4.2 Article

Synthesis and Characterization of Double Hydrophilic Block Copolymers Containing Semi-Rigid and Flexible Segments

Journal

Publisher

WILEY-BLACKWELL
DOI: 10.1002/pola.27296

Keywords

reversible addition fragmentation chain transfer (RAFT); stiffness; water-soluble polymers

Funding

  1. National Science Foundation [DMR 9905231, 1206409]
  2. REU grant from NSF DMR [0851662]
  3. Division Of Materials Research
  4. Direct For Mathematical & Physical Scien [1206409, 0851662] Funding Source: National Science Foundation

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3-Methyl-(E)-stilbene (3MSti) and 4-(diethylamino)-(E)-stilbene (DEASti) monomers are synthesized and polymerized separately with maleic anhydride (MAn) in a strictly alternating fashion using reversible addition-fragmentation chain transfer (RAFT) polymerization techniques. The optimal RAFT chain transfer agents (CTAs) for each copolymerization affect the reaction kinetics and CTA compatibilities. Psuedo-first order polymerization kinetics are demonstrated for the synthesis of poly((3-methyl-(E)-stilbene)-alt-maleic anhydride) (3MSti-alt-MAn) with a thiocarbonylthio CTA (methyl 2-(dodecylthiocarbonothioylthio)-2-methylpropionate, TTCMe). In contrast, a dithioester CTA (cumyl dithiobenzoate, CDB) controls the synthesis of poly((4-(diethylamino)-(E)-stilbene)-alt-maleic anhydride) (DEASti-alt-MAn) with pseudo-first order polymerization kinetics. DEASti-alt-MAn is chain extended with 4-acryloylmorpholine (ACMO) to synthesize diblock copolymers and subsequently converted to a double hydrophilic polyampholyte block copolymers (poly((4-(diethylamino)-(E)-stilbene)-alt-maleic acid))-b-acryloylmorpholine) (DEASti-alt-MA)-b-ACMO) via acid hydrolysis. The isoelectric point and dissociation behavior of these maleic acid-containing copolymers are determined using -potential and acid-base titrations, respectively. (c) 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015, 53, 219-227

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