Deep Photopolymerization Research of Highly Stable Thiol-ene System

doi:10.7517/issn.1674-0475.180202

Abstract

Abstract: Traditional thiol-ene photopolymerization system suffers from poor stability, odor issue and limited curing depth. In this paper, a highly stable thiol-ene photopolymerization system with low odor was prepared via optimization of monomers. Polymerization depth of 9.6 cm with about 80% double bond conversion was successfully achieved employing the strategy based on near-infrared light (NIR) induces up-conversion nanoparticles (UCNPs) luminescence. The cured sample exhibited good homogeneity and thermal stability (~335℃), which shows potential in the applications of photocuring of dental restoration materials and thick composites.

Key words: up-conversion, thiol-ene photopolymerization, deep photopolymerization, stability, near-infrared light

CHEN Li, WU Qingyang, LIU Ren, LI Zhiquan. Deep Photopolymerization Research of Highly Stable Thiol-ene System[J]. Imaging Science and Photochemistry, 2018, 36(5): 408-416.

References

[1] Kolb H C, Finn M G, Sharpless K B. Click chemistry:diverse chemical function from a few good reactions[J]. Angewandte Chemie International Edition,2001, 11(40):2004-2021.
[2] Blasco E, Wegener M, Barner-Kowollik C. Photochemically driven polymeric network formation:synthesis and applications[J]. Advanced Materials,2017, 29(15):1604005.
[3] Binder W H, Sachsenhofer R. ‘Click’ chemistry in polymer and materials science[J]. Macromolecular Rapid Communications, 2007, 28(1):15-54.
[4] Hoyle C E, Bowman C N. Thiol-ene click chemistry[J]. Angewandte Chemie International Edition, 2010, 49(9):1540-1573.
[5] O'Brien A K, Cramer N B, Bowman C N. Oxygen inhibition in thiol-acrylate photopolymerizations[J]. Journal of Polymer Science Part A:Polymer Chemistry, 2006, 44(6):2007-2014.
[6] O'Brien A K, Bowman C N. Impact of oxygen on photopoly-merization kinetics and polymer structure[J]. Macromolecules, 2006, 39(7):2501-2506.
[7] Kloxin C J, Scott T F, Bowman C N. Stress relaxation via addition-fragmentation chain transfer in a thiol-ene photopolymerization[J]. Macromolecules, 2009, 42(7):2551-2556.
[8] Lu H, Carioscia J A, Stansbury J W, Bowman C N. Investigations of step-growth thiol-ene polymerizations for novel dental restoratives[J]. Dental Materials, 2005, 21(12):1129-1136.
[9] Hoyle C E, Lowe A B, Bowman C N. Thiol-click chemistry:a multifaceted toolbox for small molecule and polymer synthesis[J]. Chemical Society Reviews, 2010, 39(4):1355-1387.
[10] Hata E, Mitsube K, Momose K, Tomita Y. Holographic nanoparticle-polymer composites based on step-growth thiol-ene photopolymerization[J]. Optical Materials Express, 2011, 1(2):207-222.
[11] Leonards H, Engelhardt S, Hoffmann A, Pongratz L, Schriever S, Bläsius J, Wehner M M,Gillner A. Advantages and drawbacks of thiol-ene based resins for 3D-printing[C]. Laser 3D Manufacturing Ⅱ. International Society for Optics and Photonics, 2015, 9353:93530F.
[12] Quick A S, Fischer J, Richter B, Pauloehrl T, Trouillet V, Wegener M, Barner-Kowollik C. Preparation of reactive three-dimensional microstructures via direct laser writing and thiol-ene chemistry[J]. Macromolecular Rapid Communications, 2013, 34(4):335-340.
[13] Bertlein S, Brown G, Lim K S, Jungst T, Boeck T, Blunk T, Tessmar J, Hooper G, Woodfield T B F,Groll J. Thiol-ene clickable gelatin:a platform bioink for multiple 3D biofabrication technologies[J].Advanced Materials, 2017, 29(44):1703404.
[14] Cramer N B, Scott J P, Bowman C N. Photopolymerizations of thiol-ene polymers without photoinitiators[J]. Macromolecules, 2002, 35(14):5361-5365.
[15] Liu R, Zou X, Xu Y, Liu X, Li Z. Deep thiol-ene photopolymerization using upconversion nanoparticle-assisted photochemistry[J]. Chemistry Letters, 2016, 45(9):1054-1056.
[16] Hoyle C E, Lee T Y, Roper T. Thiol-enes:chemistry of the past with promise for the future[J]. Journal of Polymer Science Part A:Polymer Chemistry, 2004, 42(21):5301-5338.
[17] Li Q, Zhou H, Hoyle C E. The effect of thiol and ene structures on thiol-ene networks:photopolymerization, physical, mechanical and optical properties[J]. Polymer, 2009, 50(10):2237-2245.
[18] Cramer N B, Bowman C N. Kinetics of thiol-ene and thiol-acrylate photopolymerizations with real-time fourier transform infrared[J]. Journal of Polymer Science Part A:Polymer Chemistry, 2001, 39(19):3311-3319.
[19] Li Q, Zhou H, Wicks D A, Hoyle C E. Thiourethane-based thiol-ene highTg networks:Preparation, thermal, mechanical, and physical properties[J]. Journal of Polymer Science Part A:Polymer Chemistry, 2007, 45(22):5103-5111.