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Scandium-catalyzed copolymerization of myrcene with ethylene and propylene: convenient syntheses of versatile functionalized polyolefins†
Polymer Chemistry ( IF 4.1 ) Pub Date : 2018-02-07 00:00:00 , DOI: 10.1039/c8py00039e Xiaorui Ren 1, 2, 3, 4, 5 , Fang Guo 1, 2, 3, 4, 5 , Hongran Fu 1, 2, 3, 4, 5 , Yunyun Song 1, 2, 3, 4, 5 , Yang Li 1, 2, 3, 4, 5 , Zhaomin Hou 1, 2, 3, 4, 5
Polymer Chemistry ( IF 4.1 ) Pub Date : 2018-02-07 00:00:00 , DOI: 10.1039/c8py00039e Xiaorui Ren 1, 2, 3, 4, 5 , Fang Guo 1, 2, 3, 4, 5 , Hongran Fu 1, 2, 3, 4, 5 , Yunyun Song 1, 2, 3, 4, 5 , Yang Li 1, 2, 3, 4, 5 , Zhaomin Hou 1, 2, 3, 4, 5
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The copolymerization of myrcene with ethylene and propylene using half-sandwich scandium complexes bearing various auxiliary ligands has been examined. In the copolymerization of myrcene with ethylene, the THF-free aminobenzyl scandium complex bearing a relatively small cyclopentadienyl ligand (C5H5)Sc(CH2C6H4NMe2-o)2 (1) afforded diblock myrcene–ethylene copolymers with a high myrcene content and predominant cis-1,4-structure, whereas the analogous scandium complex with a larger cyclopentadienyl ligand (C5Me4SiMe3)Sc(CH2C6H4NMe2-o)2 (2) afforded multiblock myrcene–ethylene copolymers with different myrcene contents and a predominant 3,4-structure. In contrast, the THF-containing trimethylsilylmethyl scandium complex (C5Me4SiMe3)Sc(CH2SiMe3)2(THF) (3) afforded alternating myrcene–ethylene copolymers on using a sufficient amount of myrcene. More remarkably, the terpolymerization of myrcene with ethylene and propylene has also been realized using a scandium complex 3, yielding a new family of myrcene-based ethylene–propylene–diene rubbers (EPDM) with versatile C![[double bond, length as m-dash]](https://www.rsc.org/images/entities/char_e001.gif)
C double bonds in the main and side chains. By efficiently transforming the CC double bonds of the resulting myrcene-based EPDM into other polar groups, versatile functionalized polyolefins such as thioacetic acid, sulfoacid, and epoxidized, hydroxylated–chlorinated and furan functionalized polyolefins were obtained.
中文翻译：
rc催化的月桂烯与乙烯和丙烯共聚：通用官能化聚烯烃的便捷合成†
已经研究了使用带有各种辅助配体的半三明治scan络合物使月桂烯与乙烯和丙烯共聚。在月桂烯与乙烯的共聚中，带有相对较小的环戊二烯基配体（C 5 H 5）Sc（CH 2 C 6 H 4 NMe 2 - o）2（1）的无THF氨基苄基benzyl络合物提供了二嵌段月桂烯-乙烯共聚物具有较高的月桂烯含量和主要的-1,4-顺式结构，而类似的complex配合物具有较大的环戊二烯基配体（C 5 Me 4 SiMe 3）Sc（CH 2 C 6 H 4 NMe 2 - o）2（2）提供了具有不同月桂烯含量和主要3,4-结构的多嵌段月桂烯-乙烯共聚物。相反，含THF的三甲基甲硅烷基甲基scan络合物（C 5 Me 4 SiMe 3）Sc（CH 2 SiMe 3）2（THF）（3）在使用足够量的月桂烯时提供交替的月桂烯-乙烯共聚物。更值得注意的是，月桂烯与乙烯和丙烯的三元聚合也已经通过使用complex络合物3实现了。，得到了新的月桂烯基乙烯-丙烯-二烯橡胶（EPDM）系列，在主链和侧链中具有通用的C C双键。通过有效地将所得的基于月桂烯的三元乙丙橡胶的C C双键转变为其他极性基团，可以获得通用的官能化聚烯烃，例如硫代乙酸，磺酸和环氧化，羟基化氯化和呋喃官能化的聚烯烃。
更新日期：2018-02-07
C double bonds in the main and side chains. By efficiently transforming the CC double bonds of the resulting myrcene-based EPDM into other polar groups, versatile functionalized polyolefins such as thioacetic acid, sulfoacid, and epoxidized, hydroxylated–chlorinated and furan functionalized polyolefins were obtained.
中文翻译：
rc催化的月桂烯与乙烯和丙烯共聚：通用官能化聚烯烃的便捷合成†
已经研究了使用带有各种辅助配体的半三明治scan络合物使月桂烯与乙烯和丙烯共聚。在月桂烯与乙烯的共聚中，带有相对较小的环戊二烯基配体（C 5 H 5）Sc（CH 2 C 6 H 4 NMe 2 - o）2（1）的无THF氨基苄基benzyl络合物提供了二嵌段月桂烯-乙烯共聚物具有较高的月桂烯含量和主要的-1,4-顺式结构，而类似的complex配合物具有较大的环戊二烯基配体（C 5 Me 4 SiMe 3）Sc（CH 2 C 6 H 4 NMe 2 - o）2（2）提供了具有不同月桂烯含量和主要3,4-结构的多嵌段月桂烯-乙烯共聚物。相反，含THF的三甲基甲硅烷基甲基scan络合物（C 5 Me 4 SiMe 3）Sc（CH 2 SiMe 3）2（THF）（3）在使用足够量的月桂烯时提供交替的月桂烯-乙烯共聚物。更值得注意的是，月桂烯与乙烯和丙烯的三元聚合也已经通过使用complex络合物3实现了。，得到了新的月桂烯基乙烯-丙烯-二烯橡胶（EPDM）系列，
在主链和侧链中具有通用的C C双键。通过有效地将所得的基于月桂烯的三元乙丙橡胶的C C双键转变为其他极性基团，可以获得通用的官能化聚烯烃，例如硫代乙酸，磺酸和环氧化，羟基化氯化和呋喃官能化的聚烯烃。
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