Synthesis, characterization and properties of a physically and chemically gelling polymer system using poly (NIPAAm-co-HEMA-acrylate) and poly (NIPAAm-co-cysteamine)

Hanin H. Bearat, Bae Hoon Lee, Jorge Valdez, Brent Vernon

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12 Citations (Scopus)

Abstract

The aim of this work was to develop a simultaneous physically and chemically gelling system using NIPAAm co-polymers. The in situ polymer gel was obtained by synthesizing poly(NIPAAm-co-HEMAacrylate) and poly(NIPAAm-co- cysteamine) through free radical polymerization and further nucleophilic substitution. The purpose of the dual gelation is that physical gelation would take place at higher temperatures as the NIPAAm chains associate, while chemical gelation would occur through a Michael-type addition reaction, resulting in a cross-link forming through a nucleophilic attack of the thiolate on the acrylate. The structure of each co-polymer was then verified using 1H-NMR and FT-IR spectroscopy. The corresponding lower critical solution temperature and phase transition behavior of each co-polymer was analyzed through cloud point and DSC, while mechanical properties were investigated through rheology. Swelling behavior was also monitored at different temperatures. The resulting polymer system demonstrated properties compatible with physiological conditions, forming a gel at pH 7.4 and at temperatures near body temperature. The hydrogel also showed reduced viscoelastic flow at low frequency stress, and increased strength than purely physical or chemical gels. Swelling behavior was determined to be temperature-dependent; however, no difference was observed in swelling percent beyond 48 h. Having the ability to alter these co-polymers through various synthesis parameters and techniques, this hydrogel can potentially be used as an injectable, waterborne gelling material for biomedical applications such as endovascular embolization.

Original languageEnglish (US)
Pages (from-to)1299-1318
Number of pages20
JournalJournal of Biomaterials Science, Polymer Edition
Volume22
Issue number10
DOIs
StatePublished - 2011

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Polymers
Gelation
Temperature
Swelling
Gels
Hydrogel
Hydrogels
Addition reactions
Rheology
Phase Transition
Free radical polymerization
Body Temperature
Polymerization
Free Radicals
poly(NIPAAm-co-cysteamine)
poly(N-isopropylacrylamide-co-hydroxyethyl methacrylate-acrylate)
Infrared spectroscopy
Spectrum Analysis
Substitution reactions
Phase transitions

Keywords

  • CHEMICAL CROSS-LINK
  • IN SITU POLYMER GEL
  • LOWER CRITICAL SOLUTION TEMPERATURE (LCST)
  • MICHAEL-TYPE ADDITION REACTION
  • PHYSICAL GEL
  • POLY(NIPAAM)
  • RHEOLOGY

ASJC Scopus subject areas

  • Biophysics
  • Biomaterials
  • Bioengineering
  • Biomedical Engineering

Cite this

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title = "Synthesis, characterization and properties of a physically and chemically gelling polymer system using poly (NIPAAm-co-HEMA-acrylate) and poly (NIPAAm-co-cysteamine)",
abstract = "The aim of this work was to develop a simultaneous physically and chemically gelling system using NIPAAm co-polymers. The in situ polymer gel was obtained by synthesizing poly(NIPAAm-co-HEMAacrylate) and poly(NIPAAm-co- cysteamine) through free radical polymerization and further nucleophilic substitution. The purpose of the dual gelation is that physical gelation would take place at higher temperatures as the NIPAAm chains associate, while chemical gelation would occur through a Michael-type addition reaction, resulting in a cross-link forming through a nucleophilic attack of the thiolate on the acrylate. The structure of each co-polymer was then verified using 1H-NMR and FT-IR spectroscopy. The corresponding lower critical solution temperature and phase transition behavior of each co-polymer was analyzed through cloud point and DSC, while mechanical properties were investigated through rheology. Swelling behavior was also monitored at different temperatures. The resulting polymer system demonstrated properties compatible with physiological conditions, forming a gel at pH 7.4 and at temperatures near body temperature. The hydrogel also showed reduced viscoelastic flow at low frequency stress, and increased strength than purely physical or chemical gels. Swelling behavior was determined to be temperature-dependent; however, no difference was observed in swelling percent beyond 48 h. Having the ability to alter these co-polymers through various synthesis parameters and techniques, this hydrogel can potentially be used as an injectable, waterborne gelling material for biomedical applications such as endovascular embolization.",
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author = "Bearat, {Hanin H.} and Lee, {Bae Hoon} and Jorge Valdez and Brent Vernon",
year = "2011",
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pages = "1299--1318",
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T1 - Synthesis, characterization and properties of a physically and chemically gelling polymer system using poly (NIPAAm-co-HEMA-acrylate) and poly (NIPAAm-co-cysteamine)

AU - Bearat, Hanin H.

AU - Lee, Bae Hoon

AU - Valdez, Jorge

AU - Vernon, Brent

PY - 2011

Y1 - 2011

N2 - The aim of this work was to develop a simultaneous physically and chemically gelling system using NIPAAm co-polymers. The in situ polymer gel was obtained by synthesizing poly(NIPAAm-co-HEMAacrylate) and poly(NIPAAm-co- cysteamine) through free radical polymerization and further nucleophilic substitution. The purpose of the dual gelation is that physical gelation would take place at higher temperatures as the NIPAAm chains associate, while chemical gelation would occur through a Michael-type addition reaction, resulting in a cross-link forming through a nucleophilic attack of the thiolate on the acrylate. The structure of each co-polymer was then verified using 1H-NMR and FT-IR spectroscopy. The corresponding lower critical solution temperature and phase transition behavior of each co-polymer was analyzed through cloud point and DSC, while mechanical properties were investigated through rheology. Swelling behavior was also monitored at different temperatures. The resulting polymer system demonstrated properties compatible with physiological conditions, forming a gel at pH 7.4 and at temperatures near body temperature. The hydrogel also showed reduced viscoelastic flow at low frequency stress, and increased strength than purely physical or chemical gels. Swelling behavior was determined to be temperature-dependent; however, no difference was observed in swelling percent beyond 48 h. Having the ability to alter these co-polymers through various synthesis parameters and techniques, this hydrogel can potentially be used as an injectable, waterborne gelling material for biomedical applications such as endovascular embolization.

AB - The aim of this work was to develop a simultaneous physically and chemically gelling system using NIPAAm co-polymers. The in situ polymer gel was obtained by synthesizing poly(NIPAAm-co-HEMAacrylate) and poly(NIPAAm-co- cysteamine) through free radical polymerization and further nucleophilic substitution. The purpose of the dual gelation is that physical gelation would take place at higher temperatures as the NIPAAm chains associate, while chemical gelation would occur through a Michael-type addition reaction, resulting in a cross-link forming through a nucleophilic attack of the thiolate on the acrylate. The structure of each co-polymer was then verified using 1H-NMR and FT-IR spectroscopy. The corresponding lower critical solution temperature and phase transition behavior of each co-polymer was analyzed through cloud point and DSC, while mechanical properties were investigated through rheology. Swelling behavior was also monitored at different temperatures. The resulting polymer system demonstrated properties compatible with physiological conditions, forming a gel at pH 7.4 and at temperatures near body temperature. The hydrogel also showed reduced viscoelastic flow at low frequency stress, and increased strength than purely physical or chemical gels. Swelling behavior was determined to be temperature-dependent; however, no difference was observed in swelling percent beyond 48 h. Having the ability to alter these co-polymers through various synthesis parameters and techniques, this hydrogel can potentially be used as an injectable, waterborne gelling material for biomedical applications such as endovascular embolization.

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KW - MICHAEL-TYPE ADDITION REACTION

KW - PHYSICAL GEL

KW - POLY(NIPAAM)

KW - RHEOLOGY

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SN - 0920-5063

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