Polymerization, anionic methacryloyl terminated

Living anionic polymerization of 4-vinylphenol was performed after transformation of the phenolic hydroxy group into trialkybilyl ether group and removal of the protection group after polymerization [125]. n-Butyl lithium was used for the synthesis of poly[2-hydroxy-4-methacryloyloxybenzophenone] [61] (102) or HALS terminated poly(methyl methacrylate) [126]. 2-Hydroxy-4-methacryloyl-... 

The synthesis and purification of polystyrene methacryloyl macromonomers (PS-MA) in the molecular weight range Mn= 1000-2000 g mol 1 by living anionic polymerization of styrene (S), termination with ethylene oxide (EO), and subsequent reaction with methacrylic chloride has already been described in detail elsewhere [180] (see also Scheme 16). In this context it has to be emphasized that the hydroxyethyl-terminated PS-MA macromonomer precursor (PS-OH) as obtained after purification of the crude PS-OH by silica column chromatography (cyclohexane/dichloromethane 1/1 v/v) and as charged in the PS-MA synthesis still contains up to about 15 wt-% of non-functionalized polystyrene (PS-H). This PS-H impurity of the PS-MA macromonomer does not interfere with the PS-MA synthesis and the subsequent TBA/PS-MA copolymerization and is easily and conveniently removed from the resulting PTBA-g-PS graft copolymer (see below). 

Anionic polymerization is one of the best methods for the synthesis of well-defined macromonomers. Fimctional initiation or termination by a suitable electrophilic reagents are the best ways for the incorporation of the reactive end groups (50). According to this methodology living polystyryllithium initially reacts with ethylene oxide to form the less reactive alkoxide, followed by the reaction with methacryloyl chloride for the synthesis of the macromonomer (eq. 14) (51). 

An alternative approach to the preparation of graft copolymers involves the use of macromonomers, the most important of which are prepolymers with terminal polymerizable C=C bonds. For example, anionic living polymerization can be used to prepare a prepolymer with a terminal hydroxyl group which can then be reacted with methacryloyl chloride to produce a macromonomer... 

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