Stereoselective copolymerization of 4-(N,N-diphenylamino)styrene and isoprene by a C5H5-ligated scandium catalyst: synthesis of amino-functionalized crystalline styrenic thermoplastic elastomers,Polymer Chemistry

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Stereoselective copolymerization of 4-(N,N-diphenylamino)styrene and isoprene by a C5H5-ligated scandium catalyst: synthesis of amino-functionalized crystalline styrenic thermoplastic elastomers
Polymer Chemistry ( IF 4.1 ) Pub Date : 2019/12/23 , DOI: 10.1039/c9py01789e
Fang Guo _{1,

2,

3,

4,

5} , Lei Jiang _{1,

2,

3,

4,

5} , Kaiying Diao _{1,

2,

3,

4,

5} , Zhaomin Hou _{1,

2,

3,

4,

5}

Affiliation

The copolymerization of 4-(N,N-diphenylamino)styrene (DPAS) with isoprene (IP) as catalyzed by the half-sandwich scandium compound (C₅H₅)Sc(CH₂C₆H₄NMe₂-o)₂ has afforded a new class of amino-functionalized crystalline styrenic thermoplastic elastomers. The homopolymerization of DPAS bearing a sterically demanding diphenylamino group took place in a quasi-living fashion, yielding the amino-functionalized syndiotactic polystyrene by using this scandium catalyst. In the copolymerization of DPAS with IP, the DPAS units started to become incorporated into the polymer chains after IP was almost completely consumed, yielding the diblock copolymers containing a syndiotactic poly(DPAS) block and a cis-1,4-poly(IP) block with controllable block lengths. Addition of a mixture of DPAS and IP to a completed DPAS polymerization reaction mixture in one pot afforded the DPAS–IP–DPAS triblock copolymers with controllable block lengths. The DPAS–IP–DPAS triblock copolymers showed glass transition temperatures (T_g values of −62 °C and 120 °C) and a melting point (T_m value of 219 °C) originating from the cis-1,4-poly(IP) block and syndiotactic poly(DPAS) blocks, respectively.

中文翻译：

通过C5H5连接的scan催化剂对4-（N，N-二苯氨基）苯乙烯和异戊二烯进行立体选择性共聚：氨基官能化的结晶苯乙烯热塑性弹性体的合成

半三明治scan化合物（C ₅ H ₅）Sc（CH ₂ C ₆ H ₄ NMe ₂ - o）₂催化的4-（N，N-N-二苯氨基）苯乙烯（DPAS）与异戊二烯（IP）的共聚已经提供了新型的氨基官能化的结晶苯乙烯类热塑性弹性体。带有空间要求的二苯基氨基的DPAS的均聚以准活性方式发生，通过使用这种scan催化剂得到氨基官能化的间同立构聚苯乙烯。在DPAS与IP的共聚过程中，IP几乎被完全消耗后，DPAS单元开始被并入聚合物链中，从而得到含有间同立构的聚（DPAS）嵌段和顺式的顺式二嵌段共聚物。具有可控制块长度的-1,4-poly（IP）块。在一个罐中将DPAS和IP的混合物添加到一个完整的DPAS聚合反应混合物中，即可得到具有可控制嵌段长度的DPAS-IP-DPAS三嵌段共聚物。DPAS-IP-DPAS三嵌段共聚物的玻璃化转变温度（T _g值为-62°C和120°C）和熔点（T _m值为219°C）源自顺式-1,4-聚（ IP）块和间规poly（DPAS）块。

更新日期：2020-02-19

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