右旋聚乳酸-己内酯无规共聚物对左旋聚乳酸/聚己内酯共混物的结构调控和性能
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摘要
采用熔融共混法制备左旋聚乳酸(PLLA)、聚己内酯(PCL)和右旋乳酸-己内酯无规共聚物(PDLA-r-PCL)的共混物。通过差示扫描量热仪、扫描电子显微镜、X射线衍射和拉伸测试等手段探究了相容剂PDLA-r-PCL对PLLA/PCL共混物结构和性能的影响。结果表明,随着PDLA-r-PCL含量的增加,共混物中立构晶(SC)含量增加;降温过程中,α晶结晶温度由93℃提高至108℃,表明SC晶对共混体系中α晶有异相成核作用。无规共聚物PDLA-r-PCL的加入,显著改善了PLLA与PCL的相容性,且随着无规共聚物含量增加,共混物中PCL的相尺寸减小,界面模糊;与PLLA/PCL相比,淬冷和退火处理PLLA/PCL/PDLA-r-PCL共混物的断裂伸长率提高,且强度也略微提升;并且PDLA-r-PCL可有效提高退火的PLLA/PCL样品的冲击强度。
Poly(D-lactide)-r-poly(ε-caprolactone)(PDLA-r-PCL) was used as compatibilizer for preparing poly(L-lactide) blends with poly(ε-caprolactone)(PLLA/PCL) by melt blending. The effects of PDLA-r-PCL on the structure and properties of PLLA/PCL blends were studied by differential scanning calorimetry(DSC), scanning electron microscopy(SEM) and X-ray diffraction and tensile testing(XRD). With the increase of PDLA-r-PCL content, the content of stereocomplex crystal(SC) in the blends gradually increases. And the crystallization temperature of α crystal increases from 93 ℃ to 108 ℃, which indicates that the existence of SC could improve the nucleation of α crystal. With the addition of PDLA-r-PCL, the compatibility of PLLA and PCL is significantly improved. With the increasing of PDLA-r-PCL content, the phase size of PCL decreases and the interface becomes blurred. The elongation at break of PLLA/PCL/PDLA-r-PCL after quenching and annealing is higher than that of PLLA/PCL. Meanwhile, the strength of PLLA/PCL/PDLA-r-PCL is slightly increased. The introduction of PDLA-r-PCL could effectively enhance the impact strength of PLLA/PCL annealed samples.
Poly(D-lactide)-r-poly(ε-caprolactone)(PDLA-r-PCL) was used as compatibilizer for preparing poly(L-lactide) blends with poly(ε-caprolactone)(PLLA/PCL) by melt blending. The effects of PDLA-r-PCL on the structure and properties of PLLA/PCL blends were studied by differential scanning calorimetry(DSC), scanning electron microscopy(SEM) and X-ray diffraction and tensile testing(XRD). With the increase of PDLA-r-PCL content, the content of stereocomplex crystal(SC) in the blends gradually increases. And the crystallization temperature of α crystal increases from 93 ℃ to 108 ℃, which indicates that the existence of SC could improve the nucleation of α crystal. With the addition of PDLA-r-PCL, the compatibility of PLLA and PCL is significantly improved. With the increasing of PDLA-r-PCL content, the phase size of PCL decreases and the interface becomes blurred. The elongation at break of PLLA/PCL/PDLA-r-PCL after quenching and annealing is higher than that of PLLA/PCL. Meanwhile, the strength of PLLA/PCL/PDLA-r-PCL is slightly increased. The introduction of PDLA-r-PCL could effectively enhance the impact strength of PLLA/PCL annealed samples.
引文
[1] Gustafsson G,H?ggblad H,Jonsen P,et al.Mechanical characterization and modelling of the temperature-dependent impact be haviour of a biocompatible poly(L-lactide)/poly(ε-caprolactone) polymer blend [J].J.Mech.Behav.Biomed.,2015,51:279-290.
[2] Xing Q,Li R B,Dong X,et al.Phase morphology,crystallization behavior and mechanical properties of poly(L-lactide) toughened with biodegradable polyurethane:effect of composition and hard segment ratio[J].Chin.J.Polym.Sci.,2015,33:1294-1304.
[3] Sun J R,Shao J,Huang S Y,et al.Thermostimulated crystallization of polylactide stereocomplex[J].Mater.Lett.,2012,89:169-171.
[4] 强涛,于德梅.聚乳酸增韧研究进展[J].高分子材料科学与工程,2010,26(9):167-170.Qiang T,Yu D M.Research progress in toughening of polylactic acid [J].Polymer Materials Science & Engineering ,2010,26(9):167-170.
[5] Bhardwaj R,Mohanty A K.Advances in the properties of polylactides based materials:a review[J].J.Biobased Mater.Bio.,2007,1:191-209.
[6] Rasal R M,Janorkarc A V,Hirt D E.Poly(lactic acid) modifications[J].Prog.Polym.Sci.,2010,35:338-356.
[7] Shibata M,Inoue Y,Miyoshi M.Mechanical properties,morphology,and crystallization behavior of blends of poly( L -lactide) with poly(butylene succinate- co - L -lactate) and poly(butylene succinate)[J].Polymer,2006,47:3557-3564.
[8] 赵聪.PLA/PBS共混复合材料的改性研究[D].上海:华东理工大学,2016.Zhao C.Study on modification of PLA/PBS blend composites[D].Shanghai:East China University of Science and Technology,2016.
[9] Jiang L,Wolcott M P,Zhang J.Study of biodegradable polylactide/poly(butylene adipate-co-terephthalate) blends[J].Biomacromolecules,2006,7:199-207.
[10] Oliaei E,Kaffashi B,Davoodi S.Investigation of structure and mechanical properties of toughened poly(l-lactide)/thermoplastic poly(ester urethane) blends[J].J.Appl.Polym.Sci.,2016,133:3560-3572.
[11] 王思思,庞素娟,徐鼐,等.聚乳酸/聚己二酸-对苯二甲酸丁二醇酯共混物等温结晶行为及等温热处理对力学性能的影响[J].高分子材料科学与工程,2016,32(8):38-44.Wang S S,Pang S J,Xu N,et al.Effect of isothermal crystallization behavior of poly(lactic acid/poly-adipate-terephthalic glycol ester blends) on mechanical properties[J].Polymer Materials Science & Engineering,2016,32(8):38-44.
[12] Ostafinska A,Fortelny I,Nevoralova M,et al.Synergistic effects in mechanical properties of PLA/PCL blends with optimized composition,processing,and morphology[J].Rsc Adv.,2015,5:98971-98982.
[13] Wong H M,Zhao Y,Leung F K,et al.Functionalized polymeric membrane with enhanced mechanical and biological properties to control the degradation of magnesium alloy[J].Adv.Healthc.Mater.,2017,6:DOI:10.1002/adhm.201601269.
[14] Gurlek A C,Sevinc B,Bayrak E,et al.Synthesis and characterization of polycaprolactone for anterior cruciate ligament regeneration[J].Mater.Sci.Eng.,C,2017,71:820-826.
[15] Cartier L,Okihara T,Ikada Y,et al.Epitaxial crystallization and crystalline polymorphism of polylactides[J].Polymer,2000,41:8909-8919.
[16] Na Y H,He Y,Shuai X T,et al.Compatibilization effect of poly(ε-caprolactone)-b-poly(ethylene glycol) block copolymers and phase morphology analysis in immiscible poly(lactide)/poly(ε-caprolactone) blends[J].Biomacromolecules,2002,3:1179-1186.
[17] 李琦,熊祖江,王锐,等.右旋聚乳酸-己内酯无规共聚物对左旋聚乳酸/聚己内酯共混物的结构调控和性能[J].高分子材料科学与工程,2018,34(3):43-48.Li Q,Xiong Z J,Wang R,et al.Structure and properties of toughened poly(L-lactide) by poly(D-lactide)-r-poly (ε-caprolactone) random copolymer[J].Polymer Materials Science & Engineering,2018,34(3):43-48.
[18] Zhang J M,Tashiro K,Tsuji H,et al.Investigation of phase transitional behavior of poly(L-lactide)/poly(d-lactide) blend used to prepare the highly-oriented stereocomplex[J].Macromolecules,2007,40:1049-1054.
[19] Bai H W,Xiu H,Gao J,et al.Tailoring impact toughness of poly(L-lactide)/poly(epsilon-caprolactone) (PLLA/PCL) blends by controlling crystallization of PLLA matrix[J].ACS Appl.Mater.Interfaces,2012,4:897-905.
[2] Xing Q,Li R B,Dong X,et al.Phase morphology,crystallization behavior and mechanical properties of poly(L-lactide) toughened with biodegradable polyurethane:effect of composition and hard segment ratio[J].Chin.J.Polym.Sci.,2015,33:1294-1304.
[3] Sun J R,Shao J,Huang S Y,et al.Thermostimulated crystallization of polylactide stereocomplex[J].Mater.Lett.,2012,89:169-171.
[4] 强涛,于德梅.聚乳酸增韧研究进展[J].高分子材料科学与工程,2010,26(9):167-170.Qiang T,Yu D M.Research progress in toughening of polylactic acid [J].Polymer Materials Science & Engineering ,2010,26(9):167-170.
[5] Bhardwaj R,Mohanty A K.Advances in the properties of polylactides based materials:a review[J].J.Biobased Mater.Bio.,2007,1:191-209.
[6] Rasal R M,Janorkarc A V,Hirt D E.Poly(lactic acid) modifications[J].Prog.Polym.Sci.,2010,35:338-356.
[7] Shibata M,Inoue Y,Miyoshi M.Mechanical properties,morphology,and crystallization behavior of blends of poly( L -lactide) with poly(butylene succinate- co - L -lactate) and poly(butylene succinate)[J].Polymer,2006,47:3557-3564.
[8] 赵聪.PLA/PBS共混复合材料的改性研究[D].上海:华东理工大学,2016.Zhao C.Study on modification of PLA/PBS blend composites[D].Shanghai:East China University of Science and Technology,2016.
[9] Jiang L,Wolcott M P,Zhang J.Study of biodegradable polylactide/poly(butylene adipate-co-terephthalate) blends[J].Biomacromolecules,2006,7:199-207.
[10] Oliaei E,Kaffashi B,Davoodi S.Investigation of structure and mechanical properties of toughened poly(l-lactide)/thermoplastic poly(ester urethane) blends[J].J.Appl.Polym.Sci.,2016,133:3560-3572.
[11] 王思思,庞素娟,徐鼐,等.聚乳酸/聚己二酸-对苯二甲酸丁二醇酯共混物等温结晶行为及等温热处理对力学性能的影响[J].高分子材料科学与工程,2016,32(8):38-44.Wang S S,Pang S J,Xu N,et al.Effect of isothermal crystallization behavior of poly(lactic acid/poly-adipate-terephthalic glycol ester blends) on mechanical properties[J].Polymer Materials Science & Engineering,2016,32(8):38-44.
[12] Ostafinska A,Fortelny I,Nevoralova M,et al.Synergistic effects in mechanical properties of PLA/PCL blends with optimized composition,processing,and morphology[J].Rsc Adv.,2015,5:98971-98982.
[13] Wong H M,Zhao Y,Leung F K,et al.Functionalized polymeric membrane with enhanced mechanical and biological properties to control the degradation of magnesium alloy[J].Adv.Healthc.Mater.,2017,6:DOI:10.1002/adhm.201601269.
[14] Gurlek A C,Sevinc B,Bayrak E,et al.Synthesis and characterization of polycaprolactone for anterior cruciate ligament regeneration[J].Mater.Sci.Eng.,C,2017,71:820-826.
[15] Cartier L,Okihara T,Ikada Y,et al.Epitaxial crystallization and crystalline polymorphism of polylactides[J].Polymer,2000,41:8909-8919.
[16] Na Y H,He Y,Shuai X T,et al.Compatibilization effect of poly(ε-caprolactone)-b-poly(ethylene glycol) block copolymers and phase morphology analysis in immiscible poly(lactide)/poly(ε-caprolactone) blends[J].Biomacromolecules,2002,3:1179-1186.
[17] 李琦,熊祖江,王锐,等.右旋聚乳酸-己内酯无规共聚物对左旋聚乳酸/聚己内酯共混物的结构调控和性能[J].高分子材料科学与工程,2018,34(3):43-48.Li Q,Xiong Z J,Wang R,et al.Structure and properties of toughened poly(L-lactide) by poly(D-lactide)-r-poly (ε-caprolactone) random copolymer[J].Polymer Materials Science & Engineering,2018,34(3):43-48.
[18] Zhang J M,Tashiro K,Tsuji H,et al.Investigation of phase transitional behavior of poly(L-lactide)/poly(d-lactide) blend used to prepare the highly-oriented stereocomplex[J].Macromolecules,2007,40:1049-1054.
[19] Bai H W,Xiu H,Gao J,et al.Tailoring impact toughness of poly(L-lactide)/poly(epsilon-caprolactone) (PLLA/PCL) blends by controlling crystallization of PLLA matrix[J].ACS Appl.Mater.Interfaces,2012,4:897-905.