基于反式聚异戊二烯/乙烯醋酸乙烯酯共聚三重形状记忆复合材料的制备及性能

辛华; 李阳帆; 彭琪; 陈悦; 李新琦

doi:10.13801/j.cnki.fhclxb.20221021.002

基于反式聚异戊二烯/乙烯醋酸乙烯酯共聚三重形状记忆复合材料的制备及性能

doi: 10.13801/j.cnki.fhclxb.20221021.002

陕西科技大学　化学与化工学院，西安 710021

基金项目: 国家自然科学基金 (51603117)

详细信息

通讯作者:
辛华，博士，副教授，硕士生导师，研究方向为功能高分子材料等　E-mail: xinhua@sust.edu.cn

中图分类号: O636.9
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出版历程
- 收稿日期: 2022-07-21
- 修回日期: 2022-09-24
- 录用日期: 2022-10-16
- 网络出版日期: 2022-10-21
- 刊出日期: 2023-07-15

Preparation and properties of triple shape memory composites based on trans-polyisopren/poly(ethylene-co-vinyl acetate)

College of Chemistry and Chemical Engineering, Shaanxi University of Science & Technology, Xi'an 710021, China

Funds: National Natural Science Foundation of China (51603117)

摘要

摘要: 本文将反式聚异戊二烯(TPI)和乙烯醋酸乙烯酯共聚物(EVA)复合，设计过氧化二异丙苯交联反应连接两相，制备TPI-EVA三重形状记忆复合材料。采用无转子硫化特性曲线、万能试验机、XRD、DSC、动态力学分析(DMA)对TPI-EVA复合材料进行了表征。探究了EVA质量比对TPI-EVA复合材料的力学性能、相结构、结晶性能及三重形状记忆性能的影响。结果表明，随着EVA质量比增加，TPI的结晶温度(T_c)从14.7℃降低至8.2℃，EVA的T_c略有上升。SEM结果表明，随EVA质量比增加，复合材料的相界面由光滑变为粗糙；DMA测试结果表明，EVA比例的增加使样品的第一临时形状固定率从57.6%提升至88.5%。此外，TPI-EVA复合材料表现出优异的力学强度，其中拉伸强度高达30.3 MPa，断裂伸长率达490%。
- 三重形状记忆效应 /
- 反式聚异戊二烯 /
- 乙烯醋酸乙烯酯共聚物 /
- 结晶性能 /
- 力学性能
Abstract: The TPI-EVA triple shape memory composites were prepared by compounding trans-polyisoprene and poly(ethylene-co-vinyl acetate) (TPI-EVA), and designed cross-linking reaction of dicumyl peroxide to connect the two phases. The TPI-EVA composites were characterized by rheometer, universal testing machine, XRD, DSC and dynamic thermomechanical analyzer (DMA). The effects of the mass ratio of EVA on the mechanical properties, phase structure, crystalline properties and triple shape memory properties of TPI-EVA composites were studied. The results show that with the increase of the mass ratio of EVA, the crystallization temperature (T_c) of TPI decreases from 14.7℃ to 8.2℃, and the T_c of EVA increase slightly. SEM test showed that with the increases of EVA mass ratio, the phase interface of the composites changes from smooth to rough; DMA test shows that the increase of EVA mass ratio increases the first temporary shape memory fixation rate of the samples from 57.6% to 88.5%. Moreover, the TPI-EVA composites exhibit excellent mechanical properties, the tensile strength is as high as 30.3 MPa and the elongation at break reaches 490%.
- tripe shape memory effect /
- trans-polyisopren /
- poly(ethylene-co-vinyl acetate) /
- crystallization /
- mechanical properties

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图 1 不同TPI-EVA比例的复合材料室温下的应力-应变曲线 (a) 和拉伸强度与断裂伸长率 (b)

Figure 1. Stress-strain curves (a) and tensile strength and elongation at breaking (b) of the TPI-EVA composites with different ratios

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图 2 不同TPI-EVA比例的复合材料的XRD图谱

Figure 2. XRD patterns of the TPI-EVA composites with different ratios

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图 3 不同TPI-EVA比例的复合材料的DSC曲线：(a) 第一次降温曲线；(b) 第二次升温曲线

Figure 3. DSC curves of the TPI-EVA composites with different ratios: (a) First cooling curves; (b) Secondary heating curves

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图 4 不同TPI-EVA比例的复合材料的动态力学分析(DMA)曲线：(a) T9E1；(b) T8E2；(c) T7E3；(d) T6E4；(e) T5E5

Figure 4. Dynamic mechanical analysis (DMA) curves of the TPI-EVA composites with different ratios: (a) T9E1; (b) T8E2; (c) T7E3; (d) T6E4; (e) T5E5

S_1,load, S_2,load—Strain corresponding to the first stress applied and the second stress applied; S_1,rec, S_2,rec—Increase the temperature to 55℃ and 105℃ in sequence to restore the strain of the sample; S₀—Initial strain; S₁, S₂—Final deformation of the sample after stress is applied

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图 5 TPI-EVA复合材料的三重形状记忆行为的数码照片：(a) T7E3；(b) T6E4

Figure 5. Photographs of the tripe shape memory effect of the TPI-EVA composites: (a) T7E3; (b) T6E4

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图 6 不同TPI-EVA比例的复合材料的SEM图像：(a) T9E1；(b) T8E2；(c) T7E3；(d) T6E4；(e) T5E5

Figure 6. SEM images of the TPI-EVA composites with different ratios: (a) T9E1; (b) T8E2; (c) T7E3; (d) T6E4; (e) T5E5

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图 7 TPI-EVA复合材料的三重形状记忆机制图

Figure 7. Schematic diagrams of TPI-EVA composites in tripe shape memory process

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表 1 TPI-EVA复合材料配方

Table 1. Formulation of TPI-EVA composites

Sample code	TPI/g	EVA/g
T10	100	0
T9E1	90	10
T8E2	80	20
T7E3	70	30
T6E4	60	40
T5E5	50	50
Notes: TPI—Trans-polyisoprene; EVA—Poly(ethylene-co-vinyl acetate). 2 g of stearic acid, 8 g of zinc oxide and 1 g of dicumyl peroxide were added.

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表 2 不同TPI-EVA比例复合材料在175℃下硫化特性参数

Table 2. Vulcanization characteristic parameters of TPI-EVA composites with different ratios at 175℃

Properties	T10	T9E1	T8E2	T7E3	T6E4	T5E5
M_H/(dN·m)	3.77	3.15	2.69	2.53	1.58	1.30
M_L/(dN·m)	0.37	0.27	0.14	0.47	0.00	0.00
M_H−M_L/(dN·m)	3.40	2.88	2.55	2.06	1.58	1.30
T₉₀/min	4.03	4.17	4.39	5:04	5.12	5.39
Cure rate index/min⁻¹	28.4	26.4	24.4	22.6	21.2	21.0
Notes: M_H—Maximum torque; M_L—Minimum torque; T₉₀—Optimum curing time.

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表 3 不同TPI-EVA比例的复合材料的三重形状记忆性能

Table 3. Tripe shape memory properties of the TPI-EVA composites with different ratios

Sample code	R_f(0→1)/%	R_f(1→2)/%	R_r(2→1)/%	R_r(1→0)/%
T8E2	57.6	99.0	79.6	99.8
T7E3	66.9	98.1	79.2	100.0
T6E4	77.9	97.6	78.9	99.9
T5E5	88.5	97.1	77.2	75.1
Notes: R_f—Shape fixity ratio; R_r—Shape recovery ratio.

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参考文献(31)

[1]	WANG F, ZHANG C, TAN A, et al. Photothermal and magnetocaloric-stimulated shape memory and self-healing via magnetic polymeric composite with dynamic crosslinking[J]. Polymer,2021,223:123677. doi: 10.1016/j.polymer.2021.123677
[2]	LIU Y J, LV H B, LAN X, et al. Review of electro-active shape-memory polymer composite[J]. Composites Science and Technology,2009,69(13):2064-2068. doi: 10.1016/j.compscitech.2008.08.016
[3]	SONG Q, CHEN H, ZHOU S, et al. Thermo- and pH-sensitive shape memory polyurethane containing carboxyl groups[J]. Polymer Chemistry,2016,7(9):1739-1746. doi: 10.1039/C5PY02010G
[4]	XIAO X L, KONG D Y, QIU X Y, et al. Shape-memory polymers with adjustable high glass transition temperatures[J]. Macromolecules,2015,48(11):3582-3589. doi: 10.1021/acs.macromol.5b00654
[5]	YANDE C, DONG L, CHEN G, et al. Bioinspired shape memory hydrogel artificial muscles driven by solvents[J]. ACS Nano,2021,15(8):13712-13720. doi: 10.1021/acsnano.1c05019
[6]	ZHANG H J, XIA H S, ZHAO Y. Light-controlled complex deformation and motion of shape-memory polymers using a temperature gradient[J]. ACS Macro Letters,2014,3(9):940-943. doi: 10.1021/mz500520b
[7]	LI Z, ZHANG X, WANG S, et al. Polydopamine coated shape memory polymer: Enabling light triggered shape recovery, light controlled shape reprogramming and surface functionalization[J]. Chemical Science,2016,7(7):4741-4747. doi: 10.1039/C6SC00584E
[8]	ZHANG F H, ZHANG Z C, LUO C J, et al. Remote, fast actuation of programmable multiple shape memory composites by magnetic fields[J]. Journal of Materials Chemistry C,2015,3(43):11290-11293. doi: 10.1039/C5TC02464A
[9]	KARASU F, WEDER C. Blends of poly(ester urethane)s and polyesters as a general design approach for triple-shape memory polymers[J]. Journal of Applied Polymer Science,2020,138(9):49935.
[10]	DELAEY J, DUBRUEL P, VAN VLIERBERGHE S. Shape-memory polymers for biomedical applications[J]. Advanced Functional Materials,2020,30(44):1909047. doi: 10.1002/adfm.201909047
[11]	XU C, ZHENG Z, LIN M, et al. Strengthened, antibacterial, and conductive flexible film for humidity and strain sensors[J]. ACS Applied Materials & Interfaces,2020,12(31):35482-35492. doi: 10.1021/acsami.0c10101
[12]	ARUN D I, KUMAR K S S, KUMAR B S, et al. High glass-transition polyurethane-carbon black electro-active shape memory nanocomposite for aerospace systems[J]. Materials Science and Technology,2019,35(5):596-605. doi: 10.1080/02670836.2019.1575054
[13]	ALSHEBLY Y S, NAFEA M, MOHAMED ALI M S, et al. Review on recent advances in 4D printing of shape memory polymers[J]. European Polymer Journal,2021,159:110708. doi: 10.1016/j.eurpolymj.2021.110708
[14]	RAMARAJU H, AKMAN R E, SAFRANSKI D L, et al. Designing biodegradable shape memory polymers for tissue repair[J]. Advanced Functional Materials,2020,30(44):2002014. doi: 10.1002/adfm.202002014
[15]	ZHENG X Y, ZHOU B, XUE S F. A viscoelastic-plastic constitutive model of shape memory polymer[J]. Journal of Mechanics,2019,35(5):601-611. doi: 10.1017/jmech.2018.56
[16]	HUANG Y N, FAN L F, RONG M Z, et al. External stress-free reversible multiple shape memory polymers[J]. ACS Applied Materials & Interfaces,2019,11(34):31346-31355. doi: 10.1021/acsami.9b10052
[17]	NIE J, HUANG J, FAN J, et al. Strengthened, self-healing, and conductive ENR-based composites based on multiple hydrogen bonding interactions[J]. ACS Sustainable Chemistry & Engineering,2020,8(36):13724-13733.
[18]	ZHENG Y, JI X, YIN M, et al. Strategy for fabricating multiple-shape-memory polymeric materials via the multilayer assembly of co-continuous blends[J]. ACS Applied Materials & Interfaces,2017,9(37):32270-32279. doi: 10.1021/acsami.7b10345
[19]	严瑞芳. 一种古老而又年轻的天然高分子—杜仲胶[J]. 高分子通报, 1989(2):39-44. YAN Ruifang. An age-old and young natural polymer—Gutta-percha[J]. Polymer Bulletin,1989(2):39-44(in Chinese).
[20]	张继川, 薛兆弘, 严瑞芳, 等. 天然高分子材料—杜仲胶的研究进展[J]. 高分子学报, 2011(10):1105-1117. ZHANG Jichuan, XUE Zhaohong, YAN Ruifang, et al. Natural polymer material—Recent studies on eucommia ulmoides gum[J]. Acta Polymerica Sinica,2011(10):1105-1117(in Chinese).
[21]	WANG Y, PEI X, XIA L, et al. Covalent crosslinks turn natural Eucommia ulmoides gum/polybutene-1 composites into multiple shape memory materials[J]. Polymer Composites,2021,43(3):1371-1382.
[22]	KANG H, GONG M, XU M, et al. Fabricated biobased eucommia ulmoides gum/polyolefin elastomer thermoplastic vulcanizates into a shape memory material[J]. Industrial & Engineering Chemistry Research,2019,58(16):6375-6384.
[23]	QI X, ZHAO X, LI Y, et al. A high toughness elastomer based on natural Eucommia ulmoides gum[J]. Journal of Applied Polymer Science,2020,138(11):50007.
[24]	WANG Y, LIU J, XIA L, et al. Fully biobased shape memory thermoplastic vulcanizates from poly(lactic acid) and modified natural Eucommia ulmoides gum with co-continuous structure and super toughness[J]. Polymers (Basel),2019,11(12):2040. doi: 10.3390/polym11122040
[25]	TIAN M, GAO W, HU J, et al. Multidirectional triple-shape-memory polymer by tunable cross-linking and crystallization[J]. ACS Applied Materials & Interfaces,2020,12(5):6426-6435.
[26]	WANG Y, XIA L, XIN Z. Triple shape memory effect of foamed natural Eucommia ulmoides gum/high density polyethylene composites[J]. Polymers for Advanced Technologies,2018,29(1):190-197. doi: 10.1002/pat.4102
[27]	HAN J L, LAI S M, CHIU Y T. Two-way multi-shape memory properties of peroxide crosslinked ethylene vinyl-acetate copolymer (EVA)/polycaprolactone (PCL) blends[J]. Polymers for Advanced Technologies,2018,29(7):2010-2024. doi: 10.1002/pat.4309
[28]	GU P, ZHANG J. Vinyl acetate content influence on thermal, non-isothermal crystallization, and optical characteristics of ethylenevinyl acetate copolymers[J]. Iranian Polymer Journal,2022,31:905-917. doi: 10.1007/s13726-022-01048-6
[29]	HAO C, WANG K, WANG Z, et al. Triple one-way and two-way shape memory poly(ethylene-co-vinyl acetate)/poly(ε-caprolactone) immiscible blends[J]. Journal of Applied Polymer Science,2021,139(1):51426.
[30]	LAI S M, LI C H, KAO H C, et al. Shape memory properties of melt-blended olefin block copolymer (OBC)/ethylene-vinyl acetate blends[J]. Journal of Macromolecular Science, Part B,2019,58(1):174-191. doi: 10.1080/00222348.2018.1558593
[31]	QI X M, DONG Y B, ISLAM M Z, et al. Excellent triple-shape memory effect and superior recovery stress of ethylene-vinyl acetate copolymer fiber[J]. Composites Science and Technology,2021,203:108609. doi: 10.1016/j.compscitech.2020.108609