Synthesis and Property of PDLA-PBS-PDLA Tri-block Copolymer†

doi:10.7503/cjcu20150633

Abstract

Abstract:

Poly(D-lactide)-poly(butylene succinate)-poly(D-Lactide)(PDLA-PBS-PDLA) was synthesized by the ring-opening polymerization of D-lactide(D-LA) in the presence of Sn(Oct)₂ and the pre-polymerized PBS as the macro-initiator. The PDLA-PBS-PDLA tir-block polymers were confirmed by gel permeation chromatography(GPC) and nuclear magnetic resonance(¹H NMR). Results of differential scanning calorimeter(DSC) and X-ray diffraction(XRD) revealed that with the increase of M_n of PDLA blocks, the melting temperature and enthalpy of PBS blocks decreased, and the crystallites of PBS blocks could not be detected by DSC when m(D-LA):m(PBS) was set as 2.60:1. For all the samples, PDLA segment could crystallize. With the increase of the amount of PDLA in the copolymers, the melting temperature of PDLA blocks increased gradually, but the melting enthalpy of PDLA blocks increased first and then decreased. Furthermore, both PDLA and PBS blocks could crystallize separately, and the crystal structures PDLA and PBS blocks did not change with m(D-LA):m(PBS), which revealed that the microphase separation formed in the copolymers.

Key words: Poly(butylene succinate), Poly(D-lactide), PDLA-PBS-PDLA tri-block copolymer

CLC Number:

O631.3

TrendMD:

MA Lili, SHAO Jun, YANG Chenguang, TANG Zhaohui, CHEN Xuesi. Synthesis and Property of PDLA-PBS-PDLA Tri-block Copolymer^†[J]. Chem. J. Chinese Universities, 2015, 36(11): 2329.

Figures/Tables 7

Scheme 1 Syntheses of PBS and PDLA-PBS-PDLA

Table 1 m(D-LA):m(PBS) and Mn of PBS and PDLA-PBS-PDLA

Sample	m(D-LA):m(PBS)	n(D-LA):n(PBS)^a	n(D-LA):n(PBS)^b	10^-3 $M n, GPC$	PDI
PBS	0:1	0:1	0:1	11.5	1.86
H1-2	0.51:1	1.21:1	1.05:1	18.0	1.40
H1-1	1.06:1	2.53:1	2.20:1	22.9	1.41
H3-2	1.56:1	3.72:1	3.58:1	29.2	1.67
H5-2	2.60:1	6.21:1	6.04:1	39.3	1.66
H3-1	3.04:1	7.26:1	7.56:1	39.3	1.83

Table 1 m(D-LA):m(PBS) and Mn of PBS and PDLA-PBS-PDLA

Sample	m(D-LA):m(PBS)	n(D-LA):n(PBS)^a	n(D-LA):n(PBS)^b	10^-3 $M n, GPC$	PDI
PBS	0:1	0:1	0:1	11.5	1.86
H1-2	0.51:1	1.21:1	1.05:1	18.0	1.40
H1-1	1.06:1	2.53:1	2.20:1	22.9	1.41
H3-2	1.56:1	3.72:1	3.58:1	29.2	1.67
H5-2	2.60:1	6.21:1	6.04:1	39.3	1.66
H3-1	3.04:1	7.26:1	7.56:1	39.3	1.83

Fig.1 1H NMR of PDLA-PBS-PDLA(H1-1) tri-block copolymer

Fig.2 Cooling curves of PBS and PDLA-PBS-PDLA tri-block copolymers

Table 2 Thermal data of PBS and PDLA-PBS-PDLA tri-block copolymers

Sample	Cooling		Second heating
Sample	T_c/℃	ΔH_c/(J·g^-1)	T_m1/℃	ΔH_m1/(J·g^-1)	T_m2/℃	ΔH_m2/(J·g^-1)
PBS	75.6	80.7	114.1	88.5
H1-2	72.4	53.0	111.2	52.2	133.0	4.9
H1-1	76.8	46.4	108.2	27.3	154.0	23.3
H3-2	87.8^a, 41.5^a	15.5^b, 10.7^b	99.6	14.3	163.0	28.9
H5-2	92.7	22.3	—	—	165.8	38.2
H3-1	88.9	19.9	—	—	166.2	39.8

Fig.3 Second heating curves of PBS and PDLA-PBS-PDLA tri-block copolymers

Fig.4 XRD patterns of PBS and PDLA-PBS-PDLA tri-block copolymers

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