Study on the Preparation and Properties of Thiol-ene Photosensitive Resins for DLP 3D Printing

doi:10.7517/issn.1674-0475.180407

Abstract

Abstract: 3D printing based on digital light processing (DLP) affords rapid fabrication speeds, high dimensional accuracy and enables fabrication of objects with complex geometries. Therefore, developing photosensitive resins suitable for DLP 3D printing has become essential. Compared to traditional chain growth photopolymerization based on acrylates, thiol-ene photopolymerization features rapid reaction rates, high conversions, more homogeneous networks and low volume shrinkage due to its unique step growth polymerization mechanism. In this paper, a series of thiol-ene photosensitive resin were prepared and successfully applied to DLP printing to fabricate 3D objects. We explored the influence of the content of thiol monomers on the polymerization kinetics, thermomechanical properties, tensile properties, volume shrinkage and printing accuracy. The results showed that the increased amount of thiol monomers led to significantly increased double bond conversion, improved homogeneity of polymerization network, increased elongation at break and reduced volume shrinkage after printing.

Key words: 3D printing, digital light processing, photosensitive resin, thiol-ene reaction

WANG Chong, LIU Yulong, LIU Ren, LI Zhiquan. Study on the Preparation and Properties of Thiol-ene Photosensitive Resins for DLP 3D Printing[J]. Imaging Science and Photochemistry, 2018, 36(5): 434-442.

References

[1] Berman B. 3-D printing:the new industrial revolution[J]. Business Horizons, 2012, 55(2):155-162.
[2] Peterson G I, Schwartz J J, Zhang D, Weiss B M, Ganter M A, Storti D W, Boydston A J. Production of materials with spatially-controlled cross-link density via vat photopo-lymerization[J]. ACS Applied Materials & Interfaces, 2016, 8(42):29037-29043.
[3] Murphy S V, Atala A. 3D bioprinting of tissues and organs[J]. Nature Biotechnology, 2014, 32(8):773-785.
[4] Mannoor M S, Jiang Z, James T, Kong Y L, Malatesta K A, Soboyejo W O, Verma N, Gracias D H, McAlpine M C. 3D Printed Bionic Ears[J]. Nano Letters, 2013, 13(6):2634-2639.
[5] 徐锋. 三维打印技术研究[J]. 机械制造与自动化, 2015, 44(1):98-101. Xu F. Research on 3D printing technology[J]. Machine Building & Automation, 2015, 44(1):98-101.
[6] Ligon S C, Liska R, Stampfl J, Gurr M, Mülhaupt R. Po-lymers for 3D printing and customized additive manufactu-ring[J]. Chemical Reviews, 2017, 117(15):10212-10290.
[7] 何岷洪, 宋坤, 莫宏斌, 李军, 潘道成, 梁子骐. 3D打印光敏树脂的研究进展[J]. 功能高分子学报, 2015, 28(1):102-108. He M H, Song K, Mong H B, Li J, Pan D C, Liang Z Q. Progress on photosensitive resins for 3D pringting[J]. Journal of Functional Polymers, 2015, 28(1):102-108.
[8] 黄宽, 陈继民, 方浩博, 袁艳萍. 面曝光快速成型过程中树脂收缩变形[J]. 北京工业大学学报, 2015, 41(12):1828-1831. Huang K, Chen J M, Fang H B, Yuan Y P. Shrinkage deformation research of photosensitive resin in mask projection stereolithography[J]. Journal of Beijing University of Technology, 2015, 41(12):1828-1831.
[9] Sundaram S, Kim D S, Baldo M A, Hayward R C, Matusik W. 3D-printed self-folding electronics[J]. ACS Applied Materials & Interfaces, 2017, 9(37):32290-32298.
[10] Fantino E, Chiappone A, Roppolo I, Manfredi D, Bongiovanni R, Pirri C F, Calignano F. 3D printing of conductive complex structures with in situ generation of silver nano-particles[J]. Advanced Materials, 2016, 28(19):3712-3717.
[11] Thrasher C J, Schwartz J J, Boydston A J. Modular elastomer photoresins for digital light processing additive ma-nufacturing[J]. ACS Applied Materials & Interfaces, 2017, 9(45):39708-39716.
[12] Hoyle C E, Bowman C N. Thiol-ene click chemistry[J]. Angewandte Chemie International Edition, 2010, 49(9):1540-1573.
[13] Carioscia J A, Lu H, Stanbury J W, Bowman C N. Thiol-ene oligomers as dental restorative materials[J]. Dental Materials, 2005, 21(12):1137-1143.
[14] Boulden J E, Cramer N B, Schreck K M, Couch C L, Troconis C B, Stanbury J W, Bowman C N. Thiol-ene-methacrylate composites as dental restorative materials[J]. Dental Materials, 2011, 27(3):267-272.
[15] Cramer N B, Couch C L, Schreck K M, Boulden J E, Wydra R, Stanbury J W, Bowman C N. Properties of methacrylate-thiol-ene formulations as dental restorative materials[J]. Dental Materials, 2010, 26(8):799-806.
[16] Cramer N B, Couch C L, Schreck K M, Carioscia J A, Boulden J E, Stanbury J W, Bowman C N. Investigation of thiol-ene and thiol-ene-methacrylate based resins as dental restorative materials[J]. Dental Materials, 2010, 26(1):21-28.
[17] Leonards H, Engelhardt S, Hoffmann A, Pongratz L, Schriever S, Bläsius J, Wehner M, Gillner A. Advantages and drawbacks of thiol-ene based resins for 3D-printing[C]//Laser 3D Manufacturing Ⅱ. Proceedings of the SPIE, 2015, 9353:93530F.
[18] 段玉岗, 王素琴, 陈浩, 卢秉恒. 激光快速成型中影响光固化材料收缩变形的研究[J]. 化学工程, 2000, 28(6):53-56. Duan Y G, Wang S Q, Chen H, Lu B H. Study on the effect of photocuring resin shrinkage on parts curl distortion in the process of laser rapid prototyping[J]. Chemical Engineering, 2000, 28(6):53-56.
[19] Thrasher C J, Schwartz J J, Boydston A J. Modular elastomer photoresins for digital light processing additive manu-facturing[J]. ACS Applied Materials & Interfaces, 2017, 9(45):39708-39716.
[20] Fantino E, Chiappone A, Roppolo I, Manfredi D, Bongiovanni R, Pirri C F, Calignano F. 3D printing of conductive complex structures with in situ generation of silver nano-particles[J]. Advanced Materials, 2016, 28(19):3712-3717.