Journal article
Effects of Pairwise, Self-Associating Functional Side Groups on Polymer Solubility, Solution Viscosity, and Mist Control
Macromolecules, Vol.42(4), pp.1380-1391
2009
DOI: 10.1021/ma802058s
Abstract
Solution properties are reported for homologous series of narrowly distributed polymers with systematically varied content of self-associating groups. Anionically polymerized polybutadienes of two lengths (510 and 1250 kg/mol) serve as prepolymers that are modified by incorporation of carboxylic acid side groups using thiol−ene coupling to pendant vinyl groups. Carboxylic acid groups strongly reduce polymer solubility in hydrocarbon solvents, restricting the extent of functionalization that can be examined in single-phase solutions (e.g., in chlorododecane, functionalization must be kept <1.8 mol % even for the shorter of the two backbones). In the single-phase regime, addition of hydrogen bond “stickers” weakly affects solution viscosity. Even at concentrations that produce overlap at the scale of strand length between stickers, viscosity increases are less than 1 order of magnitude. These controlled studies (using functionalized and unmodified polymer homologues of matched, well-defined length) challenge the pre-existing understanding of the rheology of self-associating polymers. The results indicate that effects of intrachain pairing are important beyond the dilute regime—behavior unaccounted for in earlier experimental and theoretical studies. The implications for mist control of aviation fuel are that self-associating polymers of acceptable solubility in the fuel are not superior to nonassociating polymers even at concentrations several times above overlap.
Details
- Title: Subtitle
- Effects of Pairwise, Self-Associating Functional Side Groups on Polymer Solubility, Solution Viscosity, and Mist Control
- Creators
- R. L AMERI DAVID - Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, California 91125, United StatesMing-Hsin WEI - Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, California 91125, United StatesDavid Liu - Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, California 91125, United StatesBrett F BATHEL - NASA Langley Research Center, Hampton, Virginia 23681, GermanyJan P PLOG - Thermo Fisher Scientific, 76227 Karlsruhe, GermanyAlbert RATNER - Department of Mechanical and Industrial Engineering, University of Iowa, Iowa City, Iowa 52242, United StatesJulia A KORNFIELD - Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, California 91125, United States
- Resource Type
- Journal article
- Publication Details
- Macromolecules, Vol.42(4), pp.1380-1391
- Publisher
- American Chemical Society; Washington, DC
- DOI
- 10.1021/ma802058s
- ISSN
- 0024-9297
- eISSN
- 1520-5835
- Language
- English
- Date published
- 2009
- Academic Unit
- Mechanical Engineering
- Record Identifier
- 9984064206002771
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