PEG与TMB-5对PLLA结晶及性能的协同影响
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摘要
聚乳酸(PLLA)结晶速率慢、韧性差,通过联合添加成核剂(TMB-5)克服PLLA难以成核,添加链段运动调节剂聚乙二醇(PEG)提高PLLA链段运动能力以实现PLLA结晶与性能的调控。采用差示扫描量热仪(DSC)、X射线衍射仪(XRD)、小角X射线衍射仪(SAXD)、偏光显微镜(POM)和力学性能测试,考察了不同配比的TMB-5和PEG对PLLA的结晶行为与韧性的影响。结果表明,在PLLA中添加TMB-5和PEG,PLLA的玻璃化转变温度下降,结晶峰温度向高温方向移动,结晶速率加快,球晶尺寸变大,同时伴随有环带球晶的出现,但对PLLA的结构和晶型没有影响。力学测试表明,TMB-5/PEG协同改善了PLLA的韧性,当添加质量分数0.5%的TMB-5和质量分数3%的PEG时,PLLA/TMB-5/PEG三元共混物的韧性达到5.05kJ/m2,比PLLA/TMB-5二元共混物、PLLA分别提高了22.9%和150%。
In order to overcome problems of slow crystallization rate and poor toughness of poly(L-lactic acid)(PLLA),the nucleating agent(TMB-5)and the chain segment motion agent polyethylene glycol(PEG)were simultaneously added to PLLA to overcome the difficulty of nucleation and improve the chain segment motion ability of PLLA. Their effects on the crystallization behaviors and toughness of PLLA were systematically investigated by differential scanning calorimetry(DSC),X-ray diffraction(XRD),small angle X-ray diffraction(SAXD),polarized optical microscopy(POM)and mechanical properties test.The results showed that the addition of TMB-5 and PEG led to the glass transition temperature decrease.The crystallization temperature of PLLA/TMB-5/PEG blends shift to the high temperature,and the nucleation rate and the crystallization rate also increase.Moreover,the banded texture could be observed with increasing of PEG content.But the structure and crystal form of PLLA was not affected.Mechanical tests showed that TMB-5 and PEG could improve the toughness of PLLA.The highest impact strength occurred when adding the mass fraction of the TMB-5/PEG was 0.5% and 3%.The value of the highest impact strength was 5.05 kJ/m2 and increased by 22.9% and 150% than PLLA/TMB-5 blends and PLLA,respectively.
In order to overcome problems of slow crystallization rate and poor toughness of poly(L-lactic acid)(PLLA),the nucleating agent(TMB-5)and the chain segment motion agent polyethylene glycol(PEG)were simultaneously added to PLLA to overcome the difficulty of nucleation and improve the chain segment motion ability of PLLA. Their effects on the crystallization behaviors and toughness of PLLA were systematically investigated by differential scanning calorimetry(DSC),X-ray diffraction(XRD),small angle X-ray diffraction(SAXD),polarized optical microscopy(POM)and mechanical properties test.The results showed that the addition of TMB-5 and PEG led to the glass transition temperature decrease.The crystallization temperature of PLLA/TMB-5/PEG blends shift to the high temperature,and the nucleation rate and the crystallization rate also increase.Moreover,the banded texture could be observed with increasing of PEG content.But the structure and crystal form of PLLA was not affected.Mechanical tests showed that TMB-5 and PEG could improve the toughness of PLLA.The highest impact strength occurred when adding the mass fraction of the TMB-5/PEG was 0.5% and 3%.The value of the highest impact strength was 5.05 kJ/m2 and increased by 22.9% and 150% than PLLA/TMB-5 blends and PLLA,respectively.
引文
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[2]李媛媛,钱祉祺,包睿莹,等.P34HB的4HB含量对PLLA/P34HB共混物结构和性能的影响[J].高分子材料科学与工程,2016,32(6):96-100.(LI Yuanyuan,QIAN Zhiqi,BAO Ruiying,et al.Effect of 4HB content of P34HB on the structure and properties of PLLA/P34HB blends[J].Polymer Materials Science&Engineering,2016,32(6):96-100.)
[3]王飞飞,夏超,靳明,等.成核剂TMB-5对聚乳酸结晶性能的影响[J].合成树脂及塑料,2015,32(6):4-7.(WANG Feifei,XIA Chao,JIN Ming,et al.Influences of nucleating agent TMB-5on crystallization properties of poly(lactic-acid)[J].China Synthetic Resin and Plastics,2015,32(6):4-7.)
[4]李孝秀.成核剂与增塑剂对聚乳酸结晶性能的影响[D].上海:上海大学,2010.
[5]颜克福,李珊珊,周翔.聚乙二醇/滑石粉共混改性聚乳酸及吹塑薄膜性能的研究[J].塑料工业,2015,43(5):98-101.(YAN Kefu,LI Shanshan,ZHOU Xiang,Blending modification of poly(lactic acid)with polyethylene glycol/talcum powder and properties of the blown film[J].China Plastics Industry,2015,43(5):98-101.)
[6]ARVANITOYANNIS I S.Totally and partially biodegradable polymer blends based on natural and synthetic macromolecules:Preparation,physical properties,and potential as food packaging materials[J].Journal of Macromolecular Science-Reviews in Macromolecular Chemistry and Physics,1999,39(2):205-271.
[7]GARICA M,MARTINO M,ZARITZKY N.Lipid addition to improve barrier properties of edible starchbased films and coatings[J].Journal of Food Science,2000,65(6):941-944.
[8]王雪红,陈智,魏杰,等.赖氨酸改性聚乳酸/聚乙二醇共聚物的制备及表征[J].高分子材料科学与工程,2016,32(9):1-6.(WANG Xuehong,CHEN Zhi,WEI Jie,et al.Preparation and characterization of L-lysine modified PLLA-PEG copolymers[J].Polymer Materials Science&Engineering,2016,32(9):1-6.)
[9]张光华,熊伟,陈淼,等.PEG增塑PLA/成核剂复合体系的结晶行为和力学性能[J].陕西科技大学学报,2014,32(1):82-86.(ZHANG Guanghua,XIONG Wei,CHEN Miao,et al.Crystallization behavior and mechanical properties of PLA/nucleating agent plasticized with PEG[J].Journal of Shanxi University of Science&Technology,2014,32(1):82-86.)
[10]罗春燕,陈卫星,李永飞.PLLA/PEG共混物结晶行为研究[J].西安工业大学学报,2013,8:638-642.(LUO Chunyan,CHEN Weixing,LI Yongfei.Crystallization behavior of PLLA/PEG blends[J].Journal of Xi’an Technological University,2013,8:638-642.)
[11]YASUNIWA M,TSUBAKIHARA S,SUGIMOTO Y,et al.Thermal analysis of the double-melting behavior of poly(L-Lactic acid)[J].Journal of Polymer Science Part B:Polymer Physics,2004,42(1):25-32.
[12]LORENZO D M L.Calorimetric analysis of the multiple melting behavior of poly(L-lactic acid)[J].Journal of Applied Polymer Science,2006,100(4):3145-3151.
[13]GE C,DING P,SHI L,et al.Isothermal crystallization kinetics and melting behavior of poly(ethylene terephthalate)/barite nanocomposites[J].Journal of Polymer Science Part B:Polymer Physics,2009,47(7):655-668.
[14]REN M,SONG J,SONG C,et al.Crystallization kinetics and morphology of poly(butylene succinate-coadipate)[J].Journal of Polymer Science Part B:Polymer Physics,2005,43(22):3231-3241.
[15]MORGAN L B,STERN P G.Crystallization phenomena in polymers V The helical theory of the morphology of crystalline polymers[J].Polymer,1968,9:375-398.
[16]边界,叶胜荣.PET,PBT结晶过程Avrami方程的探讨[J].高等学校化学学报,2000,21(9):1481-1484.(BIAN Jie,YE Shengrong.Investigation on Avrami equation of PET and PBT in crystallization[J].Chemical Journal of Chinese Universities,2000,21(9):1481-1484.)
[17]SAEIDLOU S,HUNEAULTA M A,LI H,et al.Poly(lactic acid)crystallization[J].Progress in Polymer Science,2012,37(12):1657-1677.
[18]IKADA Y,JAMSHIDI K,TSUJI H.Stereocomplex formation between enantiomeric poly(lactides)[J].Macromole-Cules,1987,20(4):904-906.
[19]张雪勤,杨琥,王治流,等.高聚物环带球晶的研究进展[J].高分子通报,2006,2:1-8.(ZHANG Xueqin,YANG Hu,WANG Zhiliu,et al.Research progress in banded spherulites of polymers[J].Chinese Polymer Bulletin,2006,2:1-8.)
[20]SUN J R,HONG Z K,YANG L X,et al.Study on crystalline morphology of poly(L-lactide)-poly(ethylene glycol)diblock copolymer[J].Polymer,2004,45:5969-5977.