Title page for ETD etd-09192007-141158


Type of Document Dissertation
Author Mao, Min
URN etd-09192007-141158
Title Synthesis and Characterization of Highly Functional Substituted Stilbene Copolymers and Semi-crystalline Poly(aryl ether sulfone)s
Degree PhD
Department Chemistry
Advisory Committee
Advisor Name Title
Turner, S. Richard Committee Chair
Davis, Richey M. Committee Member
Dillard, John G. Committee Member
Esker, Alan R. Committee Member
Long, Timothy E. Committee Member
Keywords
  • poly(aryl ether sulfone)
  • birefringence
  • polyampholyte
  • rod-coil block copolymer
  • alternating copolymerization
  • stilbene
Date of Defense 2007-09-05
Availability unrestricted
Abstract
Synthesis and Characterization of Highly Functional Substituted Stilbene Copolymers and Semi-crystalline Poly(aryl ether sulfone)s Min Mao (ABSTRACT) Novel, highly functional rod-like copolymers have been synthesized by alternating copolymerization of N, N, N’, N’-tetraalkyl-4, 4’-diaminostilbenes (TDAS) with maleic anhydride. Dynamic light scattering, 2H solid state NMR and persistence length measurement reveal high chain rigidity of the polymer backbone. Double quantum heteronuclear local field solid state NMR spectroscopy (2Q-HLF Solid State NMR) has been employed to investigate the chain structure of 13C labelled copolymer. The torsional angle of the H-13C-13C-H part of the anhydride ring was zero degrees, indicating an all cis configuration of the H-13C-13C-H moiety of the anhydride ring.

Rod-coil block copolymers containing rigid polyampholyte blocks were designed and synthesized by addition-fragmentation chain transfer (RAFT) copolymerization. The rigid polyampholytes blocks were formed by hydrolysis of alternating copolymers and the flexible coil block consists of poly(oligo(ethylene glycol) methacrylate). The rod-coil block copolymers form polyion complex (PIC) aggregates even when the polyampholyte blocks are charge imbalanced. The aggregates did not dissociate upon the addition of high concentrations of NaCl unlike the dissociation of flexible polyampholytes in NaCl solution. These unique solution properties are induced by “like-charge attractions” of the rigid polyampholytic alternating copolymer chains.

An example, of what is birefringent to be a novel class of material, has been prepared which enables the control of the birefringence of a polymer film by controlling the rotation of aromatic groups pendant to the polymer backbone.

A linear rigid bisphenol monomer, 4,4’-dihydroxyterphenyl (DHTP), has been incorporated into poly(aryl ether sulfone)s (PAES) in a study to impart crystallization to these amorphous polymers. Three bisphenols, 4, 4’-isopropylidenediphenol, 4, 4’-(hexafluoroisopropylidene)diphenol and 4,4’-dihydroxybiphenyl have been copolymerized with DHTP and dichlorodiphenylsulfone. Only the segmented polysulfone containing 50% BP and 50% DHTP was semi-crystalline. This PAES had a melting temperature (Tm) 320oC in the first heating cycle of a DSC measurement and the presence of crystallites was confirmed by wide angle X-ray diffraction (WAXS).

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