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聚合物纳米反应器内的配位化学：两亲性核壳聚合物胶乳中的金属迁移与交叉交换

Coordination Chemistry inside Polymeric Nanoreactors: Metal Migration and Cross-Exchange in Amphiphilic Core-Shell Polymer Latexes.

作者信息

Chen Si, Manoury Eric, Gayet Florence, Poli Rinaldo

机构信息

CNRS, LCC (Laboratoire de Chimie de Coordination), Université de Toulouse, UPS, INPT, 205 Route de Narbonne, BP 44099, F-31077 Toulouse Cedex 4, France.

Institut Universitaire de France, 103, bd Saint-Michel, 75005 Paris, France.

出版信息

Polymers (Basel). 2016 Jan 22;8(2):26. doi: 10.3390/polym8020026.

DOI:10.3390/polym8020026
PMID:30979121
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC6432602/
Abstract

A well-defined amphiphilic core-shell polymer functionalized with bis(-methoxy-phenylphosphino)phenylphosphine (BMOPPP) in the nanogel (NG) core has been obtained by a convergent RAFT polymerization in emulsion. This BMOPPP@NG and the previously-reported TPP@NG (TPP = triphenylphosphine) and core cross-linked micelles (L@CCM; L = TPP, BMOPPP) having a slightly different architecture were loaded with [Rh(acac)(CO)₂] or [RhCl(COD)]₂ to yield [Rh(acac)(CO)(L@Pol)] or [RhCl(COD)(L@Pol)] (Pol = CCM, NG). The interparticle metal migration from [Rh(acac)(CO)(TPP@NG)] to TPP@NG is fast at natural pH and much slower at high pH, the rate not depending significantly on the polymer architecture (CCM NG). The cross-exchange using [Rh(acac)(CO)(BMOPPP@Pol)] and [RhCl(COD)(TPP@Pol)] (Pol = CCM or NG) as reagents at natural pH is also rapid ( 1 h), although slower than the equivalent homogeneous reaction on the molecular species (<5 min). On the other hand, the subsequent rearrangement of [Rh(acac)(CO)(TPP@Pol)] and [RhCl(COD)(TPP@Pol)] within the TPP@Pol core and of [Rh(acac)(CO)(BMOPPP@Pol)] and [RhCl(COD)(BMOPPP@Pol)] within the BMOPPP@Pol core, leading respectively to [RhCl(CO)(TPP@Pol)₂] and [RhCl(CO)(BMOPPP@Pol)₂], is much more rapid (<30 min) than on the corresponding homogeneous process with the molecular species (>24 h).

摘要

通过乳液中的收敛RAFT聚合反应，在纳米凝胶（NG）核中获得了一种用双（-甲氧基-苯基膦基）苯基膦（BMOPPP）功能化的明确的两亲性核壳聚合物。将这种BMOPPP@NG与先前报道的TPP@NG（TPP = 三苯基膦）以及具有稍有不同结构的核交联胶束（L@CCM；L = TPP，BMOPPP）用[Rh(acac)(CO)₂]或[RhCl(COD)]₂负载，得到[Rh(acac)(CO)(L@Pol)]或[RhCl(COD)(L@Pol)]（Pol = CCM，NG）。在自然pH下，[Rh(acac)(CO)(TPP@NG)]到TPP@NG的颗粒间金属迁移很快，而在高pH下则慢得多，该速率对聚合物结构（CCM对NG）的依赖性不显著。在自然pH下，以[Rh(acac)(CO)(BMOPPP@Pol)]和[RhCl(COD)(TPP@Pol)]（Pol = CCM或NG）作为试剂的交叉交换也很快（<1小时），尽管比分子物种上的等效均相反应慢（<5分钟）。另一方面，[Rh(acac)(CO)(TPP@Pol)]和[RhCl(COD)(TPP@Pol)]在TPP@Pol核内以及[Rh(acac)(CO)(BMOPPP@Pol)]和[RhCl(COD)(BMOPPP@Pol)]在BMOPPP@Pol核内分别重排为[RhCl(CO)(TPP@Pol)₂]和[RhCl(CO)(BMOPPP@Pol)₂]，比相应分子物种的均相过程快得多（<30分钟）（>24小时）。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/24f0/6432602/19d69ef2a363/polymers-08-00026-g009.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/24f0/6432602/d2ef6047287b/polymers-08-00026-g001.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/24f0/6432602/fb20c6559387/polymers-08-00026-g002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/24f0/6432602/263d02fd0b18/polymers-08-00026-g003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/24f0/6432602/6927be388085/polymers-08-00026-g004.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/24f0/6432602/3f75244e58a1/polymers-08-00026-g005.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/24f0/6432602/8b58d120c9f7/polymers-08-00026-g006.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/24f0/6432602/e47b39c435a2/polymers-08-00026-g007.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/24f0/6432602/0b8b394807ec/polymers-08-00026-g008.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/24f0/6432602/4e35843b4686/polymers-08-00026-g010.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/24f0/6432602/cd740934f880/polymers-08-00026-g011.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/24f0/6432602/19d69ef2a363/polymers-08-00026-g009.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/24f0/6432602/d2ef6047287b/polymers-08-00026-g001.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/24f0/6432602/fb20c6559387/polymers-08-00026-g002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/24f0/6432602/263d02fd0b18/polymers-08-00026-g003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/24f0/6432602/6927be388085/polymers-08-00026-g004.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/24f0/6432602/3f75244e58a1/polymers-08-00026-g005.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/24f0/6432602/8b58d120c9f7/polymers-08-00026-g006.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/24f0/6432602/e47b39c435a2/polymers-08-00026-g007.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/24f0/6432602/0b8b394807ec/polymers-08-00026-g008.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/24f0/6432602/4e35843b4686/polymers-08-00026-g010.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/24f0/6432602/cd740934f880/polymers-08-00026-g011.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/24f0/6432602/19d69ef2a363/polymers-08-00026-g009.jpg

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J Am Chem Soc. 2014 Jul 23;136(29):10174-85. doi: 10.1021/ja502843f. Epub 2014 Jul 15.
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5
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6
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7
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Polymer catalysts from polymerization catalysts: direct encapsulation of metal catalyst into star polymer core during metal-catalyzed living radical polymerization.源自聚合催化剂的聚合物催化剂：在金属催化的活性自由基聚合过程中将金属催化剂直接封装到星形聚合物核中。
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