Controlled Chain Walking for the Synthesis of Thermoplastic Polyolefin Elastomers: Synthesis, Structure, and Properties
Controlled Chain Walking for the Synthesis of Thermoplastic Polyolefin Elastomers: Synthesis, Structure, and Properties
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DOI：
10.1021/acs.macromol.6b01567
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发表时间：
2016-09-27
期刊：
影响因子：
5.5
通讯作者：
Coates, Geoffrey W.
中科院分区：
文献类型：
--
作者：
O'Connor, Kyle S.;Watts, Annabelle;Coates, Geoffrey W.
与橡胶等化学交联弹性体不同，热塑性弹性体是有吸引力的材料，因为它们能够熔融加工、重复使用和回收。我们报告了聚烯烃基热塑性弹性体嵌段共聚物的合成和机械性能。采用简单的一锅法，使用活性芳基萘基-α-二亚胺Ni(II)“三明治”络合物，从1-癸烯生成高结晶度硬嵌段，从乙烯生成低结晶度软嵌段。可以获得各种嵌段结构，从二嵌段到七嵌段共聚物。还合成了1-癸烯和乙烯的统计共聚物用于比较。所有所得聚合物均表现为弹性体，其特性可通过硬嵌段和软嵌段组成、嵌段结构和聚合溶剂进行调节。三嵌段共聚物的断裂应变值高达 750%，弹性应变恢复率高达 85%。有趣的是，统计共聚物显示断裂应变值高达 1120%，弹性应变恢复高达 77%。进行蠕变实验以确定这些材料的变形弹性。研究发现，较高嵌段结构（三嵌段及以上）比较低嵌段结构（二嵌段和统计嵌段）具有更大的抗应变诱导变形能力。
Thermoplastic elastomers are attractive materials because of their ability to be melt-processed, reused, and recycled, unlike chemically cross-linked elastomers such as rubber. We report the synthesis and mechanical properties of polyolefin-based thermoplastic elastomer block copolymers. A simple one-pot procedure is employed, using a living arylnaphthyl-alpha-diimine Ni(II) "sandwich" complex to generate high crystallinity hard blocks from 1-decene and low crystallinity soft blocks from ethylene. Various block structures are accessed, ranging from a diblock up to a heptablock copolymer. Statistical copolymers of 1-decene and ethylene are also synthesized for comparison. All resulting polymers behave as elastomers, with properties that modulate with hard and soft block composition, block architecture, and polymerization solvent. Triblock copolymers demonstrate strain at break values up to 750%, with elastic strain recoveries up to 85%. Interestingly, statistical copolymers demonstrate strain at break values upward of 1120% and elastic strain recoveries up to 77%. Creep experiments were performed to determine the resilience of these materials to deformation. It is found that higher block architectures (triblock and above) have greater resistance to strain-induced deformation than lower block architectures (diblock and statistical).