Double post-polymerization modification

Functionalization of polysilanes by chemical modification (post-polymerization) was covered in COMC II (1995) (chapter Organopolysilanes, p 101), where the formation of precursor polysilanes with potentially functionalizable side groups such as chloride, type 34 (via HCI/AICI3 chlorodephenylation of PMPS), 6 triflate, type 35 (via triflate replacement of phenyl groups)135,137 or alkyl halide (via chloromethylation of phenyl groups,138,139 type 36, or addition of HC1 or HBr to double bonds140) was discussed. Four other precursor polysilanes, which utilize the reactivity of the Si-Cl or Si-H bond, have been successfully applied in functionalization since COMC (1995) perchloropolysilane, 17 (see Section 3.11.4.2.2.(i) for synthesis),103 poly[methyl(H)silylene-f >-methylphenylsilylene],... 

Abstract Polybutadiene is a versatile starting material for polymer-analogous reactions because of the high cmitent of easily accessed double bonds. It is a large scale polymeric product with relatively low costs. Polybutadiene may be tuned in its properties by consecutive chemical functionalizations to expand its range of applications. The polarity decreases content double bond hydrogenation and may be increased by the addition of heteroatoms to the olelinic entities. The functionalized of double bonds (e.g. to epoxides, aldehydes, carboxylates, hydroxyls or amines) opens the option of subsequent reactions in particular with nucleophilic reagents. This article focuses on post-modifications of polybutadiene homo-polymers by such sequential reactions and shows their relevance to applications. 

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