利用呋喃/马来酰亚胺Diels-Alder反应实现聚甲基丙烯酸丁酯/聚苯乙烯合金相容

doi:10.11944/j.issn.1000-0518.2019.04.180300

摘要/Abstract

摘要：

利用呋喃和马来酰亚胺之间的可逆Diels-Alder反应,对不相容的聚甲基丙烯酸正丁酯(Poly(n-butyl methacrylate),PBMA)/聚苯乙烯(Polystyrene,PS)合金进行了增容研究。首先,通过原子转移自由基聚合(ATRP)共聚合成侧基含呋喃基团的聚甲基丙烯酸正丁酯(P(BMA-co-FMA)),并通过后反应改性合成侧基含马来酰亚胺基团的聚苯乙烯(MPS),然后利用呋喃和马来酰亚胺基团之间的Diels-Alder反应促使该共混物中两种高分子的相容性得到明显改善,本实验通过核磁共振波谱仪(NMR)表征验证了功能化高分子及其共混物中的Diels-Alder反应,并通过透射电子显微镜观测相分离结构变化和差示扫描量热法测定相变温度证明了相容性的明显改善。共混物可以进行热塑性加工,且其相形态和力学性能可以通过控制反应时间予以调节,三点弯曲试验发现随着反应时间的延长共混物逐渐由韧性材料向脆性材料转变。

关键词: 聚甲基丙烯酸正丁酯, 聚苯乙烯, 高分子合金, 增容, Diels-Alder反应, 呋喃/马来酰亚胺

Abstract:

The compatibilization of immiscible poly(n-butyl methacrylate)(PBMA)/polystyrene(PS) blends was realized by the reaction of furan and maleimide groups. The furan-functionalized poly(n-butyl methacrylate)(P(BMA-co-FMA)) and maleimide-functionalized polystyrene(MPS) was synthesized by copolymerization and post-polymerization modification, respectively. The Diels-Alder reaction of the functionalized polymers and their blend were confirmed by nuclear magnetic resonance spectroscopy(NMR). The reaction of furan and maleimide dramatically promoted the compatibility of two components, confirmed by a homogeneous microstructure evidenced by transmission electron microscopy(TEM) observation and by the presence of a single glass transition temperature in the (P(BMA-co-FMA)/MPS blends. The properties of the blend materials could be controlled conveniently by adjusting the reaction time, and the blends transformed from tough material to brittle material gradually as the reaction processed, which was confirmed by the three point bending test.

Key words: poly(butyl methacrylate, polystyrene, polymer blend, compatibilization, diels-Alder reaction, furan/maleimide

叶霖, 张少锋, 闵嘉康, 马丽, 唐涛. 利用呋喃/马来酰亚胺Diels-Alder反应实现聚甲基丙烯酸丁酯/聚苯乙烯合金相容[J]. 应用化学, 2019, 36(4): 451-458.

YE Lin, ZHANG Shaofeng, MIN Jiakang, MA Li, TANG Tao. Poly(n-butyl methacrylate)/Polystyrene Blend Compatibilized by the Diels-Alder Reaction of Furan/Maleimide[J]. Chinese Journal of Applied Chemistry, 2019, 36(4): 451-458.

参考文献

[1]	Lipatov Y S.Polymer Blends and Interpenetrating Polymer Networks at the Interface with Solids[J]. Prog Polym Sci,2002,27(9):1721-1801.
[2]	Plate N,Litmanovich A,Kudryavtsev Y V.Reactions in Polymer Blends:Experiment and Theory(A Review)[J]. Polym Sci,Ser A,2004,46(11):1834-1874.
[3]	Ao Y H,Sun S L,Tan Z Y,et al. Compatibilization of PP/EPDM Blends by Grafting Acrylic Acid to Polypropylene and Epoxidizing the Diene in EPDM[J]. J Appl Polym Sci,2006,102(4):3949-3954.
[4]	Tang T,Huang B T.Interfacial Behaviour of Compatibilizers in Polymer Blends[J]. Polymer,1994,35(2):81-285.
[5]	Jiang M,Li M,Xiang M L,et al. Interpolymer Complexation and Miscibility Enhancement by Hydrogen Bonding[M]. Berlin:Springer-Verlag Berlin Heidelberg,1999:121-196.
[6]	Liu N C,Huang H.Types of Reactive Polymers Used in Blending[M]. Cincinati:Hanser Gardner Publications,Inc,2001:13-42.
[7]	Park T,Zimmerman S C.Interplay of Fidelity, Binding Strength, and Structure in Supramolecular Polymers[J]. J Am Chem Soc,2006,128(44):14236-14237.
[8]	Dionisio M,Ricci L,Pecchini G,et al. Polymer Blending through Host-Guest Interactions[J]. Macromolecules,2014,47(2): 632-638.
[9]	Shen J,Piunova V A,Nutt S,et al. Blends of Polystyrene and Poly(n-butyl methacrylate) Mediated by Perfluorocarbon End Groups[J]. Polymer,2013,54(21):5790-5800.
[10]	Tawney P O,Snyder R H,Bryan C E,et al. The Chemistry of Maleimide and Its Derivatives.I.N-Carbamylmaleimide[J]. J Org Chem,1960,25(1):56-60.
[11]	Tawney P O,Snyder R H,Conger R P,et al. The Chemistry of Maleimide and Its Derivatives.II.Maleimide and N-Methylolmaleimide[J]. J Org Chem,1961,26(1):15-21.
[12]	Stevens M P,Jenkins A D.Crosslinking of Polystyrene via Pendant Maleimide Groups[J]. J Polym Sci,Polym Chem Ed,1979,17(11):3675-3685.
[13]	Gandini A.The Furan/Maleimide Diels-Alder Reaction:A Versatile Click Unclick Tool in Macromolecular Synthesis[J]. Prog Polym Sci,2013,38(1):1-29.

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