高度支化聚乳酸共聚物的合成-应用化学专业论文.docxVIP

摘 要 本论文以辛酸亚锡 Sn(Oct)2 为催化剂，脂肪三级胺引发左旋-乳酸（LLA） 与支化单体 2,2-二羟甲基丁酸（BHB）共聚制备高度支化聚乳酸（PLA）共聚物 进行了系统的研究，并提出了相应的反应机理。 在聚合反应中控制 LLA、BHB 和 Sn(Oct)2 的投料摩尔比为 5:1:0.05，反应温 度为 135℃，在没有任何添加剂的情况下，得到的是具有不均一结构的低分子量 共聚物，由 MALDI-TOF 质谱分析可知，低分子量部分主要是 BHB 的均聚产物， 而高分子量的部分则主要是由带有一个 BHB 单元的线形 PLA 组成。 在聚合体系中加入脂肪三级胺能够有效地增加得到的共聚物的分子量，而芳 香三级胺、脂肪伯胺和仲胺却不能起到有效的促进作用。所得的 PLA 共聚物用 GPC、1H NMR、13C NMR 和 MALDI-TOF 质谱进行表征，证实了所得共聚物的 结构是由 LLA 和 BHB 单元组成的，并且具有高度支化的结构。支化度大约在 0.23-0.30 之间。通过 TGA 和 DSC 所做的热力学??析数据可知，所得的高度支化 的 PLA 共聚物是非晶型的。与线形的 PLA 相比，此高度支化的 PLA 共聚物热 力学稳定性更好且具有更低的玻璃化转变温度。 关键词：缩聚；聚乳酸；开环聚合；三级胺；高度支化  ABSTRACT In this article we demonstrated, in the Sn(Oct)2 catalyzed bulk copolymerization of L-lactide (LLA) and a large amount of branching comonomer 2,2-bis (hydroxymethyl)butyric acid (BHB) activated by aliphatic tertiary amine, low molecular weight of copolymers with inhomogeneous structure were generated. Meanwhile the mechanism of the highly branched PLA copolymers was proposed. In the experiment, we controlled the temperature of the reaction was 135 oC and the molar ratio of LLA, BHB and Sn(Oct)2 was 5: 1: 0.05. Without the addition of aliphatic tertiary amine to this polymerization system, MALDI-TOF mass spectrum demonstrated that the lower molar mass fraction was dominated with the BHB homo-polycondensation products; whereas the higher molar mass fraction was mainly composed of linear chains of poly(L-lactide) (PLA) bearing one BHB unit. The addition of aliphatic tertiary amine to this polymerization system could effectively enhance the molecular weight of the obtained copolymers, whereas, aromatic tertiary amines and aliphatic primary and secondary ones were not so effective. The obtained PLA copolymers were characterized by GPC, 1H NMR, 13C NMR and MALDI-TOF MS, which verified that they were composed of LLA and BHB units and had the highly branched structure. The degree of branching was about 0.23-0.30. Thermal analyses by TGA and DSC demonstrated that the resulting highly branched PLA copol