Unentangled Star-Shape Poly(ε-caprolactone)s as Phthalate-Free PVC Plasticizers Designed for Non-Toxicity and Improved Migration Resistance
Unentangled Star-Shape Poly(ε-caprolactone)s as Phthalate-Free PVC Plasticizers Designed for Non-Toxicity and Improved Migration Resistance
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DOI：
10.1021/am500740v
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发表时间：
2014-07-23
影响因子：
9.5
通讯作者：
Kwak, Seung-Yeop
中科院分区：
文献类型：
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作者：
Choi, Woohyuk;Chung, Jae Woo;Kwak, Seung-Yeop
我们开发了一种无毒的无缠结星形聚（e-己内酯）（UESPCL）增塑剂，具有优异的抗迁移性，用于生产无邻苯二甲酸酯的柔性聚氯乙烯（PVC），通过开环聚合的e-己内酯，从多功能核引发，结合封端，和真空纯化过程。UESPCL在室温下是透明的液体，并且由于其极短的支化链段而表现出非纠缠的牛顿行为。UESPCL生物安全，不会产生急性毒性反应。扭矩分析测量结果表明，与典型的增塑剂邻苯二甲酸二（2-乙基己基）酯（DEHP）相比，UESPCL具有更快的熔融速率和更高的PVC溶解性。固态H-1核磁共振（NMR）谱表明，PVC和UESPCL是可混溶的，平均微区尺寸小于8 nm。PVC/UESPCL混合物，即不含邻苯二甲酸酯的柔性PVC的柔韧性和透明性与PVC/DEHP混合物的相应性能相当，PVC/UESPCL的拉伸性和断裂韧性上级PVC/DEHP体系的相应性能。最重要的是，PVC/UESPCL显示出优异的抗迁移性，在液相中的重量损失小于0.6%，而DEHP从PVC/DEHP迁移到液相中，重量损失约为10%。
We develop a nontoxic unentangled star-shape poly(e-caprolactone) (UESPCL) plasticizer with excellent migration resistance for the production of phthalate-free flexible poly(vinyl chloride) (PVC) by means of the ring-opening polymerization of e-caprolactone, initiated from the multifunctional core, combined with end-capping, and vacuum purification processes. UESPCL is a transparent liquid at room temperature and exhibits unentangled Newtonian behavior because of its extremely short branched segments. UESPCL is biologically safe without producing an acute toxicity response. Torque analysis measurements reveals that UESPCL offers a faster fusion rate and a higher miscibility with PVC compared to a typical plasticizer, di(2-ethylhexyl phthalate (DEHP). The solid-state H-1 nuclear magnetic resonance (NMR) spectrum reveals that PVC and UESPCL are miscible with an average domain size of less than 8 nm. The flexibility and transparency of the PVC/UESPCL mixture, that is, phthalate-free flexible PVC, are comparable to the corresponding properties of the PVC/DEHP mixture, and the stretchability and fracture toughness of PVC/UESPCL are superior to the corresponding properties of the PVC/DEHP system. Most of all, PVC/UESPCL shows excellent migration resistance with a weight loss of less than 0.6% in a liquid phase, whereas DEHP migrated out of PVC/DEHP into a liquid phase with a weight loss of about 10%.