Living anionic polymerization allows for facile synthesis of block copolymers with a high degree of control over the volume fraction of each block and overall polydispersity. Because this method subjects monomers to highly basic conditions, many functional groups are unable to be used. This work reports the synthesis of an acetal protected hydroxystyrene, 4-(2-tetrahydropyranyloxy)styrene (4OTHPSt), that is able to able to undergo living anionic polymerization and chain extension with a variety of other monomers (styrene, tert-butylstyrene, DMS, POSS). Quantitative deprotection achieved with catalytic HCl or through thermal annealing at elevated temperatures (180oC for 2h). The influence of change in substitution of OTHP group from 4- to 3- position in the monomer on the anionic polymerization and the thermal properties of the resulting polymer is also explored and discussed. For both P3HS-PtBuSt and P4HS-PS bulk assembly with minimum feature sizes in the sub-10nm is demonstrated. More notably, poly(3-hydroxystyrene) [P3HS] exhibits a lower Tg, at 167oC (Tg [P4HS] = 182oC) leading to more accessible conventional thin film processing methods, particularly useful for block copolymer lithography.

Accessing hydroxystyrene-containing block copolymers using living anionic polymerization of 3- and 4-(2-tetrahydropyranyloxy)styrene

249th National Meeting (2015)

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