Synthesis and characterization of novel acid-sensitive tert-butyl methacrylate and isobutyl methacrylate containing star-shaped polymers

Timothy Edward Long, Lars Kilian, Zhen He Wang, Alan R. Esker

Research output: Contribution to journalConference article

4 Citations (Scopus)

Abstract

Star-shaped polymers containing poly(isobutyl methacrylate) (iBMA) and poly(tert-butyl methacrylate) (t-BMA) arms coupled to a 2,5-dimethyl-2,5-hexanediol dimethacrylate (DHDMA) core were synthesized using arm-first living anionic polymerization. Gel permeation chromatography (GPC) indicated that coupling efficiencies were high and coupled products exhibited a monomodal molecular weight distribution. The star-shaped polymer number-average molecular weights were 8-10 times higher than the precursor arm molecular weights. The ratio of coupling reagent to living chain end concentration controlled the molecular weight of the star-shaped polymer and the number of coupled arms. The molecular weight distributions of the star-shaped polymers ranged from 1.5-2.0. Due to the labile tertiary-butyl esters contained in the DHDMA cores, these star-shaped polymers were readily hydrolyzed in the presence of acid catalysts. For example, poly(iBMA) star-shaped polymers were hydrolytically stable at 25 °C and hydrolyzed readily at 65 °C in the presence of hydrochloric acid. In addition, the poly(t-BMA) containing star-shaped polymers degraded under similar conditions. The degradation process for the iBMA and t-BMA containing star-shaped polymers was confirmed using 1H NMR spectroscopy, and poly(iBMA)-block-poly(methacrylic acid) and poly(methacrylic acid) were obtained, respectively.

Original languageEnglish
Pages (from-to)65-74
Number of pages10
JournalProceedings of SPIE - The International Society for Optical Engineering
Volume4512
DOIs
Publication statusPublished - 2001 Dec 1
Externally publishedYes
EventComplex Adaptive Structures - Hutchinson Island, FL, United States
Duration: 2001 Jun 42001 Jun 6

Fingerprint

Methacrylates
Stars
Star
Polymers
Synthesis
stars
acids
Acids
polymers
molecular weight
synthesis
Weight Distribution
Molecular weight
Molecular weight distribution
gel chromatography
Living polymerization
Anionic polymerization
butyl methacrylate
Hydrochloric Acid
hydrochloric acid

Keywords

  • Anionic polymerization
  • Coupling
  • Degradable
  • Hydrolysis
  • Methacrylate
  • Star-shaped polymer
  • Synthesis

ASJC Scopus subject areas

  • Electrical and Electronic Engineering
  • Condensed Matter Physics

Cite this

Synthesis and characterization of novel acid-sensitive tert-butyl methacrylate and isobutyl methacrylate containing star-shaped polymers. / Long, Timothy Edward; Kilian, Lars; Wang, Zhen He; Esker, Alan R.

In: Proceedings of SPIE - The International Society for Optical Engineering, Vol. 4512, 01.12.2001, p. 65-74.

Research output: Contribution to journalConference article

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abstract = "Star-shaped polymers containing poly(isobutyl methacrylate) (iBMA) and poly(tert-butyl methacrylate) (t-BMA) arms coupled to a 2,5-dimethyl-2,5-hexanediol dimethacrylate (DHDMA) core were synthesized using arm-first living anionic polymerization. Gel permeation chromatography (GPC) indicated that coupling efficiencies were high and coupled products exhibited a monomodal molecular weight distribution. The star-shaped polymer number-average molecular weights were 8-10 times higher than the precursor arm molecular weights. The ratio of coupling reagent to living chain end concentration controlled the molecular weight of the star-shaped polymer and the number of coupled arms. The molecular weight distributions of the star-shaped polymers ranged from 1.5-2.0. Due to the labile tertiary-butyl esters contained in the DHDMA cores, these star-shaped polymers were readily hydrolyzed in the presence of acid catalysts. For example, poly(iBMA) star-shaped polymers were hydrolytically stable at 25 °C and hydrolyzed readily at 65 °C in the presence of hydrochloric acid. In addition, the poly(t-BMA) containing star-shaped polymers degraded under similar conditions. The degradation process for the iBMA and t-BMA containing star-shaped polymers was confirmed using 1H NMR spectroscopy, and poly(iBMA)-block-poly(methacrylic acid) and poly(methacrylic acid) were obtained, respectively.",
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AU - Kilian, Lars

AU - Wang, Zhen He

AU - Esker, Alan R.

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N2 - Star-shaped polymers containing poly(isobutyl methacrylate) (iBMA) and poly(tert-butyl methacrylate) (t-BMA) arms coupled to a 2,5-dimethyl-2,5-hexanediol dimethacrylate (DHDMA) core were synthesized using arm-first living anionic polymerization. Gel permeation chromatography (GPC) indicated that coupling efficiencies were high and coupled products exhibited a monomodal molecular weight distribution. The star-shaped polymer number-average molecular weights were 8-10 times higher than the precursor arm molecular weights. The ratio of coupling reagent to living chain end concentration controlled the molecular weight of the star-shaped polymer and the number of coupled arms. The molecular weight distributions of the star-shaped polymers ranged from 1.5-2.0. Due to the labile tertiary-butyl esters contained in the DHDMA cores, these star-shaped polymers were readily hydrolyzed in the presence of acid catalysts. For example, poly(iBMA) star-shaped polymers were hydrolytically stable at 25 °C and hydrolyzed readily at 65 °C in the presence of hydrochloric acid. In addition, the poly(t-BMA) containing star-shaped polymers degraded under similar conditions. The degradation process for the iBMA and t-BMA containing star-shaped polymers was confirmed using 1H NMR spectroscopy, and poly(iBMA)-block-poly(methacrylic acid) and poly(methacrylic acid) were obtained, respectively.

AB - Star-shaped polymers containing poly(isobutyl methacrylate) (iBMA) and poly(tert-butyl methacrylate) (t-BMA) arms coupled to a 2,5-dimethyl-2,5-hexanediol dimethacrylate (DHDMA) core were synthesized using arm-first living anionic polymerization. Gel permeation chromatography (GPC) indicated that coupling efficiencies were high and coupled products exhibited a monomodal molecular weight distribution. The star-shaped polymer number-average molecular weights were 8-10 times higher than the precursor arm molecular weights. The ratio of coupling reagent to living chain end concentration controlled the molecular weight of the star-shaped polymer and the number of coupled arms. The molecular weight distributions of the star-shaped polymers ranged from 1.5-2.0. Due to the labile tertiary-butyl esters contained in the DHDMA cores, these star-shaped polymers were readily hydrolyzed in the presence of acid catalysts. For example, poly(iBMA) star-shaped polymers were hydrolytically stable at 25 °C and hydrolyzed readily at 65 °C in the presence of hydrochloric acid. In addition, the poly(t-BMA) containing star-shaped polymers degraded under similar conditions. The degradation process for the iBMA and t-BMA containing star-shaped polymers was confirmed using 1H NMR spectroscopy, and poly(iBMA)-block-poly(methacrylic acid) and poly(methacrylic acid) were obtained, respectively.

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