Highly cis‐1,4 Selective Living Polymerization of Unmasked Polar 2‐(2‐Methylidenebut‐3‐enyl)Furan and Diels–Alder Addition,Macromolecular Rapid Communications

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Highly cis‐1,4 Selective Living Polymerization of Unmasked Polar 2‐(2‐Methylidenebut‐3‐enyl)Furan and Diels–Alder Addition
Macromolecular Rapid Communications ( IF 4.2 ) Pub Date : 2017-07-27 , DOI: 10.1002/marc.201700227
Shiyu Long _{1,

2} , Fei Lin _{1,

2} , Changguang Yao ₁ , Dongmei Cui ₁

Affiliation

The polymerization of a new polar diene‐based monomer 2‐(2‐methylidenebut‐3‐enyl)furan (MBEF) without masking is achieved by using the bis(phosphino)carbazoleide‐ligated yttrium (Y) alkyl complex upon the activation of [Ph₃C][B(C₆F₅)₄]. Under mild conditions, the polymerizations under the monomer‐to‐Y ratios ranging from 100:1 to 500:1 perform fluently in high yields. The afforded polydienes bearing pendant terminal furan groups have high cis‐1,4‐regularity up to 98.6% and molecular weights close to the theoretic values and narrow polymer dispersity index(PDI) (1.13–1.17) suggesting a livingness polymerization mode. In addition, this novel polydiene is an excellent building block for preparing functional rubber materials. For example, via Diels–Alder addition of furan groups under mild conditions, hydroxyl groups are successfully introduced on the side chains efficiently in a 75% conversion. Furthermore, the copolymerization of polar MBEF and nonpolar isoprene is also successfully realized by the bis(phosphino) carbazoleide‐ligated scandium analog to access furan‐modified cis‐1,4 (>97%) polyisoprene with different MBEF contents (5.3%, 8.7%).

中文翻译：

未掩蔽的极性2-（2-亚甲基亚丁基-3-烯基）呋喃和Diels-Alder加成反应的高度顺式1,4选择性活性聚合

新型的基于极性二烯的单体2-（2-亚甲基亚丁基-3-烯基）呋喃（MBEF）的聚合无需掩蔽，可通过使用双（膦基咔唑基）连接的钇（Y）烷基络合物在[ Ph ₃ C] [B（C ₆ F ₅）₄ ]。在温和的条件下，单体与Y的比率从100：1到500：1的聚合可以高收率地流畅地进行。所提供的带有悬垂末端呋喃基团的聚二烯具有高的顺式-1,4-正则化率高达98.6％，分子量接近理论值，窄的聚合物分散指数（PDI）（1.13-1.17）表明存在活性聚合模式。另外，这种新型的聚二烯是制备功能性橡胶材料的极好基石。例如，通过在温和条件下通过Diels–Alder添加呋喃基团，羟基成功地以75％的转化率成功地引入了侧链。此外，双（膦基）咔唑连接的analog类似物还成功实现了极性MBEF和非极性异戊二烯的共聚，从而获得具有不同MBEF含量的呋喃改性的顺式-1,4（> 97％）聚异戊二烯（5.3％，8.7）％）。

更新日期：2017-07-27

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