Shape-memory Properties and Molecular Mechanism of Poly(methyl methacrylate)/Star-shaped Poly(ethylene glycol) Semi-interpenetrating Polymer Network†

doi:10.7503/cjcu20160202

Abstract

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)

CLC Number:

O631.1⁺1

TrendMD:

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^†[J]. Chem. J. Chinese Universities, 2016, 37(10): 1932.

Figures/Tables 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.

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