稀土催化聚ε-癸内酯-聚丙交酯-聚乙二醇热塑性弹性体的合成及自组装

doi:10.7503/cjcu20160064

高等学校化学学报 ›› 2016, Vol. 37 ›› Issue (6): 1182.doi: 10.7503/cjcu20160064

稀土催化聚ε-癸内酯-聚丙交酯-聚乙二醇热塑性弹性体的合成及自组装

王晓青, 凌君(), 沈之荃

教育部高分子合成与功能构造重点实验室, 浙江大学高分子科学与工程学系, 杭州 310027

收稿日期:2016-01-24 出版日期:2016-06-10 发布日期:2016-04-12
作者简介:联系人简介: 凌君, 男, 博士, 副教授, 主要从事可控配位聚合与阴离子聚合方法、可降解高分子材料的设计与应用、量子化学计算及分子模拟计算研究. E-mail:lingjun@zju.edu.cn
基金资助:
浙江省自然科学基金(批准号: LR15B040001)和国家自然科学基金(批准号: 21174122)资助

Synthesis and Self-assembly of Thermoplastic Elastomer Poly(ε-decalactone)-Poly(L-lactide)-PEG with Rare Earth Catalyst^†

WANG Xiaoqing, LING Jun^*(), SHEN Zhiquan

Key Laboratory of Macromolecular Synthesis and Functionalization, Ministry of Education, Department of Polymer Science and Engineering, Zhejiang University, Hangzhou 310027, China

Received:2016-01-24 Online:2016-06-10 Published:2016-04-12
Contact: LING Jun E-mail:lingjun@zju.edu.cn
Supported by:
† Supported by the Natural Science Foundation of Zhejiang Province, China(No.LR15B040001) and the National Natural Science Foundation of China(No.21174122)

摘要/Abstract

摘要：

以三(2,6-二叔丁基-4-甲基苯氧基)镧为催化剂, 1,4-丁二醇为引发剂, ε-癸内酯(ε-DL)和L-丙交酯(L-LA)为单体进行开环聚合, 采用“一锅两步法”合成了3种不同比例的三嵌段聚合物(PLLA-PDL-PLLA). 以L-赖氨酸二异氰酸酯(LDI)为扩链剂, 将PLLA-PDL-PLLA和生物相容性好的聚乙二醇6000(PEG6000)用LDI进行偶联, 制备了两亲性多嵌段聚合物(PLLA-PDL-PLLA-PEG)_m. 多嵌段聚合物(PLLA-PDL-PLLA-PEG)_m的断裂伸长率高达1200%, 是一种拉伸性能较好的热塑性弹性体. 由于PEG6000的亲水性, 使两亲性多嵌段聚合物可以自组装形成具有较低临界胶束浓度的胶束, 有望应用于生物医药领域.

关键词: ε-癸内酯, 稀土催化剂, 多嵌段聚合物, 热塑性弹性体, 胶束

Abstract:

Three triblock copolymers PLLA-PDL-PLLA with different compositions were synthesized by lanthanum tris(2,6-di-tert-butyl-4-methylphenolate) [La(OAr)₃] as the catalyst and 1,4-butanediol(BDO) as the initiator via a “one-pot two steps” block copolymerization strategy without PDL puriflcation. With biobased L-lysine diisocyanate(LDI) as the chain-extender, triblock copolymers were successively chain extended with biocompatible PEG6000 to produce multiblock copolymers. In tensile tests, the elongation at break of multiblock copolymers was up to 1200%, and they were good thermoplastic elastomers with an excellent mechanical property. In addition, the amphiphilic copolymers self-assembled into micelles in aqueous solution with a low critical micelle concentration(cmc) value of 4×10^-3 mg/mL.

Key words: ε-Decalactone, Rare earth catalyst, Multiblock copolymer, Thermoplastic elastomer, Micelle

中图分类号:

O632
O643

TrendMD:

王晓青, 凌君, 沈之荃. 稀土催化聚ε-癸内酯-聚丙交酯-聚乙二醇热塑性弹性体的合成及自组装. 高等学校化学学报, 2016, 37(6): 1182.

WANG Xiaoqing, LING Jun, SHEN Zhiquan. Synthesis and Self-assembly of Thermoplastic Elastomer Poly(ε-decalactone)-Poly(L-lactide)-PEG with Rare Earth Catalyst^†. Chem. J. Chinese Universities, 2016, 37(6): 1182.

图/表 13

Scheme 1 Synthesis of PLLA-PDL-PLLA triblock copolymer

Table 1 “One-pot two-step” synthesis of triblock copolymers catalyzed by La(OAr)3 in the presence of BDOa

Sample	n(BDO)∶n(DL)∶n(LLA) in feed	n(BDO)∶n(DL)∶n(LLA) in polymer^b	10^-3 $M n, NMR b$	10^-3 $M n, SEC c$	PDI^c
D₁₈-L₃₁	1∶20∶40	1∶18∶31	7.6	12.9	1.15
D₁₄-L₆₉	1∶59∶69	1∶14∶69	12.4	16.5	1.31
D₁₀-L₅₅	1∶10∶50	1∶10∶55	9.6	13.2	1.29

Table 1 “One-pot two-step” synthesis of triblock copolymers catalyzed by La(OAr)3 in the presence of BDOa

Sample	n(BDO)∶n(DL)∶n(LLA) in feed	n(BDO)∶n(DL)∶n(LLA) in polymer^b	10^-3 $M n, NMR b$	10^-3 $M n, SEC c$	PDI^c
D₁₈-L₃₁	1∶20∶40	1∶18∶31	7.6	12.9	1.15
D₁₄-L₆₉	1∶59∶69	1∶14∶69	12.4	16.5	1.31
D₁₀-L₅₅	1∶10∶50	1∶10∶55	9.6	13.2	1.29

Scheme 2 Structural formula of D18-L31

Fig.1 1H NMR spectra of D18-L31(a) and D18-L31-PEG(b) block copolymers

Fig.2 SEC traces of D18-L31(a), D14-L69(b), D10-L55(c), D18-L31-PEG(d), D14-L69-PEG(e) and D10-L55-PEG(f)

Table 2 Chain extension of triblock copolymers with PEG6000 by LDI in toluenea

Sample	n(D-L)∶n(PEG)∶n(LDI)^b	10^-3	PDI^c
D₁₈-L₃₁-PEG	1∶1∶2.2	109.7	1.73
D₁₄-L₆₉-PEG	1∶1∶2.2	78.7	1.59
D₁₀-L₅₅-PEG	1∶1∶2.2	90.6	1.59

Scheme 3 Synthesis of D-L-PEG multiblock copolymer

Fig.3 XRD(A) and DSC(B) curves of D18-L31-PEG(a), D14-L69-PEG(b) and D10-L55-PEG(c) multiblock copolymers

Fig.4 DMA storage modulus(E')(A), loss modulus(E″)(B) and tanδ(C) curves of D18-L31-PEG(a) and D14-L69-PEG(b) multiblock copolymers

Table 3 Tensile data for multiblock copolymers

Sample	w(PDL)(%)	Young’s modulus^a/MPa	Tensile stress^b/MPa	Tensile strain^c(%)
D₁₈-L₃₁-PEG	23	23	6.6	1200
D₁₄-L₆₉-PEG	13	60	6.4	880
D₁₀-L₅₅-PEG	11	123	7.5	410

Fig.5 Stress-strain curves of D18-L31-PEG(a), D14-L69-PEG(b) and D10-L55-PEG(c) multiblock copolymers

Fig.6 Particle size distribution of D18-L31-PEG(A) and D14-L69-PEG(B) micelles measured by DLS

Fig.7 Plot of fluorescence intensity ratio I338/I332 from the pyrene excitation spectrum vs. concentration for D18-L31-PEG

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稀土催化聚ε-癸内酯-聚丙交酯-聚乙二醇热塑性弹性体的合成及自组装

Synthesis and Self-assembly of Thermoplastic Elastomer Poly(ε-decalactone)-Poly(L-lactide)-PEG with Rare Earth Catalyst^†

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稀土催化聚ε-癸内酯-聚丙交酯-聚乙二醇热塑性弹性体的合成及自组装

Synthesis and Self-assembly of Thermoplastic Elastomer Poly(ε-decalactone)-Poly(L-lactide)-PEG with Rare Earth Catalyst†

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Synthesis and Self-assembly of Thermoplastic Elastomer Poly(ε-decalactone)-Poly(L-lactide)-PEG with Rare Earth Catalyst^†