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具有窄分子量分布的高1,4-聚丁二烯的合成——一种基于钕的二元催化剂。

Synthesis of high -1,4 polybutadiene with narrow molecular weight distribution a neodymium-based binary catalyst.

作者信息

Liu Jie, Fan Xiaodong, Min Xin, Zhu Xiuzhong, Zhao Na, Wang Zichao

机构信息

The Key Laboratory of Space Applied Physics and Chemistry, Ministry of Education, Shaanxi Key Laboratory of Macromolecular Science and Technology, School of Science, Northwestern Polytechnical University Xi'an 710072 P. R. China

出版信息

RSC Adv. 2018 Jun 14;8(39):21926-21932. doi: 10.1039/c8ra02656d. eCollection 2018 Jun 13.

Abstract

This work explores the synthesis of polybutadiene (PB) with high -1,4 unit content and narrow molecular weight distribution using a neodymium-based complex, consisting of neodymium(iii) trifluoromethane sulfonate (Nd(CFSO)) and coordinated with tris(2-ethylhexyl)phosphate (TOP). The complex's composition and structure are characterized by elemental analysis, XPS and FT-IR. Combined with Al(i-Bu), a binary catalyst is obtained and then applied to initiate the polymerization of butadiene. Results indicate that the catalyst system displays a high catalyst activity and the product polymer (PB) features a high -1,4 content (98.8%) and a remarkably narrow molecular weight distribution ( / = 1.32). Compared with PB initiated by the current well-studied catalyst Nd(CFSO)*3TBP/Al(i-Bu), the Nd(CFSO)*3TOP allows significantly narrowing the molecular weight distribution of the PB, because the Nd(CFSO)*3TOP is more easily dissolved in hexane. Therefore, butadiene was polymerized in a homogenous system and each monomer's polymerization was initiated in the single molecular state.

摘要

本工作探索了使用一种钕基配合物合成具有高1,4-单元含量和窄分子量分布的聚丁二烯(PB),该配合物由三氟甲磺酸钕(Nd(CF₃SO₃)₃)与磷酸三(2-乙基己基)酯(TOP)配位组成。通过元素分析、X射线光电子能谱(XPS)和傅里叶变换红外光谱(FT-IR)对该配合物的组成和结构进行了表征。将其与三异丁基铝(Al(i-Bu)₃)结合,得到一种二元催化剂,然后将其用于引发丁二烯的聚合反应。结果表明,该催化剂体系表现出高催化活性,产物聚合物(PB)具有高1,4-含量(98.8%)和非常窄的分子量分布(Mw/Mn = 1.32)。与目前研究充分的催化剂Nd(CF₃SO₃)₃·3TBP/Al(i-Bu)₃引发的PB相比,Nd(CF₃SO₃)₃·TOP能显著缩窄PB的分子量分布,因为Nd(CF₃SO₃)₃·TOP更易溶于己烷。因此,丁二烯在均相体系中聚合,且每个单体的聚合反应以单分子状态引发。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/82aa/9081107/009912ff725c/c8ra02656d-s1.jpg

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