微波驱动咪唑类聚离子液体/聚乙烯醇形状记忆材料

doi:10.11949/j.issn.0438-1157.20171539

摘要/Abstract

摘要：

结合微波驱动原理、聚离子液体（PIL）及形状记忆聚合物的结构特性，目的是设计合成完全基于聚合物、能在微波驱动下快速回复的聚离子液体/聚乙烯醇（PVA）形状记忆复合材料。首先合成了乙烯基咪唑功能性离子液体单体（[ViEtIm][BF₄]，ILM），之后在含有戊二醛的PVA溶液中对ILM进行原位聚合生成PIL，将PIL引入到交联PVA中，形成聚乙烯基咪唑PIL/PVA形状聚合物复合材料（SMPC）。用核磁对ILM和PIL的结构进行了表征，证明了所合成目标化合物的结构准确性。介电性能测试结果显示PIL/PVA有较高的介电常数和介电损耗，当P[ViEtIm][BF₄]含量从0增加到30%时PIL/PVA复合材料的介电损耗因子呈增大趋势，可见PIL是一种有效的微波吸收介质。弯曲法测试结果表明该复合材料在微波驱动下具有很好的形状记忆效应，所有复合材料的形变固定率都接近100%且形变回复率都高达80%以上，且PIL的含量和微波输出功率的大小对材料回复率和回复时间有显著影响。140 W的微波足以驱动PIL/PVA SMPC发生回复，280 W下40 s内可以完成，微波功率增大到420 W时SMPC在20 s内可回复到起始形状。

关键词: 形状记忆, 微波驱动, 聚合物, 离子液体, 复合材料

Abstract:

The present work combines the microwave mechanism, the structure characteristic of poly(ionic liquids) and shape memory polymers to design and synthesize microwave induced shape memory polymer composites (SMPC) completely based on polymers. Ionic liquid (IL) monomer ethylene imidazole was synthesized initially, and then ILM was polymerized in poly(vinyl alcohol)/glutaric dialdehyde solution by using in suit polymerization to introduce PIL into PVA matrix, obtaining the PIL/PVA shape memory polymer composites (SMPC). ¹H NMR was used to characterize the structure of ILM and PIL to prove the structural accuracy of the targeted compounds. Dielectric performance test results show PIL/PVA samples have high dielectric constant and dielectric loss. The dielectric loss factor of PIL/PVA composites gradually increase when the P[ViEtIm] [BF₄] content increases from 0 to 30%, indicating PIL is one effective microwave absorption medium. The bending test results show the composites have good shape memory effect under microwave irradiation. For all samples, the shape fixity ratio nearly gets 100%, and the shape recovery ratio could over 80%. Moreover, the PIL content and the microwave output power have obvious effects on the shape recovery and recovery time. 140 W output power is enough to drive PIL/PVA to recover to its original shape, and the shape recovery could finish within 40 s under 280 W irradiation. When the output power increases to 420 W, SMPC could recover to its original shape within 20 s.

Key words: shape memory, microwave induced, polymers, ionic liquid, composite

中图分类号:

杜海燕, 许玉玉, 任哲, 杨慧敏. 微波驱动咪唑类聚离子液体/聚乙烯醇形状记忆材料[J]. 化工学报, 2018, 69(7): 3279-3285.

DU Haiyan, XU Yuyu, REN Zhe, YANG Huimin. Microwave-induced imidazole poly(ionic liquid)/poly(vinyl alcohol) shape memory materials[J]. CIESC Journal, 2018, 69(7): 3279-3285.

参考文献 31

[1]	LIU T, ZHOU T, YAO Y, et al. Stimulus methods of multi-functional shape memory polymer nanocomposites:a review[J]. Composites:Part A, 2017, 100:20-30.
[2]	HAGER M D, BODE S, WEBER C, et al. Shape memory polymers:past, present and future developments[J]. Prog. Polym. Sci., 2015, 49:3-33.
[3]	ZHANG Z, QI X, LI S, et al. Water-actuated shape-memory and mechanically-adaptive poly(ethylenevinyl acetate) achieved by adding hydrophilic poly (vinyl alcohol)[J]. Eur. Polym. J., 2018, 98:237-245.
[4]	BROWN R, SINGH K V, KHAN F. Fabrication and vibration characterization of electrically triggered shape memory polymer beams[J]. Polymer Testing, 2017, 61:74-82.
[5]	BABAAHMADI M, SABZI M, MAHDAVINIA G R, et al. Preparation of amorphous nanocomposites with quick heat triggered shape memory behavior[J]. Polymer, 2017, 112:26-34.
[6]	BERG G J, MCBRIDE M K, WANG C, et al. New directions in the chemistry of shape memory polymers[J]. Polymer, 2014, 55(23):5849-5872.
[7]	MA Y, YI G, WANG J, et al. Shape-controllable and -tailorable multiwalled carbon nanotube/MnO2/shape-memory polyurethane composite film for supercapacitor[J]. Synthetic Met., 2017, 223:67-72.
[8]	XIE Z J, SEBALD G, GUYOMAR D. Temperature dependence of the elastocaloric effect in natural rubber[J]. Physics Letters A, 2017, 381(25/26):2112-2116.
[9]	LENG J S, WU X L, LIU Y J. Infrared light-active shape memory polymer filled with nanocarbon particles[J]. J. Appl. Polym. Sci., 2009, 114(4):2455-2460.
[10]	KOERNER H, PRICE G, PEARCE N A, et al. Remotely actuated polymer nanocomposites-stress-recovery of carbon-nanotube-filled thermoplastic elastomers[J]. Nat. Mater., 2004, 3(2):115-120.
[11]	魏堃, 朱光明, 唐玉生. 电致型形状记忆聚合物复合材料的研究进展[J]. 材料导报, 2011, 25(7):9-12. WEI K, ZHU G M, TANG Y S. Research progress in electro-induced shape memory polymer composites[J]. Mater. Rev., 2011, 25(7):9-12.
[12]	MOHR R, KRATZ K, WEIGEL T, et al. Initiation of shape-memory effect by inductive heating of magnetic nanoparticles in thermoplastic polymers[J]. Proceeding of the National Academy of Sciences of the United States of America, 2006, 103(10):3540-3545.
[13]	LI G, YAN Q, XIA H S, et al. Therapeutic-ultrasound-triggered shape memory of a melamine-enhanced poly(vinyl alcohol) physical hydrogel[J]. ACS Appl. Mater. Interfaces, 2015, 7(22):12067-12073.
[14]	HE Z W, SATARKAR N, XIE T, et al. Remote controlled multishape polymer nanocomposites with selective radio frequency actuations[J]. Adv. Mater., 2011, 23(28):3192-3196.
[15]	YU K, LIU Y J, LENG J S. Shape memory polymer/CNT composites and their microwave induced shape memory behaviors[J]. RSC Adv., 2014, 4(6):2961-2968.
[16]	ZHANG F H, ZHOU T Y, LIU Y J, et al. Microwave synthesis and actuation of shape memory polycaprolactone foams with high speed[J]. Sci. Rep., 2015, 5:11152-11164.
[17]	MALLAKPOUR S, RAFIEE Z. New developments in polymer science and technology using combination of ionic liquids and microwave irradiation[J]. Prog. Polym. Sci., 2011, 36(12):1754-1765.
[18]	KEMPE K, BECER C R, SCHUBERT U S. Microwave-assisted polymerizations:recent status and future perspectives[J]. Macromolecules, 2011, 44(15):5825-5842.
[19]	张恒, 周志彬, 聂进. 离子液体聚合物的研究进展[J]. 化学进展, 2013, 25(5):761-774. ZHANG H, ZHOU Z B, NIE J. Recent advances of polymeric ionic liquids[J]. Prog. Chem., 2013, 25(5):761-774.
[20]	TANG J B, TANG H D, SUN W L, et al. Poly(ionic liquid)s as new materials for CO2 absorption[J]. Journal of Polymer Science:Part A:Polymer Chemistry, 2005, 43:5477-5489.
[21]	SUSAN M A, KANEKO T, NODA A, et al. Ion gels prepared by in situ radical polymerization of vinyl monomers in an ionic liquid and their characterization as polymer electrolytes[J]. J. Am. Chem. Soc., 2005, 127(13):4976-4983.
[22]	BREGAR V B. Advantages of ferromagnetic nanoparticle composites in microwave absorbers[J]. Trans. Magn., 2004, 40:1679-1684.
[23]	TANG J B, RADOSZ M, SHEN Y Q. Poly(ionic liquid)s as optically transparent microwave-absorbing materials[J]. Macromolecules, 2008, 41(2):493-496.
[24]	MECERREYES D. Polymeric ionic liquids:broadening the properties and applications of polyelectrolytes[J]. Prog. Polym. Sci., 2011, 36(12):1629-1648.
[25]	LEE S, BECHT G A, LEE B, et al. Electropolymerization of a bifunctional ionic liquid monomer yields as electroactive liquidcrystalline polymer[J]. Adv. Funct. Mater., 2010, 20(13):2063-2070.
[26]	OHKI T, NI Q Q, OHSAKO N, et al. Mechanical and shape memory behavior of composites with shape memory polymer[J]. Compos. Part A, 2004, 35(9):1065-1073.
[27]	DU H Y, ZHOU T, ZHANG J H, et al. Moving-window twodimensional correlation infrared spectroscopy study on structural variations of partially hydrolyzed poly(vinyl alcohol)[J]. Anal. Bioanal. Chem., 2010, 397(7):3127-3132.
[28]	MALLAKPOUR S, RAFIEE Z. New developments in polymer science and technology using combination of ionic liquids and microwave irradiation[J]. Prog. Polym. Sci., 2011, 36(12):1754-1765.
[29]	MICHEL A, FRANK E, DOUGLAS R. Ionic-liquid materials for the electrochemical challenges of the future[J]. Nature Material, 2009, 8:621-629.
[30]	NAKAMURA K, FUKAO K, INOUE T. Dielectric relaxation and viscoelastic behavior of polymerized ionic liquids with various counteranions[J]. Macromolecules, 2012, 45(9):3850-3858.
[31]	GUO M, HAYAKAWA T, KAKIMOTO M, et al. Organic macromolecular high dielectric constant materials:synthesis, characterization, and applications[J]. J. Phys. Chem. B, 2011, 115(46):13419-13432.