自由基型紫外光固化氧阻聚作用的定量描述

doi:10.11949/j.issn.0438-1157.20180155

摘要/Abstract

摘要：

基于自由基型光固化过程一般由多个活性中心引起的考虑，利用分峰的方法对光固化速率曲线进行多峰拟合，同时定义速率曲线上拐点处的切线与时间轴的交点横坐标t_V-inh作为一个光固化时间参数，来研究氧气的阻聚作用效果。通过对光固化参数与引发剂含量进行拟合分析，定量地考察了分峰分析方法及所选择的参数用以描述氧阻聚的可行性。结果表明，分峰可以清晰地分离出对氧气较敏感的固化反应部分，t_V-inh与引发剂含量x的关系可用函数模型t_V-inh=A/x+B进行表达，（A+B）值的大小可以定量地反映固化体系对氧气的敏感程度。

关键词: 紫外光固化, 氧阻聚, 自由基, 分峰拟合

Abstract:

Curing rate curve was multimodally fitted by the peak separation method based on the consideration that free radical UV-curing process is generally caused by multiple active centers. A parameter of t_V-inh, which is the intersection of abscissa and the tangent line of the inflection point of curing rate curve, is assigned to evaluate oxygen inhibition extent. The results showed a more oxygen-sensitive curing reaction could be isolated by overlapping peak resolving, and the relationship between t_V-inh and initiator content x turned out to be fulfilled the algebraic expression of t_V-inh=A/x+B optimally, and the value of (A+B) could be used to describe the oxygen inhibition trend for a given curing formula.

Key words: UV-curing, oxygen inhibition, radical, overlapping peak resolving

中图分类号:

朱国建, 范天锋, 王德海, 鲍刘兵. 自由基型紫外光固化氧阻聚作用的定量描述[J]. 化工学报, 2018, 69(8): 3740-3746.

ZHU Guojian, FAN Tianfeng, WANG Dehai, BAO Liubing. Quantitative description of oxygen inhibition in radical UV-curing[J]. CIESC Journal, 2018, 69(8): 3740-3746.

参考文献 31

[1]	WONG J, KAASTRUP K, AGUIRRE SOTO A, et al. A quantitative analysis of peroxy-mediated cyclic regeneration of eosin under oxygen-rich photopolymerization conditions[J]. Polymer, 2015, 69:169-177.
[2]	DECKER C, LORINCZOVA I. UV-radiation curing of waterborne acrylate coatings[J]. Journal of Coatings Technology and Research, 2004, 1(4):247-256.
[3]	贺锡挺, 王德海, 马国杰. 环氧树脂/环氧丙烯酸酯混杂光固化材料的结构与性能[J]. 化工学报, 2009, 60(3):769-774. HE X T, WANG D H, MA G J. Structure and properties of epoxy resin/epoxy acrylate hybrid UV-cured material[J]. CIESC Journal, 2009, 60(3):769-774.
[4]	KIM S K, GUYMON C A. Effects of polymerizable organoclays on oxygen inhibition of acrylate and thiol-acrylate photopolymerization[J]. Polymer, 2012, 53(8):1640-1650.
[5]	HOEFER M, MOSZNER N, LISKA R. Oxygen scavengers and sensitizers for reduced oxygen inhibition in radical photopolymerization[J]. J. Polym. Sci., Part A:Polym. Chem., 2008, 46(20):6916-6927.
[6]	O'BRIEN A K, CRAMER N B, BOWMAN C N. Oxygen inhibition in thiol-acrylate photopolymerizations[J]. J. Polym. Sci., Part A:Polym. Chem., 2006, 44(6):2007-2014.
[7]	TAKI K, WATANABE Y, ITO H, et al. Effect of oxygen inhibition on the kinetic constants of the UV-radical photopolymerization of diurethane dimethacrylate/photoinitiator systems[J]. Macromolecules, 2014, 47(6):1906-1913.
[8]	BALTA D K, ARSU N, YAGCI Y, et al. Thioxanthone-anthracene:a new photoinitiator for free radical polymerization in the presence of oxygen[J]. Macromolecules, 2007, 40(12):4138-4141.
[9]	O'BRIEN A K, BOWMAN C N. Impact of oxygen on photopolymerization kinetics and polymer structure[J]. Macromolecules, 2006, 39(7):2501-2506.
[10]	BELON C, ALLONAS X, CROUTXE B C, et al. Overcoming the oxygen inhibition in the photopolymerization of acrylates:a study of the beneficial effect of triphenylphosphine[J]. J. Polym. Sci., Part A:Polym. Chem., 2010, 48(11):2462-2469.
[11]	HUSAR B, LIGON S C, WUTZEL H, et al. The formulator's guide to anti-oxygen inhibition additives[J]. Prog. Org. Coat., 2014, 77(11):1789-1798.
[12]	ANDRZEJEWSKA E. Photopolymerization kinetics of multifunctional monomers[J]. Prog. Polym. Sci., 2001, 26(4):605-665.
[13]	FEDOROV A V, ERMOSHKIN A A, MEJIRITSKI A, et al. New method to reduce oxygen surface inhibition by photorelease of boranes from borane/amine complexes[J]. Macromolecules, 2007, 40(10):3554-3560.
[14]	肖鸣. 多官能度单体的合成及光聚合性能研究[D]. 北京:北京化工大学, 2009. XIAO M. Synthesis and photopolymerzation of multifunctional monomers[D]. Beijing:Beijing University of Chemical Technology, 2009.
[15]	COURTECUISSE F, CEREZO J, CROUTXE BARGHORN C, et al. Depth characterization by confocal Raman microscopy of oxygen inhibition in free radical photopolymerization of acrylates:contribution of the thiol chemistry[J]. J. Polym. Sci., Part A:Polym. Chem., 2013, 51(3):635-643.
[16]	TEHFE M A, MONOT J, BRAHMI M, et al. N-Heterocyclic carbene-borane radicals as efficient initiating species of photopolymerization reactions under air[J]. Polym. Chem., 2011, 2(3):625-631.
[17]	COURTECUISSE F, BELBAKRA A, CROUTXE BARGHORN C, et al. Zirconium complexes to overcome oxygen inhibition in free-radical photopolymerization of acrylates:kinetic, mechanism, and depth profiling[J]. J. Polym. Sci., Part A:Polym. Chem., 2011, 49(24):5169-5175.
[18]	SONG L, YE Q, GE X, et al. Tris(trimethylsilyl)silane as a co-initiator for dental adhesive:photo-polymerization kinetics and dynamic mechanical property[J]. Dent. Mater., 2016, 32(1):102-113.
[19]	OYTUN F, KAHVECI M U, YAGCI Y. Sugar overcomes oxygen inhibition in photoinitiated free radical polymerization[J]. J. Polym. Sci., Part A:Polym. Chem., 2013, 51(8):1685-1689.
[20]	CORCIONE C E, STRIANI R, FRIGIONE M. UV-cured methacrylic-silica hybrids:effect of oxygen inhibition on photo-curing kinetics[J]. Thermochimica Acta, 2014, 576:47-55.
[21]	钱夏庆, 王德海, 李恒. 单体结构对紫外光固化氧阻聚影响的研究[J]. 影像科学与光化学, 2013, 31(4):276-285. QIAN X Q, WANG D H, LI H. Effect of monomer structure on oxygen inhibition of UV-curing[J]. Imading Science and Photochemistry, 2013, 31(4):276-285.
[22]	HRISTOVA NEELEY D, NESHCHADIN D, GESCHEIDT G. Time-resolved epr as a tool to investigate oxygen quenching in photoinitiated radical polymerizations[J]. J. Phys. Chem. B, 2015, 119(43):13883-13887.
[23]	程诚, 黄亚继, 孙宇, 等. 高斯拟合在污泥热重曲线解析中的应用[J]. 中南大学学报(自然科学版), 2014, 45(11):4081-4086. CHENG C, HUANG Y J, SUN Y, et al. Application of Gaussian fitting in resolution of sludge thermo-gravimetric curves analyzing[J]. Journal of Central South University (Science and Technology), 2014, 45(11):4081-4086.
[24]	李睿, 金保昇, 仲兆平, 等. 高斯多峰拟合用于生物质热解三组分模型的研究[J]. 太阳能学报, 2010, 31(7):806-810. LI R, JIN B S, ZHONG Z P, et al. Research on biomass pyrolysis three-pseudocomponent model by Gaussian multi-peaks fitting[J]. Acta Energiae Solaris Sinica, 2010, 31(7):806-810.
[25]	倪秋如, 倪礼忠, 夏宏伟, 等. TBPB-TBPO引发不饱和聚酯树脂固化的动力学[J]. 功能高分子学报, 2014, 27(3):348-352. NI Q R, NI L Z, XIA H W, et al. Kinetic of unsaturated polyester resin with TBPB-TBPO[J]. Journal of Functional Polymers, 2014, 27(3):348-352.
[26]	MARTIN J L. Kinetic analysis of two DSC peaks in the curing of an unsaturated polyester resin catalyzed with methylethylketone peroxide and cobalt octoate[J]. Polymer Engineering and Science, 2007, 47(1):62-70.
[27]	周启超, 杨红亮, 季妮芝, 等. 酚醛树脂热解高斯分峰法[J]. 宇航材料工艺, 2015, 45(3):11-14. ZHOU Q C, YANG H L, JI N Z, et al. Gaussian peak separation method for thermal decomposition of phenolic resin[J]. Aerospace Materials & Technology, 2015, 45(3):11-14.
[28]	WANG S J, LIU X, KONG J, et al. Synthesis and UV curing kinetics of rapidly UV-curable hyperbranched polycarbosiloxanes[J]. Polymer International, 2010, 59(10):1323-1330.
[29]	朱凯汉, 王月娟. DTA重叠峰的高斯函数解析法[J]. 计算机与应用化学, 1997, 14(4):303-306. ZHU K H, WAN Y J. Gauss function method for DTA overlapping peak[J]. Computers and Applied Chemistry, 1997, 14(4):303-306.
[30]	LIGON S C, HUSAR B, WUTZEL H, et al. Strategies to reduce oxygen inhibition in photoinduced polymerization[J]. Chem. Rev., 2014, 114(1):557-589.
[31]	LALEVEE J, ALLONAS X, JRADI S, et al. Role of the medium on the reactivity of cleavable photoinitiators in photopolymerization reactions[J]. Macromolecules, 2006, 39(5):1872-1879.