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- W2898060868 abstract "The synthesis of charged polymers often requires the polymerization of protected monomers, followed by a polymer-analogous reaction to the polyelectrolyte product. We present a mild, facile method to cleave tert-butyl groups from poly(tert-butyl acrylate) blocks that yields poly(acrylic acid) (pAA) blocks free of traces of the ester. The reaction utilizes a slight excess of HCl in hexafluoroisopropanol (HFIP) at room temperature and runs to completion within 4 h. We compare deprotection in HFIP with the common TFA/DCM method and show that the latter does not yield clean pAA. We show the effect of complete tert-butyl cleavage on a ABA triblock copolymer, where poly(N-isopropylacrylamide) (pNIPAM) is A and pAA is B, by means of viscosimetry, DLS, and SAXS on solutions above overlap. The pNIPAM blocks dehydrate, and their increased self-affinity above the lower critical solution temperature (LCST) results in network formation by the triblocks. This manifests itself as an increase in viscosity and a slowing down of the first-order correlation function in light scattering. However, this stickering effect manifests itself exclusively when the pAA block is tert-butyl-free. Additionally, SAXS shows that the conformational properties of tert-butyl-free pAA copolymers are markedly different from those with residual esters. Thus, we illustrate a surprising effect of hydrophobic impurities that act across blocks and assert the usefulness of HCl/HFIP in pAA synthesis." @default.
- W2898060868 created "2018-10-26" @default.
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- W2898060868 date "2018-10-12" @default.
- W2898060868 modified "2023-10-15" @default.
- W2898060868 title "Rapid and Quantitative De-<i>tert</i>-butylation for Poly(acrylic acid) Block Copolymers and Influence on Relaxation of Thermoassociated Transient Networks" @default.
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- W2898060868 doi "https://doi.org/10.1021/acs.macromol.8b01440" @default.
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