Redox initiation of bulk thiol-ene polymerizations

被引:37
作者
Cole, Megan A. [1 ]
Jankousky, Katherine C. [1 ]
Bowman, Christopher N. [1 ,2 ]
机构
[1] Univ Colorado, Dept Chem & Biol Engn, Boulder, CO 80309 USA
[2] Univ Colorado, Hlth Sci Ctr, Denver, CO USA
关键词
GLUCOSE-OXIDASE; PEROXIDE/AMINE SYSTEM; PHOTOPOLYMERIZATION; MECHANISM; KINETICS; CHEMISTRIES; NETWORKS; POLYMER; ENZYME; AMINE;
D O I
10.1039/c2py20843a
中图分类号
O63 [高分子化学(高聚物)];
学科分类号
070305 ; 080501 ; 081704 ;
摘要
The unique formation-structure-property attributes and reaction behavior of the thiol-ene "click" reaction have been explored extensively for photochemically and thermally initiated reactions but have been much less explored for redox initiation. Therefore, the objective of this work is to characterize fully the impact of the initiation system, monomer structure, degree of functionalization, and inhibitor level on the redox-mediated thiol-ene polymerization rate and behavior. Moreover, this study confirms the ability of redox initiation to achieve full conversion of desired thiol-ene "click" products for small molecules in solution. For the multifunctional thiol-ene systems, polymerization rate was shown to be comparable to photo- and thermally initiated systems, but with the additional advantages of unlimited depth of cure and mild reaction conditions. Additionally, the network properties of the redox-initiated thiol-ene systems were on par with a photocured material formulated with identical monomers and radical initiating potential. Lastly, control over the polymerization rate and preceding induction period was garnered from the concentration of inhibitor included in the reaction mixture. The mechanism of action of quinone inhibition in redox-mediated thiol-ene polymerizations is shown to depend on both the presence of an aniline reducing agent and the concentration of inhibitor, with quinone concentrations in great excess of oxidizing agent concentrations actually leading to heightened polymerization rates when aniline is present.
引用
收藏
页码:1167 / 1175
页数:9
相关论文
共 42 条
  • [1] The role of hydroquinone monomethyl ether in the stabilization of acrylic acid
    Becker, Holger
    Vogel, Herbert
    [J]. CHEMICAL ENGINEERING & TECHNOLOGY, 2006, 29 (10) : 1227 - 1231
  • [2] Glucose Oxidase-Mediated Polymerization as a Platform for Dual-Mode Signal Amplification and Biodetection
    Berron, Brad J.
    Johnson, Leah M.
    Ba, Xiao
    McCall, Joshua D.
    Alvey, Nicholas J.
    Anseth, Kristi S.
    Bowman, Christopher N.
    [J]. BIOTECHNOLOGY AND BIOENGINEERING, 2011, 108 (07) : 1521 - 1528
  • [3] Preparation of a very stable immobilized biocatalyst of glucose oxidase from Aspergillus niger
    Betancor, L
    López-Gallego, F
    Hidalgo, A
    Alonso-Morales, N
    Dellamora-Ortiz, G
    Guisán, JM
    Fernández-Lafuente, R
    [J]. JOURNAL OF BIOTECHNOLOGY, 2006, 121 (02) : 284 - 289
  • [4] Toward an Enhanced Understanding and Implementation of Photopolymerization Reactions
    Bowman, Christopher N.
    Kloxin, Christopher J.
    [J]. AICHE JOURNAL, 2008, 54 (11) : 2775 - 2795
  • [5] Thiol-ene oligomers as dental restorative materials
    Carioscia, JA
    Lu, H
    Stanbury, JW
    Bowman, CN
    [J]. DENTAL MATERIALS, 2005, 21 (12) : 1137 - 1143
  • [6] Fabrication of poly(methyl methacrylate) microfluidic chips by redox-initiated polymerization
    Chen, Jiang
    Lin, Yuehe
    Chen, Gang
    [J]. ELECTROPHORESIS, 2007, 28 (16) : 2897 - 2903
  • [7] Photopolymerization of Thiol-Ene Systems Based on Oligomeric Thiols
    Clark, Tolecia
    Kwisnek, Luke
    Hoyle, Charles E.
    Nazarenko, Serge
    [J]. JOURNAL OF POLYMER SCIENCE PART A-POLYMER CHEMISTRY, 2009, 47 (01) : 14 - 24
  • [8] Thermal polymerization of thiol-ene network-forming systems
    Cook, Wayne D.
    Chen, Fei
    Pattison, Derek W.
    Hopson, Peyton
    Beaujon, Mathieu
    [J]. POLYMER INTERNATIONAL, 2007, 56 (12) : 1572 - 1579
  • [9] Thiol-ene photopolymerization mechanism and rate limiting step changes for various vinyl functional group chemistries
    Cramer, NB
    Reddy, SK
    O'Brien, AK
    Bowman, CN
    [J]. MACROMOLECULES, 2003, 36 (21) : 7964 - 7969
  • [10] Flory P J., PRINCIPLES POLYM CHE