原位聚合改性纳米层状黏土/脂肪族聚酯嵌段共聚物复合材料的制备与性能  

Synthesis and Properties of Aliphatic Polyester Block Copolymers Filled with Nano Layered Clay Prepared by In-situ Graft Polymerization

作　　者：毛龙[1,2] 刘跃军[1,2] 姚进[2] 吴慧青[1] 白永康 MAO Long;LIU Yue-jun;YAO Jin;WU Hui-qing;BAI Yong-kang(Fujian Provincial Key Laboratory of Functional Materials and Applications,Xiamen University of Technology,Xiamen 361024,Fujian,China;Key Laboratory of Advanced Packaging Materials and Technology of Hunan Province,Hunan University of Technology,Zhuzhou 412007,Hunan,China;Institute of Polymer Science in Chemical Engineering,Xi＇an Jiaotong University,Xi＇an 710049,China)

机构地区：[1]厦门理工学院福建省功能材料及应用重点实验室,福建厦门361024 [2]湖南工业大学先进包装材料与技术湖南省重点实验室,湖南株洲412007 [3]西安交通大学高分子化工研究所,西安710049

出　　处：《材料工程》2018年第12期70-77,共8页Journal of Materials Engineering

基　　金：国家自然科学基金(11872179;21704085);福建省自然科学基金(2018JJ4072);福建省科技计划项目(2018H6024);聚合物分子工程国家重点实验室开发课题(复旦大学)(K2017-29);福建省中青年教师教育科研项目(JAT160354;JT180420);福建省教育厅研究项目(JK2017035);福建省功能材料及应用重点实验室开放课题(厦门理工学院)(fma2017110)

摘　　要：分别以预聚体聚丁二酸丁二醇酯(PBS)封端羟基引发ε-己内酯(ε-CL)开环聚合得到了脂肪族聚酯三嵌段共聚物(PCL-PBS-PCL),以纳米层状双羟基金属氧化物(LDHs)表面羟基引发ε-CL原位开环聚合得到了PCL原位聚合接枝改性LDHs(LDHs-g-PCL),然后再将两者采用溶液浇筑法制备出原位聚合改性纳米层状黏土/脂肪族聚酯嵌段共聚物(LDHs-g-PCL/PCL-PBS-PCL)纳米复合材料,研究了PCL-PBS-PCL和LDHs-g-PCL的化学结构以及所制备出的纳米复合材料的结晶特性、力学性能、阻隔性能等。结果表明,成功制备出LDHs-g-PCL/PCL-PBS-PCL纳米复合材料。随着LDHs-g-PCL的加入,PBS嵌段的结晶受限程度逐渐加强,PCL分子链的结晶却逐渐增多,这导致纳米复合材料的高温熔融峰向低温移动,低温熔融峰向高温移动。当LDHs-g-PCL的质量分数为20%时,纳米复合材料的断裂伸长率达到最大值772%,相比纯的PCL-PBS-PCL提高了35%,而拉伸强度相比纯的PCL-PBS-PCL(25.27 MPa)仅降低6%。当LDHs-g-PCL的质量分数为50%时,纳米复合材料对氧气的渗透性达到最低值,其相比纯的PCL-PBS-PCL降低幅度达到52%。这不仅与层状结构LDHs发挥的阻隔效应(显著延长氧气分子在纳米复合材料的曲折渗透路径)密不可分,还可能与LDHs-g-PCL加入引起的体积效应有关。Aliphatic polyester block copolymers poly（ε-caprolactone）-poly（butylene succinate）-poly（ε-caprolactone） （PCL-PBS-PCL） were synthesized by the ring-opening polymerization of ε-CL in the presence of the pre-polymerized PBS as the macro-initiator. LDHs- g -PCL were prepared by in-situ ring-opening polymerization of ε-CL. Then LDHs- g -PCL/PCL-PBS-PCL nanocomposites were prepared by blending PCL-PBS-PCL and LDHs- g -PCL via solution casting method. The chemical structures of PCL-PBS-PCL and LDHs- g -PCL were investigated. And crystallization behavior, mechanical properties and barrier properties of nanocomposites were also deeply studied. The results of thermal analysis confirm that the crystallization of PBS blocks is restrained markedly with the addition of LDHs- g -PCL. On the contrary, the crystallization of PCL chains is gradually increasing. The changes of crystallization for nanocomposites lead to the decrease in the high temperature melting peaks and the increase in the low temperature melting peaks. Even though a slight decrease （6%） in tensile strength, elongation at break of nanocomposites reaches to the maximum value of 772% （increased by 35%） in the presence of LDHs- g -PCL containing 20% （mass fraction）. Compared with pure PCL-PBS-PCL, the O 2 permeability of nanocomposites decreased by nearly 52% as LDHs- g -PCL content increase up to 50% （mass fraction）. The key parameters to improve the barrier properties of nanocomposites are not only the barrier effect of the LDHs （a decrease in diffusion is expected because of a more tortuous path for diffusing molecules） but also the bulk effect that they develop in the polymer matrix.

关 键 词：层状黏土 脂肪族聚酯嵌段共聚物 原位聚合 阻隔性能 力学性能 

分 类 号：O633.14[理学—高分子化学]