Synthesis of multisegmented block copolymer by Friedel–Crafts hydroxyalkylation polymerization

Abstract

Friedel–Crafts (FC) polycondensation of 1,4-dimethoxybenzene with 4-substituted benzaldehyde species was used to prepare telechelic oligomers and high-molar-mass multisegmented block copolymers.

Synthesis of Linear Polymers in High Molecular Weights via Reaction-Enhanced Reactivity of Intermediates Using Friedel–Crafts Polycondensation

“…For instance, polymerizations of DMB with various BA monomers afforded a library of triarylmethane-backboned oligomers with nitro, fluoro, alkyl ester, dimethylamino, and tertbutyl pendant functional groups (Scheme 2B). 30 A mixture of several oligomers was used as macromonomers in a subsequent polymerization to produce MSBCPs with tunable compositions and properties, such as tunable glass transition temperature and surface contact angle. The features identified during the synthesis of these MSBCPs, including the facile reaction setup, tunable segment lengths, and substituent groups in each block, demonstrate promising applicability of these triarylmethanebackboned polymers and copolymers for use in specialty membrane applications.…”

“…Thus, possibility arises that different oligomers could be mixed together being used as macromonomers for reaction with additional BA monomers to construct a multisegmented block copolymer (MSBCP) that carries various functional substituent groups along the polymer backbone. For instance, polymerizations of DMB with various BA monomers afforded a library of triarylmethane-backboned oligomers with nitro, fluoro, alkyl ester, dimethylamino, and tert -butyl pendant functional groups (Scheme B) . A mixture of several oligomers was used as macromonomers in a subsequent polymerization to produce MSBCPs with tunable compositions and properties, such as tunable glass transition temperature and surface contact angle.…”

Polymer Synthesis Based on Self‐Accelerating 1,3‐Dipolar Cycloaddition Click Reactions†

“…To date, several stoichiometric imbalance‐promoted homogeneous step polymerization methods have been developed based on varied self‐accelerating reactions. They include palladium‐catalyzed allylation [ 53 ] and etherification polymerization, [ 54 ] palladium‐catalyzed Suzuki‐Miyaura and Stille coupling polycondensations, [ 13,55‐56 ] rhodium‐catalyzed oxidative polycoupling of internal diynes and phenylpyrazole [ 14 ] or arylboronic acids, [ 57 ] polycondensation of Friedel−Crafts acylation [ 17,58 ] or hydroxyalkylation reaction, [ 59‐61 ] poly‐Radziszewski reaction, [ 16 ] polycondensations of dibromomethane and 4,4’‐thiobisbenzenethiol [ 62 ] or bisphenol A, [ 63 ] and polycondensation of bisphenol A with 2,2‐dichloro‐1,3‐benzodioxole. [ 64 ] These stoichiometric imbalance‐ promoted homogeneous step polymerization methods have been summarized in recent review papers.…”

Cascade synthesis of architecture-transformable thermo-labile multisite multiblock copolymers

“…In general, MMBPs and their derivatives can be synthesized by some strategies such as chain polymerization [44][45][46][47][48][49][50] and stepwise polymerization/linking reaction. [51][52][53][54][55][56][57][58][59][60][61][62][63][64] Chain polymerization via "living"/controlled procedures allows to synthesize well-defined MMBPs with controlled block order and relatively low dispersity, while other methods using presynthesized telechelic polymers or reactive precursors usually afford MMBPs with predetermined block order and relatively high dispersity. MMBPs can be potentially synthesized by either multi-step or one-pot 24,31,33,[59][60][61][62][63][64] route.…”

“…40–43 As reactive linkers and side groups are incorporated into multiblock copolymers, the resultant multisite multiblock copolymers (MMBPs) may exhibit more flexible topological transformations among linear, cyclic, branched and single-chain folding architectures. 44–64 In general, MMBPs and their derivatives can be synthesized by some strategies such as chain polymerization 44–50 and stepwise polymerization/linking reaction. 51–64 Chain polymerization via “living”/controlled procedures allows to synthesize well-defined MMBPs with controlled block order and relatively low dispersity, while other methods using presynthesized telechelic polymers or reactive precursors usually afford MMBPs with predetermined block order and relatively high dispersity.…”