聚甲基丙烯酸甲酯/星形聚乙二醇半互穿聚合物网络的形状记忆性能和分子机理

doi:10.7503/cjcu20160202

摘要/Abstract

摘要：

采用非共价复合方法, 设计并合成了具有星形结构的聚甲基丙烯酸甲酯/星形聚乙二醇半互穿聚合物网络(PMMA/SPEG)和聚甲基丙烯酸甲酯/线性聚乙二醇半互穿聚合物网络(PMMA/LPEG). 研究了PEG分子量对PMMA/SPEG和PMMA/LPEG的热性能、机械性能、动态机械性能和形状记忆性能的影响. 结果表明, 与PMMA/LPEG相比, 星形结构的嵌入显著提高了PMMA/SPEG复合物的机械性能、形状回复率和回复速度. 采用Edwards管道模型理论对其形状记忆效应的分子机理进行了阐释, 利用材料的应力松弛特性对机理分析进行了验证.

关键词: 星形结构, 形状记忆高分子, 半互穿聚合物网络, 聚乙二醇, 聚甲基丙烯酸甲酯

Abstract:

Poly(methyl methacrylate)/star-shaped poly(ethylene glycol) semi-interpenetrating networks(PMMA/SEPG) with star-shaped structure were synthesized by non-covalent interactions. In order to confirm the effect of star polymer structure on the shape memory and mechanical properties, poly(methyl methacrylate)/line poly(ethylene glycol) semi-interpenetrating networks(PMMA/LPEG) were also synthesized. The effect of molecular weight of PEG in the PMMA network on thermal properties, mechanical properties, dynamic mechanical properties and shape memory properties containing shape fixed ratio, recovery ratio and recovery rate was studied. The results show that, the embedding of the star-shaped structure greatly improved shape recovery ratio and recovery rate of the PMMA/SPEG with excellent mechanical properties compared to PMMA/LPEG. The shape memory effect was explained according to the tube model proposed by Edwards, which was demonstrated by the stress relaxation characteristics of the materials.

Key words: Star-shaped structure, Shape memory polymer, Semi-interpenetrating polymer network, Poly(ethylene glycol), Poly(methyl methacrylate)

中图分类号:

O631.1⁺1

TrendMD:

李兴建, 吴瑞清, 来婧娟, 潘毅, 郑朝晖, 丁小斌. 聚甲基丙烯酸甲酯/星形聚乙二醇半互穿聚合物网络的形状记忆性能和分子机理. 高等学校化学学报, 2016, 37(10): 1932.

LI Xingjian, WU Ruiqing, LAI Jingjuan, PAN Yi, ZHENG Zhaohui, DING Xiaobin. Shape-memory Properties and Molecular Mechanism of Poly(methyl methacrylate)/Star-shaped Poly(ethylene glycol) Semi-interpenetrating Polymer Network^†. Chem. J. Chinese Universities, 2016, 37(10): 1932.

图/表 13

Table 1 Thermal properties of PMMA/SPEG and PMMA/LPEG

Sample	M_w of PEG	T_m/℃	ΔH_m/ (J·g^-1)	Crystallinity (%)
A1	3000(SPEG)
A2	6000(SPEG)
A3	15000(SPEG)	52	5.7	2.9
B1	1000(LPEG)	50	7.1	3.7
B2	2000(LPEG)	51	7.5	3.9
B3	5000(LPEG)	53	7.6	4.0

Fig.1 Mechanical properties of PMMA/SPEG(a, b) and PMMA/LPEG(c, d) obtained at 25 ℃ as a function of PEG molecular weight in the PMMA networks, respectively

Fig.2 Storage modulus(E')-temperature(a—c) and loss angle(tanδ)-temperature(a'—c') curves of PMMA/SPEG(A) and PMMA/LPEG(B)

Fig.3 Free-strain recovery shape-memory effect of sample A1 at Td=Tr=Tg=66 ℃ and Tf=10 ℃(Rf=98.8%, Rr=100%)

Fig.4 Free-strain recovery shape-memory effect of sample B1 at Td=Tr=Tg=67 ℃ and Tf=10 ℃(Rf=99.6%, Rr=91.3%)

Fig.5 Free-strain recovery shape-memory effect of sample A2 at Td=Tr=Tg=70 ℃ and Tf=10 ℃(Rf=98.6%, Rr=100%)

Fig.6 Free-strain recovery shape-memory effect of sample B2 at Td=Tr=Tg=75 ℃ and Tf=10 ℃(Rf=99.5%, Rr=92.2%)

Fig.7 Free-strain recovery shape-memory effect of sample A3 at Td=Tr=Tg=77 ℃ and Tf=10 ℃(Rf=98.8%, Rr=99.9%)

Fig.8 Free-strain recovery shape-memory effect of sample B3 at Td=Tr=Tg=79 ℃ and Tf=10 ℃(Rf=99.2%, Rr=95.0%)

Fig.9 Cyclic shape memory effect of sample A1(A) and sample B1(B) at Td=40, 50, 60, 75,90 ℃, Tf=10 ℃ and Tr=90 ℃

Table 2 Relationship between Vr and Td of PMMA/SPEG and PMMA/LPEG

T_d/℃	V_r/min^-1
T_d/℃	A1	B1
40	0.30	0.27
50	0.33	0.30
60	0.31	0.24
75	0.21	0.16
90	0.09	0.08

Fig.10 Series of photographs showing the macroscopic shape-memory effect of A1(red) and B1(black) samplePermanent shape is a spiral(A), temporary shape(B) is a rod. The pictures show the transition from temporary to permanent shape(B—G) at Tg. t/s: (B) 0; (C) 10; (D) 20; (E) 30; (F) 43; (G) 67.

Fig.11 Stress relaxation of PMMA/SPEG(A) and PMMA/LPEG(B) at Tg(A) a. A1; b. A2; c. A3; (B) a. B1; b. B2; c. B3.

参考文献 31

[1]	Lendlein A., Kelch S., Angew. Chem. Int. Ed., 2002, 41(12), 2034—2057
[2]	Xie T., Polymer, 2011, 52(22), 4985—5000
[3]	Meng Q. H., Hu J. L., Zhu Y., Lu J., Liu B. H., Text Res. J., 2009, 79(16), 1522—1533
[4]	Hu J. L., Meng H., Li G. Q., Ibekwe S. I., Smart Mater. Struct., 2012, 21(5), 053001
[5]	Lendlein A., Langer R., Science, 2002, 296(5573), 1673—1676
[6]	Brosnan S. M., Brown A. H., Ashby V. S., J. Am. Chem. Soc., 2013, 135(8), 3067—3072
[7]	Reed J. L., Hemmelgarn C. D., Pelley B. M., Havens E., Proc. SPIE, 2005, 5762,132—142
[8]	Sokolowski W. M., Tan S. C., J. Spacecr. Rocket., 2007, 44(4), 750—754
[9]	Pretsch T., Ecker M., Schildhauer M., Maskos M., J. Mater. Chem., 2012, 22(16), 7757—7766
[10]	Gall K., Kreiner P., Turner D., Hulse M., J. Microelectromech. Syst., 2004, 13(3), 472—483
[11]	Ebara M., Uto K., Idota N., Hoffman J. M., Aoyagi T., Adv. Mater., 2012, 24(2), 273—278
[12]	Ebara M., Uto K., Idota N., Hoffman J. M., Aoyagi T., Soft Matter, 2013, 9(11), 3074—3080
[13]	Zhao Q., Qi H. J., Xie T., Prog. Polym. Sci., 2015, 49,79—120
[14]	Hu J. L., Zhu Y., Huang H. H., Lu J., Prog. Polym. Sci., 2012, 37(12), 1720—1763
[15]	Li X. J., Wang Y. R., Zheng Z. H., Ding X. B., Peng Y. X., Prog. Chem., 2013, 25(10), 1726—1738
	(李兴建, 王亚茹, 郑朝晖, 丁小斌, 彭宇行.化学进展, 2013,25(10), 1726—1738)
[16]	Liu G. Q., Ding X. B., Cao Y. P., Zheng Z. H., Peng Y. X., Macromolecules, 2004, 37(6), 2228—2232
[17]	Liu G. Q., Guan C. L., Xia H. S., Guo F. Q., Ding X. B., Peng Y. X., Macromol. Rapid. Commun., 2006, 27(14), 1100—1104
[18]	Li J., Liu T., Xia S., Pan Y., Zheng Z. H., Ding X. B., Peng Y. X., J. Mater. Chem., 2011, 21(33), 12213—12217
[19]	Li X. J., Liu T., Wang Y. R., Zheng Z. H., Ding X. B., Peng Y. X., RSC Adv., 2014, 4(37), 19273—19282
[20]	Lendlein A., Schmidt A. M., Langer R., Proc. Natl. Acad. Sci., 2001, 98(3), 842—847
[21]	Behl M., Bellin I., Kelch S., Wagermaier W., Lendlein A., Adv. Funct. Mater., 2009, 19(1), 102—108
[22]	Alteheld A., Feng Y. K., Kelch S., Lendlein A., Angew. Chem. Int. Ed., 2005, 44(8), 1188—1192
[23]	Zotzmann J., Behl M., Hofmann D., Lendlein A., Adv. Mater., 2010, 22(31), 3424—3429
[24]	Zotzmann J., Behl M., Feng Y., Lendlein A., Adv. Funct. Mater., 2010, 20(20), 3583—3594
[25]	Wei M., Zhan M. Q., Yu D. Q., Xie H., He M. J., Yang K. K., Wang Y. Z., ACS Appl. Mater. Interfaces, 2015, 7(4), 2585—2596
[26]	Zhang T. H., Wen Z. B., Hui Y., Yang M. N., Yang K. K., Zhou Q., Wang Y. Z., Polym. Chem., 2015, 6(22), 4177—4184
[27]	Xiao L. P., Wei M., Zhan M. Q., Zhang J. J., Xie H., Deng X. Y., Yang K. K., Wang Y. Z., Polym. Chem., 2014, 5(7), 2231—2241
[28]	Doi M., Edwards S.F., The theory of Polymer Dynamics, Clarendon, Oxford, 1986
[29]	Na Y. H., Kurokawa T., Katsuyama Y., Tsukeshiba H., Gong J. P., Osada Y., Okabe S., Karino T., Shibayama M., Macromolecules, 2004, 37(14), 5370—5374
[30]	Milner S. T., Mcleish T. C. B., Macromolecules, 1997, 30(7), 2159—2166
[31]	Ratna D., Karger-Kocsis J., Polymer, 2011, 52(4), 1063—1070