黄酮/叔胺引发三丙二醇二丙烯酸酯的光聚合反应

doi:10.7503/cjcu20130700

高等学校化学学报 ›› 2014, Vol. 35 ›› Issue (3): 660.doi: 10.7503/cjcu20130700

• 高分子化学 • 上一篇

黄酮/叔胺引发三丙二醇二丙烯酸酯的光聚合反应

史素青¹(), 杨扬¹, 蔡天源¹, 高娜¹, 宫永宽¹, 聂俊²

1. 西北大学合成与天然功能分子化学教育部重点实验室, 西安 710069
2. 北京化工大学化工资源有效利用国家重点实验室, 北京 100029

收稿日期:2013-07-22 出版日期:2014-03-10 发布日期:2019-08-01
作者简介:联系人简介: 史素青, 女, 博士, 副教授, 主要从事光聚合及防污表/界面方面的研究. E-mail: shisq@nwu.edu.cn
基金资助:
国家自然科学基金(批准号: 21004047, J1210057, J1103311)、陕西省教育厅专项科研计划(批准号: 09JK767)、陕西省自然科学基础研究计划(批准号: 2010JQ2004)和中国博士后科学基金(批准号: 20100471629, 201104673)资助

Flavone/Tertiary Amine as Free Radical Photoinitiator for UV Photopolymerization of Tripropylene Glycol Diacrylate(TPGDA)^†

SHI Suqing^1,^*(), YANG Yang¹, CAI Tianyuan¹, GAO Na¹, GONG Yongkuan¹, NIE Jun²

1. Key Laboratory of Synthetic and Natural Functional Molecule Chemistry of Ministry of Education, Northwest University, Xi’an 710069, China
2. State Key Laboratory of Chemical Resource Engineering, Beijing University of Chemical Technology, Beijing 100029, China

Received:2013-07-22 Online:2014-03-10 Published:2019-08-01
Contact: SHI Suqing E-mail:shisq@nwu.edu.cn
Supported by:
† Supported by the National Natural Science Foundation of China(Nos.21004047, J1210057, J1103311), the Scientific Research Program Funded by Shaanxi Provincial Education Department of China(No.09JK767), the Natural Science Basic Research Plan in Shaanxi Province of China(No.2010JQ2004) and the China Postdoctoral Science Foundation(Nos.20100471629, 201104673)

摘要/Abstract

摘要：

采用实时红外光谱(RTIR)研究了黄酮(FL)为紫外光光敏剂, 不同氢给体(如叔胺)为助引发剂时三丙二醇二丙烯酸酯(TPGDA)的光聚合反应. 结果表明, FL分子中的大π共轭体系使其UV吸收峰的摩尔消光系数(ε_max)远远高于商业化光敏剂二苯甲酮(BP). 当FL与不同助引发剂配合使用时, TPGDA光聚合动力学有较大差异, 其中叔胺体系助引发剂能够与激发态FL发生有效的电子/质子转移过程, 产生胺烷基自由基活性种引发TPGDA的光聚合反应, 所得固化膜的最终双键转化率(DC_f)为93%~97%, 接近完全固化; 而芝麻素(SM)及胡椒环(BDO)作为助引发剂时TPGDA的聚合速率则很低, 固化膜的DC_f仅为32%~38%. 当光敏剂质量分数为1.0%, 4-N,N'-二甲氨基苯甲酸乙酯(EDAB)质量分数为1.0%时, FL/EDAB引发TPGDA的聚合动力学与商业化BP/EDAB的相同, 所得固化膜的DC_f均为97%.

关键词: 黄酮, 光引发剂, 氢给体, 丙烯酸酯, 光聚合反应

Abstract:

The polymerization kinetics of tripropylene glycol diacrylate(TPGDA) was monitored by real time near infrared(RTIR) with favone(FL) as photosensitizer and different hydrogen donor as coinitiator. The commercial photosensitizer benzophenone(BP) was used as control. The results showed that the molar extinction coefficient(ε_max) of FL was much higher than that of BP. When FL was used in combination with tertiary amine hydrogen donor ethyl 4-N,N'-dimethylaminobenzoate(EDAB), the rate of polymerization(R_p) and final double bond conversion(DC_f) could reach 0.58 s^-1 and 97%, respectively, which was very close to that of commercial BP/EDAB system. However, using sesamin(SM) and benzodioxole(BDO) as coinitiator for FL, the R_p and DC_f were both very low, which indicated that the excited FL and tertiary amine could generate aminoalkyl free radical species via electron/proton transfer process and initiate the efficient photopolymerization of TPGDA. More importantly, when the co-polymerizable tertiary amines such as EBERYL P115 and dimethy-laminoethyl methacrylate(DMEM) are used, the natural component characteristics of FL make it a promising photoinitiator in biomedical and food-packaging fields.

Key words: Flavone, Photoinitiator, Hydrogen donor, Acrylate, Photopolymerization

中图分类号:

O631

TrendMD:

史素青, 杨扬, 蔡天源, 高娜, 宫永宽, 聂俊. 黄酮/叔胺引发三丙二醇二丙烯酸酯的光聚合反应. 高等学校化学学报, 2014, 35(3): 660.

SHI Suqing, YANG Yang, CAI Tianyuan, GAO Na, GONG Yongkuan, NIE Jun. Flavone/Tertiary Amine as Free Radical Photoinitiator for UV Photopolymerization of Tripropylene Glycol Diacrylate(TPGDA)^†. Chem. J. Chinese Universities, 2014, 35(3): 660.

图/表 10

Fig.1 Chemical structures of TPGDA, photosensitizer(FL, EDAB, DMEM) and hydrogen donors(BP, BDO, SM)

Fig.2 UV-Vis absorption spectra of FL(a)and BP(b, c) in cyclohexanea. cFL=5×10-5 mol/L; b. cBP=5×10-5 mol/L; c. cBP=5×10-3 mol/L.

Table 1 UV spectra data of FL and BP in cyclohexane

Material	λ_max/nm	ε_max/(L·mol^-1·cm^-1)
BP	250	21580
	346	154
	258	22480
FL	293	28980
	310	23780

Fig.3 Fluorescence spectra of FL at different concentrations EDAB in cyclohexane (A)λex=354 nm, cFL=5×10-5 mol/L, PMT voltage 950 V; (B) plot of I0/I vs. cEDAB.

Fig.4 Effects of concentrations of EDAB on DC(A) and Rp(B) of TPGDA with 1.0%(mass fraction) FL as photosensitizer

Fig.5 Effects of concentrations of FL on DC(A) and Rp(B) of TPGDA with 1.0%(mass fraction) EDAB as photosensitizer

Fig.6 Effects of hydrogen donors(1.0%) on photo-polymerization kinetics of TPGDA with 1.0%FL as photosensitizer

Fig.7 Photoinitiating process of FL/EDAB system

Table 2 Rp,max and DCf of TPGDA photopolymerization by 1.0%FL in combination with 1.0%hydrogen donor

Hydrogen donor	R_{p, max}/s^-1	DC_f(%)
Without hydrogen donor		27±2
BDO		32±1
SM		38±2
DMEM	0.31±0.01	93±1
EBERYL P115	0.37±0.02	95±1
EDAB	0.58±0.01	97±1

Fig.8 Comparison of FL/EDAB(a) and BP/EDAB(b) on photopolymerization kinetics of TPGDA

参考文献 19

[1]	Decker C., Progress in Polymer Science, 1996, 21, 593—650
[2]	Fouassier J.P., Photoinitiation, Photopolymerization, and Photocuring, Fundamentals and Application, Munich, Hanser, 1995, 1—330
[3]	Chen Y.L., Zeng Z. H, Yang J. W., Radcured Materials and Its Application, Chemical Industry Press, Beijing, 2003, 3—277
	(陈用烈, 曾兆华, 杨建文. 辐射固化材料及其应用, 北京: 化学工业出版社, 2003, 3—277)
[4]	Shi S., Xiao P., Wang K. M., Gong Y. L., Nie J., Acta Biomaterialia,2010, 6, 3067—3071
[5]	Shi S., Nie J., Dental Materials,2008, 24, 530—535
[6]	Shi S., Gao H., Wu G., Nie J., Polymer,2007, 48, 2860—2865
[7]	Zhang Q., Gao N., Yang Y., Gong Y. K., Wang Y. B., Zhang S. P., Shi S. Q., Chem. J. Chinese Universities,2013, 34(5), 1270—1276
	(张琴, 高娜, 杨扬, 宫永宽, 王彦兵, 张世平, 史素青. 高等学校化学学报, 2013, 34(5), 1270—1276)
[8]	Moin J. C., Nomura Y., Urabe H., Okazaki M., Shintani H., J. Biomed. Mater. Res. Part B: Appl. Biomater. ,2001, 58, 42—46
[9]	Lis P. A., Vazquez B., Rebuelta M., Hemaez M. L., Roman J. S., Biomaterials,1997, 18, 15—20
[10]	Angiolini L., Caretti D., Rossetti S., Salatelli E., Scoponi M., J. Polym. Sci. Part A: Polym. Chem., 2005, 43, 5879—5888
[11]	Shi S., Nie J., J. Biomed. Mater. Res. Part B: Appl. Biomater., 2007, 82B, 44—50
[12]	Hou G., Shi S., Liu S., Nie J., Polym. J., 2008, 40(3), 228—232
[13]	Wu G., Nie J., J. Photochem. Photobiol. A. Chem., 2006, 183, 154—158
[14]	Rao Y. K., Harikishore P., Rao C. K., Gunasekar D., Bolnd A., Bodo B., Phytochemistry,2002, 61, 927—929
[15]	Cao Y., Tan N., Chen J., Zeng G., Ma Y., Wu Y., Han H., Yang J., Lu L., Wang Q., Fitoterapia,2010, 81, 253—258
[16]	Valls J., Millan S., Pilar Marti M., Borras E., Arola L., J. Chromatography A,2009, 1216, 7143—7172
[17]	Sampson L., Rimm E., Hollman P. C. H., de Vries J. H. M., Katan M. B., Journal of the American Dietetic Association,2002, 102, 1414—1420
[18]	Engler G., Nispel M., Marian C., Kleinermanns K., Chemical Physics Letters,2009, 473, 167—170
[19]	Stansbury J. W., Dickens S. H., Dental Materials,2001, 17, 71—79

黄酮/叔胺引发三丙二醇二丙烯酸酯的光聚合反应

Flavone/Tertiary Amine as Free Radical Photoinitiator for UV Photopolymerization of Tripropylene Glycol Diacrylate(TPGDA)^†

RichHTML

PDF (PC)

可视化

被引次数

摘要/Abstract

引用本文

使用本文

图/表 10

参考文献 19

相关文章 15

编辑推荐

Metrics

本文评价

[1]	徐丹丹, 邹修成, 罗静, 刘仁. 吩噻嗪席夫碱可见光引发剂的合成与性能[J]. 高等学校化学学报, 2022, 43(4): 20210857.
[2]	李伦, 张静妍, 罗静, 刘仁, 朱乙. UV/Vis-LED激发的香豆素吡啶鎓盐光引发剂的合成及性能[J]. 高等学校化学学报, 2022, 43(10): 20220178.
[3]	黄罗仪, 翁约约, 黄旭慧, 王朝杰. 车前草中黄酮类成分结构和性质的理论研究[J]. 高等学校化学学报, 2021, 42(9): 2752.
[4]	李文红, 王丹阳, 曹津津, 魏永巨. 黄豆黄素与黄豆黄苷吸收光谱和荧光光谱的比较研究[J]. 高等学校化学学报, 2019, 40(1): 47.
[5]	石玉军, 方源, 李阳, 陈佳, 李刚, 汪清民, 戴红. 新型含5-芳基异噁唑结构的氰基丙烯酸酯类化合物的合成及生物活性[J]. 高等学校化学学报, 2017, 38(3): 421.
[6]	汪争光, 胡朵, 吴东蔚, 鲁路, 周长忍. 结冷胶与聚乙二醇丙烯酸酯双网络凝胶的制备及生物相容性评价[J]. 高等学校化学学报, 2017, 38(2): 275.
[7]	鲍艳, 高敏, 董雨菲, 康巧玲, 高智鹏, 吴国栋, 李妍. 中空TiO₂微球的制备及对聚丙烯酸酯薄膜性能的影响[J]. 高等学校化学学报, 2017, 38(12): 2328.
[8]	邱林子, 王桂容, 潘艳, 王溢文, 李新庆, 邓林红, 张嵘. 用于人类脂肪干细胞的纯化和体外长期培养的聚合物涂层[J]. 高等学校化学学报, 2017, 38(10): 1897.
[9]	刘本国, 刘江伟, 李嘉琪, 耿升, 莫海珍, 梁桂兆. 类黄酮抑制P糖蛋白的三维定量构效关系与作用模式[J]. 高等学校化学学报, 2017, 38(1): 41.
[10]	高婷婷, 李志英, 高歌, 刘凤岐. 直链型与支链型疏水缔合水凝胶的机械性能与溶胀行为[J]. 高等学校化学学报, 2016, 37(9): 1744.
[11]	张涛, 汤永嘉, 徐亮, 刘克良. 新型可用于荧光标记的α-氰基丙烯酸酯单体的合成及在小鼠活体成像中的应用[J]. 高等学校化学学报, 2016, 37(6): 1168.
[12]	徐朝华, 陈婵, 孙宁, 李珩, 李亦彪. 双键可控紫外光固化超支化聚氨酯丙烯酸酯的制备与表征[J]. 高等学校化学学报, 2016, 37(6): 1224.
[13]	杨大雷, 张袅娜, 胡求学, 魏英聪, 闫茹, 张明耀, 张会轩, 呼微. 木质素基环氧丙烯酸酯的合成及紫外光固化[J]. 高等学校化学学报, 2016, 37(3): 426.
[14]	徐燕, 田沙沙, 俞和, 杨文智, 朱华结. 棘孢曲霉中分离的2个新化合物[J]. 高等学校化学学报, 2015, 36(6): 1107.
[15]	李秀云, 万川, 杜士杰, 李红, 袁会珠, 蒋家珍, 肖玉梅, 覃兆海. 二芳基肟苄醚类化合物的合成及杀菌活性[J]. 高等学校化学学报, 2015, 36(12): 2415.

黄酮/叔胺引发三丙二醇二丙烯酸酯的光聚合反应

Flavone/Tertiary Amine as Free Radical Photoinitiator for UV Photopolymerization of Tripropylene Glycol Diacrylate(TPGDA)†

RichHTML

PDF (PC)

可视化

被引次数

摘要/Abstract

引用本文

使用本文

图/表 10

参考文献 19

相关文章 15

编辑推荐

Metrics

本文评价

Flavone/Tertiary Amine as Free Radical Photoinitiator for UV Photopolymerization of Tripropylene Glycol Diacrylate(TPGDA)^†