Organic-metalloblock copolymers via photocontrolled living anionic ring-opening polymerization
Organic-metalloblock copolymers via photocontrolled living anionic ring-opening polymerization
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DOI：
10.1039/c1py00298h
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发表时间：
2011-01-01
影响因子：
4.6
通讯作者：
Manners, Ian
中科院分区：
文献类型：
--
作者：
Chabanne, Laurent;Matas, Inmaculada;Manners, Ian
报道了一种通过光控开环聚合（ROP）制备含聚二茂铁基硅烷（PFS）金属嵌段的有机-金属有机二嵌段共聚物的新方法。以聚苯乙烯（PS）均聚物（1）为大分子引发剂，对二茂铁硅烷[Fe（eta-C5 H4）（2）Si {CtBu}（2）] 3a和[Fe（eta-C5 H4）（2）Si（Me）（C-CSiMe 3）] 3b进行了光控ROP反应，得到了分子量和嵌段比可控、多分散性低（PDI < 1.2）的二嵌段共聚物。将嵌段共聚物PSm-b-[Fe（eta-C5 H4）（2）Si{C-C（t-Bu）}（2）]（n）4与[Co-2（CO）（8）]进行簇合，形成高度金属化的PSm-b-[Fe（eta-C5 H4）（2）Si{Co-2（CO）（6）C-2（t-Bu）}（2）]（n）（PS-b-（Co-PFS），7）。PSm-b-[Fe通过PSm-b-[Fe]的选择性脱硅反应制备了（eta-C5 H4）（2）Si（Me）（CH）]（n）6（eta-C5H4）（2）Si（Me）然后在作为HCl受体的胺的存在下，使（C CSiMe 3）]（n）5与ClAuP（n-Bu）（3）反应，得到PSm-b-[Fe（eta-C5 H4）（2）Si（Me）{C CAuP（n-Bu）（3）}]（n）（PS-b-（Au-PFS），8）。对这些材料在薄膜中自组装的初步研究表明，在有机基质中具有富含金属的纳米畴的相分离。
A new method for the preparation of organic-organometallic diblock copolymers including a polyferrocenylsilane (PFS) metalloblock through photocontrolled ring-opening polymerization (ROP) is reported. Polystyrene (PS) homopolymers end-capped with a cyclopentadienyl group (1) were used as macroinitiators for the photocontrolled ROP of sila[1]ferrocenophanes [Fe(eta-C5H4)(2)Si {C CtBu}(2)] 3a and [Fe(eta-C5H4)(2)Si(Me)(C CSiMe3)] 3b to afford diblock copolymers with controlled molecular weights and block ratios, as well as low polydispersities (PDI < 1.2). Block copolymer PSm-b-[Fe(eta-C5H4)(2)Si{C C(t-Bu)}(2)](n) 4 was clusterized with [Co-2(CO)(8)], forming the highly metallized PSm-b-[Fe(eta-C5H4)(2)Si{Co-2(CO)(6)C-2(t-Bu)}(2)](n) (PS-b-(Co-PFS), 7). The diblock PSm-b-[Fe(eta-C5H4)(2)Si(Me)(C CH)](n) 6 was prepared by selective desilylation of PSm-b-[Fe(eta-C5H4)(2)Si (Me)(C CSiMe3)](n) 5 was then reacted with ClAuP(n-Bu)(3) in the presence of an amine as HCl acceptor to afford PSm-b-[Fe(eta-C5H4)(2)Si(Me){C CAuP(n-Bu)(3)}](n) (PS-b-(Au-PFS), 8). Preliminary studies on the self-assembly of these materials in thin films showed phase separation with metal-rich nanodomains within an organic matrix.