聚乳酸/聚己内酯/聚(ε-己内酯-L-丙交酯)共聚物三元共混体系的结构与性能

doi:10.11944/j.issn.1000-0518.2016.09.150429

摘要/Abstract

摘要：

通过开环共聚合,合成了3种不同单元比例的ε-己内酯(ε-CL)与L-丙交酯(L-LA)的共聚物P(CL-co-LA)。通过熔融共混制备了聚乳酸(PLA)/聚己内酯(PCL)/P(CL-co-LA)三元共混材料,研究了P(CL-co-LA)对共混材料微观形貌、热性能以及力学性能的影响。结果表明,共聚物P(CL-co-LA)作为PLA/PCL不相容体系的界面增容剂,减小了PCL分散相的尺寸,改善了PLA/PCL共混体系的相容性,提高了共混材料的韧性。固定m(PLA):m(PCL):m(P(CL-co-LA))=80:20:10时,以P(CL49/LA51)(其中数字代表摩尔分数(%))作为界面增容剂效果最佳,共混材料的断裂伸长率可达到(210±30)%。

关键词: 聚乳酸, 聚己内酯, 共混, 增韧, 相容性

Abstract:

Three copolymers P(CL-co-LA) made from ε-caprolactone(ε-CL) and L-lactide(L-LA) have been synthesized via the ring-opening polymerization(ROP). Copolymers and PCL were added to PLA by melt blending, and then the PLA/PCL/P(CL-co-LA) blends were obtained. The compatibility, thermal and mechanical properties of the blends were studied. The results show that the interface compatibilizer of PLA/PCL blends, P(CL-co-LA) reduces the size of the PCL dispersed phase, moreover, the compatibility and toughness of PLA/PCL blends are enhanced. When the mass ratio of PLA/PCL/P(CL-co-LA) is 80/20/10, P(CL49/LA51), is which the numbers reprent the molar fraction(%), is the most suitable interface compatibilizer, and the elongation at break of the blends reaches as high as (210±30)%.

Key words: polylactide, poly(ε-caprolactone), blends, toughened, compatibility

张涵, 孙志强, 庞烜, 周林尧, 李帅, 孙海波, 陈文启, 陈学思. 聚乳酸/聚己内酯/聚(ε-己内酯-L-丙交酯)共聚物三元共混体系的结构与性能[J]. 应用化学, 2016, 33(9): 1026-1032.

ZHANG Han, SUN Zhiqiang, PANG Xuan, ZHOU Linyao, LI Shuai, SUN Haibo, CHEN Wenqi, CHEN Xuesi. Structure and Properties of Polylactide/Polycaprolactone/Poly(ε-caprolactone-L-lactide) Ternary Blends[J]. Chinese Journal of Applied Chemistry, 2016, 33(9): 1026-1032.

参考文献

[1]	Flieger M,Kantorova M,Prell A,et al.Biodegradable Plastics from Renewable Sources[J]. Folia Microbiol,2003,48(1):27-44.
[2]	YU Tongzhen,ZHANG Zheng,CHANG Yuanliang. Progress in Synthetic Technology and Application of Poly(lactic acid)[J]. Shandong Chem Ind,2005,34(4):25-28(in Chinese). 于同珍,张峥,常源亮. 聚乳酸的合成技术及应用进展[J]. 山东化工,2005,34(4):25-28.
[3]	XING Yuqing,WU Guiguo,XING Jun. Chemosynthesis of Perfectly Degradable Plastics Polylactic Acid[J]. Eng Plast Appl,2002,30(12):57-58(in Chinese). 邢玉清,吴贵国,邢军. 化学合成全降解塑料-聚乳酸[J]. 工程塑料应用,2002,30(12):57-58.
[4]	Engelberg I,Kohn J. Physico-Mechanical Properties of Degradable Polymers Used in Medical Applications:A Comparative Study[J]. Biomaterials,1991,12(3):292-304.
[5]	Ajioka M,Enomoto K,Suzuki K,et al.The Basic Properties of Poly(lactic acid) Produced by the Direct Condensation Polymerization of Lactic Acid[J]. J Environ Polym Degrad,1995,3(4):225-234.
[6]	Jacobsen S,Fritz H G. Plasticizing Polylactide-The Effect of Different Plasticizers on the Mechanical Properties[J]. Polym Eng Sci,1999,39(7):1303-1310.
[7]	KANG Hongliang,CHEN Cheng,DONG Lisong. Review of Poly(lactid acid) Based Blends[J]. Polym Bull,2004,(5):10-19(in Chinese). 康宏亮,陈成,董丽松. 聚乳酸共混体系的研究进展[J]. 高分子通报,2004,(5):10-19.
[8]	ZHANG Han,SUN Zhiqiang,PANG Xuan,et al.Preparation and Properties of Blends from Poly(ε-caprolactone-ran-L-lactide) Random Copolymer and Amorphous Poly(lactic acid)[J]. Chinese J Appl Chem,2015,32(11):1268-1274(in Chinese). 张涵,孙志强,庞烜,等. 聚(ε-己内酯-L-丙交酯)无规共聚物与聚乳酸共混材料的制备与性能[J]. 应用化学,2015,32(11):1268-1274.
[9]	YANG Yanhui,YAN Han,KANG Xiaomei,et al.Advances in Application Research of Polycaprolactone[J]. New Chem Mater,2011,39(12):13-15(in Chinese). 杨延慧,严寒,康晓梅,等. 聚己内酯的应用研究进展[J]. 化工新型材料,2011,39(12):13-15.
[10]	Sarazin P,Li G,Orts W J,et al.Binary and Ternary Blends of Polylactide, Polycaprolactone and Thermoplastic Starch[J]. Polymer,2008,49(2):599-609.
[11]	ZHANG Yisheng,WU Defeng,ZHANG Ming. Phase Morphology and Rheological Behavior of Poly(ε-caprolactone)/Polylactide Blend[J]. J Chem Ind Eng,2008,59(10):2645-2651(in Chinese). 张义盛,吴徳峰,张明. 聚己内酯/聚乳酸共混体系的相形态及其流变行为[J]. 化工学报,2008,59(10):2645-2651.
[12]	Dell'Erba R,Groeninckx G,Maglio G,et al. Immiscible Polymer Blends of Semicrystalline Biocompatible Components:Thermal Properties and Phase Morphology Analysis of PLLA/PCL Blends[J]. Polymer,2001,42(18):7831-7840.
[13]	Broz M E,Vanderhart D L,Washburn N R. Structure and Mechanical Properties of Poly(D,L-lactic acid)/Poly(ε-caprolactone) Blends[J]. Biomaterials,2003,24(23):4181-4190.
[14]	Naito K,Johnson G E,Allara D L,et al.Compatibility in Blends of Poly(methylmethacrylate) and Poly(styrene-co-acrylonitrile).1.Physical Properties[J]. Macromolecules,1978,11(6):1260-1265.
[15]	Vion J M,Jerome R,Teyssie P,et al.Synthesis, Characterization, and Miscibility of Caprolactone Random Copolymers[J]. Macromolecules,1986,19(7):1828-1838.
[16]	Ural E,Kesenci K,Fambri L,et al.Poly(D,L-lactide/ε-caprolactone)/Hydroxyapatite Composites[J]. Biomaterials,2000,21(21):2147-2154.
[17]	Nalampang K,Molloy R,Punyodom W. Synthesis and Characterization of Poly(L-lactide-co-ε-caprolactone) Copolymers:Influence of Sequential Monomer Addition on Chain Microstructure[J]. Polym Adv Technol,2007,18(3):240-248.
[18]	Choi E J,Park J K,Chang H N. Effect of Polymerization Catalyst on the Microstructure of P(LLA-co-ε-CL)[J]. J Polym Sci Polym Phys,1994,32(15):2481-2489.
[19]	Shen Y Q,Zhu K J,Shen Z Q,et al.Synthesis and Characterization of Highly Random Copolymer of ε-Caprolactone and D,L-lactide Using Rare Earth Catalyst[J]. J Polym Sci Polym Chem,1996,34(9):1799-1805.
[20]	Ingrid K S,Hans R K. Zn Lactate-Catalyzed Copolymerization of L-Lactide with Glycolide or ε-Caprolactone[J]. Macromol Chem Phys,1998,199(6):1081-1087.
[21]	Hans R K,Kirstin B,Heiko H T,et al.Bismuth(Ⅲ) n-Hexanoate and Tin(Ⅱ) 2-Ethylhexanoate Initiated Copolymerizations of ε-Caprolactone and L-lactide[J]. Macromolecules,2005,38(12):5017-5024.
[22]	Fabrice S,Robert J. Polymerization of (L,L)-Lactide and Copolymerization with ε-Caprolactone Initiated by Dibutyltin Dimethoxide in Supercritical Carbon Dioxide[J]. J Polym Sci Polym Chem,2005,43(13):2777-2789.
[23]	Nomura N,Akita A,Ishii R,et al.Random Copolymerization of ε-Caprolactone with Lactide Using a Homosalen-Al Complex Oxides[J]. J Am Chem Soc,2010,132(6):1750-1751.
[24]	Kim C H,Cho K Y,Choi E J,et al.Effect of P(L-LA-co-ε-CL) on the Compatibility and Crystallization Behavior of PCL/PLLA Blends[J]. J Appl Polym Sci,2000,77(1):226-231.
[25]	Yang J M,Chen H L,You J W,et al.Miscibility and Crystallization of Poly(L-lactide)/Poly(ethylene glycol) and Poly(L-lactide)/Poly(ε-caprolactone) Blends[J]. Polym J,1997,29(8):657-662.