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Synthesis of Hyperbranched Side-Chain Liquid Crystalline Polyacrylates: Effect of the Architecture on the Rheological Properties

Singh, Anirudha
http://rave.ohiolink.edu/etdc/view?acc_num=akron1207619514

Abstract Details

2008, Doctor of Philosophy, University of Akron, Polymer Science.
A new class of inimer (a molecule containing an initiating site and a polymerizable group in the same molecule) was synthesized from a key halohydrin-based intermediate, which was obtained from serine by a diazotization synthetic route. Polymerization of these inimers resulted in hyperbranched polyacrylates using the concepts of self-condensing vinyl polymerization (SCVP) and atom transfer radical polymerization (ATRP). These hyperbranched polyacrylates contain an ester group attached to every other carbon atom along the polymer backbone, with a non-initiator-containing alkyl ester attached as a free side chain. This is in contrast to previously reported hyperbranched polyacrylates, which have these ester groups along the polymer backbone upon reaction. The architecture of our new polymers is therefore more chemically analogous to linear polyacrylates. We have synthesized and characterized polyacrylates with different ester functional side chains such as alkyl, perfluoro, siloxane, oligo(oxyethylene) and mesogenic side chains . The hyperbranched side-chain liquid crystalline polyacrylates (SCLCPs) were synthesized and characterized intensively by 1H, 13C and 2D nuclear magnetic resonance (NMR) spectroscopy, matrix assisted laser desorption ionization-time of flight (MALDI-TOF) mass spectrometry, differential scanning calorimetry (DSC), polarized optical microscopy (POM), gel permeation chromatography (GPC), light scattering (LS), solution viscosity and rheological techniques. In this work, the structure was qualitatively analyzed by 1H, 13C and 2D NMR techniques to obtain the branching units . Solution properties, e.g. radius of gyration and intrinsic viscosity, thermal properties (glass transition and isotropization temperatures) and rhelogical peroperties (isotropic and anisotropic viscosity) of the hyperbranched side-chain liquid crystalline polyacrylate were compared with those of the linear , three-arm star , six-arm star and comb analogues. This work provides greater flexibility of synthesizing a variety of hyperbranched functional polyacrylates in a single-pot, single-step reaction and helps us in our understanding of the effect on the physical properties due to architectural differences of the polymers.
Coleen Pugh (Advisor)
Stephen Cheng (Committee Chair)
Peter Rinaldi (Committee Member)
Roderic Quirk (Committee Member)
Li Jia (Committee Member)
187 p.
Polymers
Hyperbranched Polyacylates; ATRP; Inimers; Hyperbranched Side-Chain Liquid Crystalline Polyacrylates

Recommended Citations

Citations

  • Singh, A. (2008). Synthesis of Hyperbranched Side-Chain Liquid Crystalline Polyacrylates: Effect of the Architecture on the Rheological Properties [Doctoral dissertation, University of Akron]. OhioLINK Electronic Theses and Dissertations Center. http://rave.ohiolink.edu/etdc/view?acc_num=akron1207619514

    APA Style (7th edition)

  • Singh, Anirudha. Synthesis of Hyperbranched Side-Chain Liquid Crystalline Polyacrylates: Effect of the Architecture on the Rheological Properties. 2008. University of Akron, Doctoral dissertation. OhioLINK Electronic Theses and Dissertations Center, http://rave.ohiolink.edu/etdc/view?acc_num=akron1207619514.

    MLA Style (8th edition)

  • Singh, Anirudha. "Synthesis of Hyperbranched Side-Chain Liquid Crystalline Polyacrylates: Effect of the Architecture on the Rheological Properties." Doctoral dissertation, University of Akron, 2008. http://rave.ohiolink.edu/etdc/view?acc_num=akron1207619514

    Chicago Manual of Style (17th edition)

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© 2008, all rights reserved.
This open access ETD is published by University of Akron and OhioLINK.