazines as a novel type of phenolic resin [J]. Polymer Journal, 2008, 40: 1121-1131.
[13]	TAREK A, TSUTOMU T. Preparation, characterization, and polymerization of maleimidobenzoxazine monomers as a novel class of thermosetting resins [J]. Journal of Polymer Science, 2006, 44: 1424-1435.
[14]	SUN J X, SHI T J, XU H, et al. Synthesis, structure and thermal properties of bisphenol fluorene diamine benzoxazine [J]. Chemical Journal of Chinese Universities, 2011, 32: 1216-1220.
[15]	JIN L, AGAG T, ISHIDA H. Bis(benzoxazine-maleimide)s as a novel class of high performance resin: synthesis and properties [J]. European Polymer Journal, 2010, 46: 354-363.
[16]	TAKEICHI T, AGAG T. High performance polybenzoxazines as novel thermosets [J]. High Performance Polymers, 2006, 18: 777-797.
[17]	KUMAR K, NAIR C, SADHANA R, et al. Benzoxazine-bismaleimide blends: curing and thermal properties [J]. European Polymer Journal, 2007, 43: 5084-5096.
[18]	TAKEICHI T, SAITO Y, AHAH T, et al. High-performance polymer alloys of polybenzoxazine and bismaleimide [J]. Polymer, 2008, 49: 1173-1179.
[19]	ARDTANANTA H, WAHID M H, SASAKI M, et al. Performance enhancement of polybenzoxazine by hybridization with polysiloxane [J]. Polymer, 2008, 49: 4585-4591.
[20]	LEVENTIS N, CHARIKIA S L, DHAIRYASHIL P, et al. Polyimide aerogels by ring-opening metathesis polymerization (ROMP) [J]. Chemistry of Materials, 2011, 23: 2250-2261.