Catalytic Chain Transfer Polymerization to Functional Reactive End Groups for Controlled Free Radical Growth
Catalytic Chain Transfer Polymerization to Functional Reactive End Groups for Controlled Free Radical Growth
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催化链转移聚合至功能性反应性端基以控制自由基生长
DOI：
10.1021/acs.macromol.0c00241
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发表时间：
2020
期刊：
影响因子：
5.5
通讯作者：
Stefan
中科院分区：
文献类型：
--
作者：
Stadler;Sonja M;Göttker-Schnetmann;Amelie S;Fischer;Stephan R. R;Mecking;Stefan
烷氧胺功能化硅烷作为链转移试剂在阳离子钯二亚胺配合物催化的乙烯聚合中起作用，对生产效率和产率没有明显的不利影响。在通过β-氢化物消除的有限链转移条件下，该方法高度选择性地产生端烷氧胺超支化聚乙烯（PEs）和每个活性金属位点多个（最多5个）功能化PE链。化学计量核磁共振光谱研究表明，第一个链转移产生了一个饱和的链端，而所有随后的聚合物链都是由（功能化的）硅基引发的。通过这种方法得到的烷氧胺官能化超支化pe是氮氧基介导自由基聚合的合适前体。这允许利用不同的链生长机制（催化插入/自由基）生成pe -聚丙烯酸酯和pe -聚苯乙烯嵌段共聚物。
Alkoxyamine-functionalized silane functions as a chain transfer reagent in ethylene polymerization catalyzed by cationic palladium diimine complexes, without significant adverse effects in productivity or yield. Under conditions of limited chain transfer by β-hydride elimination, this approach highly selectively results in alkoxyamine-terminated hyperbranched polyethylenes (PEs) and multiple (up to 5) functionalized PE chains per active metal site. Stoichiometric NMR spectroscopic investigations indicate that the first chain transfer generates a saturated chain end, while all following polymer chains are initiated by (functionalized) silyl groups. Alkoxyamine-functionalized hyperbranched PEs obtained by this approach are suitable precursors for nitroxide-mediated radical polymerizations. This allows for harnessing different chain growth mechanisms (catalytic insertion/free radical) for generation of PE–polyacrylate and PE–polystyrene block copolymers.
影响因子：
2.8
作者：
Michael G. Hyatt;Damien Guironnet
通讯作者：
Michael G. Hyatt;Damien Guironnet
硫醇末端官能化聚乙烯
DOI：
--
发表时间：
2010
期刊：
影响因子：
--
作者：
Jérôme Mazzolini;Ilham Mokthari;Rémi Briquel;O. Boyron;F. Delolme;V. Monteil;D. Bertin;D. Gigmes;F. D’Agosto;C. Boisson
通讯作者：
C. Boisson