造纸用纳米粒子复合香豆素荧光乳液的制备及性能

doi:10.11949/0438-1157.20190752

摘要/Abstract

摘要：

以7-羟基-4-甲基香豆素为母核与丙烯酰氯反应，得到香豆素荧光单体。在乳化剂聚氧乙烯辛基苯酚醚-10(OP-10)与引发剂过硫酸铵的作用下，将其与丙烯酰胺、苯乙烯和改性纳米粒子经乳液聚合制备得到荧光乳液。采用红外光谱、核磁共振氢谱、粒径分析、紫外光谱、荧光光谱及紫外加速老化试验等对产物进行结构表征，光学性能研究及应用性能考察。结果表明，复合纳米粒子的荧光乳液粒径分布更加均匀，性质更稳定，且具有良好的光学性能，涂覆于纸张表面，发现纸张白度得到改善，纸张强度和抗水性均大幅提高，且经过紫外老化后，发现目标产物有更好的抑制纸张返黄的作用。

关键词: 香豆素, 纳米粒子, 乳液, 粒度分布, 稳定性, 白度

Abstract:

7-Hydroxy-4-methylcoumarin was used as the core to react with acryloyl chloride to obtain a fluorescent monomer. Under the action of emulsifier polyoxyethylene octylphenol ether-10 (OP-10) and initiator ammonium persulfate, it was prepared by emulsion polymerization with acrylamide, styrene and modified nanoparticles to obtain a fluorescent emulsion. The products were characterized by infrared spectroscopy, nuclear magnetic resonance spectroscopy, particle size analysis, ultraviolet spectroscopy, fluorescence spectroscopy and ultraviolet accelerated aging test. The optical properties and application properties were investigated. The particle size distribution of the fluorescent emulsion of the composite nanoparticles is more uniform and the properties are more stable. When applied to the surface of the paper, it was found that the initial whiteness of the paper was improved, and the paper strength and water resistance were greatly improved. After UV aging, it was found that the target product has a better effect of inhibiting the yellowing of the paper.

Key words: coumarin, nanoparticles, emulsions, size distribution, stability, whiteness

中图分类号:

TQ 610.495

张光华, 唐进霞, 郭明媛, 刘丹, 倪美乐, 王帆. 造纸用纳米粒子复合香豆素荧光乳液的制备及性能[J]. 化工学报, 2019, 70(12): 4889-4897.

Guanghua ZHANG, Jinxia TANG, Mingyuan GUO, Dan LIU, Meile NI, Fan WANG. Preparation and properties of nanoparticle composite coumarin fluorescent emulsion for papermaking[J]. CIESC Journal, 2019, 70(12): 4889-4897.

图/表 14

图1 改性纳米粒子的制备路线

Fig.1 Preparation route of modified nanoparticles

图2 香豆素荧光单体的合成路线

Fig.2 Chemical reaction for coumarin fluorescent monomer

图3 纳米粒子复合荧光乳液的制备路线

Fig.3 Preparation route of nanoparticle composite fluorescent emulsion

图4 香豆素荧光单体的核磁氢谱图与红外光谱图

Fig.4 Nuclear magnetic resonance spectrum and infrared spectrum of coumarin fluorescent monomer

图5 荧光乳液的红外光谱图

Fig.5 Infrared spectra of fluorescent emulsion

图6 CFBE、SiO2-CFBE与ZnO-CFBE的稳定性

Fig.6 Stability of CFBE，SiO2-CFBE and ZnO-CFBE

表1 乳液粒径及PDI值

Table 1 Emulsion particle size and PDI value

乳液类型	粒径/nm	PDI	静置沉淀情况
CFBE	229	0.561	少量沉淀
ZnO-CFBE	189.9	0.011	无沉淀
SiO₂-CFBE	192.5	0.054	无沉淀

图7 CFBE、SiO2-CFBE与ZnO-CFBE的热失重曲线

Fig.7 TG curves of CFBE，SiO2-CFBE and ZnO-CFBE

图8 CFB、CFBE、SiO2-CFBE与ZnO-CFBE的紫外光谱图

Fig.8 UV-vis spectra of CFB, CFBE, SiO2-CFBE and ZnO-CFBE

图9 SiO2-CFBE与ZnO-CFBE在水中的荧光光谱图

Fig.9 Absorption/fluorescence spectra of SiO2-CFBE and ZnO-CFBE in water a—CFBE excitation spectra； b—ZnO-CFBE excitation spectra； c—SiO2-CFBE excitation spectra； d—CFBE emission spectra； e—ZnO-CFBE emission spectra； f—SiO2-CFBE emission spectra

图10 纸张涂覆前后的SEM图

Fig.10 SEM images of surface of paper sheet before and after coating

表2 纸张涂覆前后表面接触角

Table 2 Surface contact angle of paper before and after coating

参数	空白	CFBE	SiO₂-CFBE	ZnO-CFBE
接触角照片
接触角	48.21°	69.18°	74.48°	76.51°

表3 纸张涂覆前后抗张强度

Table 3 Tensile strength of paper before and after coating

纸张类型	绝对抗张力/N	抗张强度/(kN/m)
空白纸样	47.36	3.16
涂覆CFBE纸样	62.43	4.16
涂覆ZnO-CFBE纸样	68.77	4.58
涂覆SiO₂-CFBE纸样	67	4.47

图11 纸张涂覆前后的白度和PC值变化

Fig.11 Change in whiteness and PC value before and after paper coating

参考文献 32

1	房桂干, 沈兆邦, 黄德裕 . 发展高得率浆生产是保证我国造纸工业可持续发展的重要途径之一[J]. 林产化工通讯, 2000, (4): 29-31.
	Fang G G , Shen Z B , Huang D Y . Sustainable development of China s papermaking industry relying on high yield pulping technologies[J]. Journal of Chemical Industry of Forest Products, 2000, (4): 29-31.
2	周亚军, 袁志润 . 高得率浆白度稳定性及返黄抑制的研究[J]. 国际造纸, 2007, 26(4): 5-11.
	Zhou Y J , Yuan Z R . HYP brightness stability and research in yellowing inhibition[J]. World Pulp and Paper, 2007, 26(4): 5-11.
3	林本平, 王双飞 . 高得率浆光诱导返黄机理及其抑制技术的研究进展[J]. 中国造纸学报, 2007, 28(1): 92-98.
	Lin B P , Wang S F . Research progress in the mechanism of light-induced yellowing of high yield pulps[J]. Transactions of China Pulp & Paper, 2007, 28(1): 92-98.
4	Mcgarry P , Heitner C , Schmidt J , et al . A dramatic solvent effect on high-yield pulp yellowing inhibition for a benzophenone-based ultraviolet absorber[J]. Journal of Photochemistry and Photobiology A-Chemistry, 2002, 151(1): 145-155.
5	Dimitris S . Argyropoulos P H, Philip P. Photoyellowing inhibition of bleached high yield pulps using novel water-soluble UV screens[J]. Photochemistry and Photobiology, 2000, 71(2): 141-148.
6	赵艳娜, 赵瑶, 赵春艳, 等 . 荧光水性聚氨酯纸张表面施胶剂的制备及应用[J]. 化工学报, 2018, 69(4): 1783-1789.
	Zhao Y N , Zhao Y , Zhao C Y , et al . Preparation and properties of fluorescent waterborne polyurethane as paper sizing agent[J]. CIESC Journal, 2018, 69(4): 1783-1789.
7	郭明媛, 张光华, 王子儒 . 香豆素修饰的碳量子点光稳定剂的制备与性能[J]. 精细化工, 2018, 35(11): 1948-1955+1973.
	Guo M Y , Zhang G H , Wang Z R . Preparation and properties of coumarin-modified carbon quantum dots as light stabilizer[J]. Fine Chemicals, 2018, 35(11): 1948-1955+1973.
8	Zhang R , Ni Y , Wong D , et al . Interactions of optical brightening agents with high yield pulps[J]. Journal of Wood Chemistry and Technology, 2009, 29(4): 358-370.
9	张红杰, 胡惠仁, 魏德津, 等 . 荧光增白剂对杨木BCTMP浆光致返黄的抑制作用[J]. 中国造纸学报, 2008, 23(4): 32-36.
	Zhang H J , Hu H R , Wei D J , et al . Use of fluorescent whitening agents against light-induced color reversion of aspen BCTMP[J]. Transactions of China Pulp & Paper, 2008, 23(4): 32-36.
10	Zhang G H , Zheng H , Guo M Y , et al . A novel polymeric fluorescent brightener agent based on 4,4′-diamino-stilbene-2,2′-disulfonic acid-triazine structure: synthesis, characterization, photo-property, and performance on paper as light stabilizer, fluorescent brightener, and surface-sizing[J]. Journal of Wood Science, 2016, 62(6): 1-11.
11	Baltzly R . compounds New . Some coumarin derivatives[J]. Journal of the American Chemical Society, 1952, 74(10): 2692-2692.
12	张光华, 王鹏, 相瑞, 等 . 基于香豆素荧光增白剂的高分子型光稳定剂的合成及应用[J]. 高分子材料科学与工程, 2014, 30(3): 25-30.
	Zhang G H , Wang P , Xiang R , et al . Synthesis and application of polymer light stabilizer based on coumarin fluorescent brightener[J]. Polymer Materials Science & Engineering, 2014, 30(3): 25-30.
13	Zhang G H , Zheng H , Guo M Y , et al . Synthesis of polymeric fluorescent brightener based on coumarin and its performances on paper as light stabilizer, fluorescent brightener and surface sizing agent[J]. Applied Surface Science, 2016, 367: 167-173.
14	孔令义 . 香豆素化学[M]. 北京: 化学工业出版社, 2008.
	Kong L Y . Coumarin Chemistry[M]. Beijing: Chemical Industry Press, 2008.
15	Abdel-Mottaleb M S A , Antonious M S , Ali M M A , et al . Photophysics and dynamics of coumarin laser dyes and their analytical implications[J]. Journal of Chemical Sciences, 1992, 104(2): 185-196.
16	Gong H L , Jiang Y , Hou R C , et al . A sensitive and selective fluorescent coumarin-based probe for detection of hypochlorite ion and its application to cellular imaging[J]. Journal of Fluorescence, 2016, 26(2): 403-406.
17	Danko M , Szabo E , Hrdlovic P . Synthesis and spectral characteristics of fluorescent dyes based on coumarin fluorophore and hindered amine stabilizer in solution and polymer matrices[J]. Dyes & Pigments, 2011, 90(2): 129-138.
18	Ma H H , Song Q S , Xu Y H , et al . Synthesis and performance of coumarin containing polymeric fluorescent dyes[J]. Pigment & Resin Technology, 2013, 42(6): 388-393.
19	王鹏, 张光华, 相瑞, 等 . 两种光稳定剂复配使用对纸张光致返黄的抑制作用[J]. 中国造纸, 2013, 32(12): 8-12.
	Wang P , Zhang G H , Xiang R , et al . Preliminary studies on prohibition of paper light-induced yellowing by using mixtures of stabilizers[J]. China Pulp & Paper, 2013, 32(12): 8-12.
20	Yu J , Wang L , Walzem R L , et al . Antioxidant activity of citrus limonoids, flavonoids, and coumarins[J]. Journal of Agricultural & Food Chemistry, 2005, 53(6): 2009-2014.
21	Abdel-Mottaleb M S A , Antonious M S , Ali M M A , et al . Photophysics and dynamics of coumarin laser dyes and their analytical implications[J]. Journal of Chemical Sciences, 1992, 104(2): 185-196.
22	罗清龙 . 香豆素类光电材料的合成与表征及其在OLED中的应用[D]. 兰州: 兰州交通大学, 2018.
	Luo Q L . Synthesis and characterization of coumarin photoelectric materials and application in OLED[D]. Lanzhou: Lanzhou Jiaotong University, 2018.
23	Elgemeie G H , Ahmed K A , Ahmed E A , et al . A simple approach for the synthesis of coumarin fluorescent dyes under microwave irradiation and their application in textile printing[J]. Pigment & Resin Technology, 2016, 45(4): 217-224.
24	王鹏, 张光华, 付小龙, 等 . 基于香豆素型荧光增白剂的返黄抑制剂的合成与性能[J]. 精细化工, 2013, 30(3): 333-338.
	Wang P , Zhang G H , Fu X L , et al . Synthesis of yellowing inhibitor based on the coumarin type fluorescent brighteners and its performance[J]. Fine Chemicals, 2013, 30(3): 333-338.
25	郑华, 张光华, 相瑞 . 阳离子香豆素的合成及其对高得率浆的返黄抑制作用[J]. 中国造纸, 2015, 34(8): 13-17.
	Zheng H , Zhang G H , Xiang R . Synthesis and application of cationic coumarin fluorescent brighteners[J]. China Pulp & Paper, 2015, 34(8): 13-17.
26	刘国俊 . 香豆素类荧光聚合物制备及其返黄抑制性能研究[D]. 西安: 陕西科技大学, 2018.
	Liu G J . Preparation and performance research on yellowing inhibition of coumarin fluorescent polymers[D]. Xi an：Shaanxi University of Science and Technology, 2018.
27	梁起, 于丽 . 纳米粒子综述[J]. 河南大学学报(自然科学版), 1997, (2): 56-58.
	Liang Q , Yu L . Review of nanoparticles[J]. Journal of Henan University (Natural Science), 1997, (2): 56-58.
28	王东波, 田言, 冯玉杰, 等 . SiO₂-g-PS纳米微球的制备及其在增韧PP中的应用[J]. 化工学报, 2007, 58(12): 3180-3184.
	Wang D B , Tian Y , Feng Y J , et al . Preparation of polystyrene/SiO₂ nanosphere and its application in toughening PP matrix[J]. Journal of Chemical Industry and Engineering(China), 2007, 58 (12): 3180-3184.
29	Xu M H , Cao Y Y , Gao S G . Surface modification of nano-silica with silane coupling agent[J]. Key Engineering Materials, 2014, 636: 23-27.
30	Fajzulin I , Zhu X , Möller M . Nanoparticulate inorganic UV absorbers: a review[J]. Journal of Coatings Technology and Research, 2015, 12(4): 617-632.
31	余红雨, 杨荣静, 严波, 等 . 纳米级防紫外无机材料的研究进展[J]. 上海纺织科技, 2019, 47(2): 8-13.
	Yu H Y , Yang R J , Yan B , et al . Research progress of nanoscale inorganic materials for ultraviolet resistant fabrics[J]. Shanghai Textile Science & Technology, 2019, 47(2): 8-13.
32	Xue C H , Yin W , Jia S T , et al . UV-durable superhydrophobic textiles with UV-shielding property by coating fibers with ZnO/SiO₂ core/shell particles[J]. Advanced Materials Research, 2012, 441: 351-355.

[1]	江河, 袁俊飞, 王林, 邢谷雨. 均流腔结构对微细通道内相变流动特性影响的实验研究[J]. 化工学报, 2023, 74(S1): 235-244.
[2]	仪显亨, 周骛, 蔡小舒, 蔡天意. 光纤后向动态光散射测量纳米颗粒的浓度适用范围研究[J]. 化工学报, 2023, 74(8): 3320-3328.
[3]	孟令玎, 崇汝青, 孙菲雪, 孟子晖, 刘文芳. 改性聚乙烯膜和氧化硅固定化碳酸酐酶[J]. 化工学报, 2023, 74(8): 3472-3484.
[4]	郑玉圆, 葛志伟, 韩翔宇, 王亮, 陈海生. 中高温钙基材料热化学储热的研究进展与展望[J]. 化工学报, 2023, 74(8): 3171-3192.
[5]	汤晓玲, 王嘉瑞, 朱玄烨, 郑仁朝. 基于Pickering乳液的卤醇脱卤酶催化合成手性环氧氯丙烷[J]. 化工学报, 2023, 74(7): 2926-2934.
[6]	张澳, 罗英武. 低模量、高弹性、高剥离强度丙烯酸酯压敏胶[J]. 化工学报, 2023, 74(7): 3079-3092.
[7]	蔡斌, 张效林, 罗倩, 党江涛, 左栗源, 刘欣梅. 导电薄膜材料的研究进展[J]. 化工学报, 2023, 74(6): 2308-2321.
[8]	李勇, 高佳琦, 杜超, 赵亚丽, 李伯琼, 申倩倩, 贾虎生, 薛晋波. Ni@C@TiO₂核壳双重异质结的构筑及光热催化分解水产氢[J]. 化工学报, 2023, 74(6): 2458-2467.
[9]	毛磊, 刘冠章, 袁航, 张光亚. 可捕集CO₂的纳米碳酸酐酶粒子的高效制备及性能研究[J]. 化工学报, 2023, 74(6): 2589-2598.
[10]	徐文超, 孙志高, 李翠敏, 李娟, 黄海峰. 静态条件下表面活性剂E-1310对HCFC-141b水合物生成的影响[J]. 化工学报, 2023, 74(5): 2179-2185.
[11]	王瑞恒, 何品晶, 吕凡, 章骅. 垃圾焚烧飞灰水洗后三种固液分离方法参数比较及优化[J]. 化工学报, 2023, 74(4): 1712-1723.
[12]	王子健, 柯明, 李佳涵, 李舒婷, 孙巾茹, 童燕兵, 赵治平, 刘加英, 任璐. 短b轴ZSM-5分子筛制备方法及应用研究进展[J]. 化工学报, 2023, 74(4): 1457-1473.
[13]	刘润竹, 储甜甜, 张孝阿, 王成忠, 张军营. α，ω-端羟基亚苯基氟硅聚合物的合成及性能[J]. 化工学报, 2023, 74(3): 1360-1369.
[14]	陈向上, 马振杰, 任希华, 贾悦, 吕晓龙, 陈华艳. 三维网络萃取膜的制备及传质效率研究[J]. 化工学报, 2023, 74(3): 1126-1133.
[15]	黄心童, 耿宇昊, 刘恒源, 陈卓, 徐建鸿. 微流控制备新型功能纳米粒子研究进展[J]. 化工学报, 2023, 74(1): 355-364.