用于高得率浆纸张增白的二苯乙烯型水性聚氨酯荧光乳液的合成及其性能

doi:10.16085/j.issn.1000-6613.2019-0329

化工进展 ›› 2019, Vol. 38 ›› Issue (11): 5084-5090.DOI: 10.16085/j.issn.1000-6613.2019-0329

用于高得率浆纸张增白的二苯乙烯型水性聚氨酯荧光乳液的合成及其性能

张光华(),刘丹,王帆,郭明媛,唐进霞

陕西科技大学陕西省轻化工助剂重点实验室，陕西西安 710021

收稿日期:2019-03-10 出版日期:2019-11-05 发布日期:2019-11-05
通讯作者: 张光华
作者简介:张光华，教授，博士生导师，研究方向为高分子功能材料及造纸化学品的制备与应用。E-mail：zhanggh@sust.edu.cn。
基金资助:
国家自然科学基金(31670596);陕西省教育厅重点实验室项目(13JS019)

Synthesis and properties of stilbene type waterborne polyurethane emulsion with fluorescent for high yield pulp paper whitening

Guanghua ZHANG(),Dan LIU,Fan WANG,Mingyuan GUO,Jinxia TANG

Shaanxi Key Laboratory of Chemical Additives for Industry，Shaanxi University of Science and Technology，Xi’an 710021，Shaanxi，China

Received:2019-03-10 Online:2019-11-05 Published:2019-11-05
Contact: Guanghua ZHANG

摘要/Abstract

摘要：

为了改善二苯乙烯型荧光增白剂的光异构现象及在高得率浆纸表面的吸附性，以三聚氯氰为交联单体，将4,4'-二氨基二苯乙烯-2,2'-二磺酸、乙醇胺和对氨基苯磺酸依次引入同一个分子中制得荧光单体（SFBs），进一步将其作为扩链剂制备了二苯乙烯型水性聚氨酯荧光(SWPU)乳液。采用¹H NMR、FTIR、UV-vis、荧光光谱、乳液粒径分析仪和稳定性分析仪等对所制备的荧光单体和乳液的结构和性能进行表征，最后其SWPU乳液用于高得率（杨木化机浆APMP）纸张表面施胶，通过紫外光加速老化试验对比了空白纸样和经SWPU乳液涂布后纸样的白度值，通过抗张强度检测、纸样吸水性Cobb值检测对比纸样的物理性能变化。结果发现，制备的二苯乙烯型水性聚氨酯荧光乳液粒径分布窄，平均粒径为66.78nm，乳液稳定性良好，经SWPU乳液涂布后的纸样初始白度比空白纸样增加了15.6%(ISO)；经48h光老化处理，空白纸样白度降低了17.56%(ISO)，而涂布纸样的白度只降低了13.39%(ISO)；另外，涂布后纸样的抗张强度增大，Cobb值减小；说明制得的SWPU乳液在高得率浆纸表面有良好的吸附性，并具有一定的增白、抑制纸张返黄和提高纸张物理强度效果。

关键词: 二苯乙烯, 荧光单体, 荧光增白剂, 水性聚氨酯乳液, 高得率浆纸, 返黄抑制

Abstract:

In order to improve the photoisomerism of the stilbene type fluorescent brighteners and its adsorbability on the surface of high yield paper,fluorescent monomer named SFBs was firstly synthesized by using cyanuric chloride, 4,4'-diamino stilbene-2,2'-disulfonic acid ,diethanolamine and p-aminobenzene sulfonic acid as raw materils. Afterward, a novel stilbene type waterborne polyurethane emulsion with fluorescence (SWPU) was synthesized by using SFBs as chain extender. ¹H NMR,FTIR,UV-vis, fluorescence spectrum, stability analyzer and dynamic lights scattering(DLS) were employed to verify the structures and properties of SFBs and SWPU emulsion. The whiteness and physical properties of papers before and after coating by SWPU emulsion were compared systematically by ultraviolet light accelerated aging tests, tensile strength tests and water absorption tests, respectively. The results showed that the SWPU emulsion presented a narrow polydispersity , superior stability, and an average particle size of 66.78nm. The initial whiteness of paper coated by SWPU emulsion increased by 15.6%(ISO) as compared to that of uncoated, and declined by 13.39% (ISO) after 48 h UV accelerated irradiation, which was obviously lower than that of uncoated paper (declined by 17.56% ). Additionally, the tensile strength of the paper was enhanced and the Cobb index decreased after coating. Therefore, SWPU emulsion synthesized in this work exhibits excellent film forming, whitening and anti-yellowing ability simultaneously.

Key words: stilbene, fluorescence monomer, flourescent brightener, waterborne polyurethane emulsion, high yield pulp paper, inhibition of yellowing

中图分类号:

TQ610.495

张光华,刘丹,王帆,郭明媛,唐进霞. 用于高得率浆纸张增白的二苯乙烯型水性聚氨酯荧光乳液的合成及其性能[J]. 化工进展, 2019, 38(11): 5084-5090.

Guanghua ZHANG,Dan LIU,Fan WANG,Mingyuan GUO,Jinxia TANG. Synthesis and properties of stilbene type waterborne polyurethane emulsion with fluorescent for high yield pulp paper whitening[J]. Chemical Industry and Engineering Progress, 2019, 38(11): 5084-5090.

图/表 10

图1 二苯乙烯型荧光增白单体的合成反应式

图3 SFBs、SWPU乳液和PU预聚体的红外吸收光谱

图4 SFBs的1H NMR光谱

图5 乳胶膜的紫外吸收光谱

图6 SFBs和SWPU乳液水溶液的荧光发射和激发光谱

图7 乳液的粒径分布

图8 乳液的稳定性指数变化曲线

图9 涂布后纸张表面白度随紫外老化时间的变化

表1 经SWPU乳液涂布前后纸张的物理性能

纸样类型	抗张强度/kN·m	Cobb值（60 s）
涂布前	2.36	104
涂有5%的SWPU乳液的纸样	4.83	69
涂有8%的SWPU乳液的纸样	5.40	52
涂有10%的SWPU乳液的纸样	6.26	43

图10 聚氨酯荧光乳液涂布前后的SEM图

参考文献 11

1	MANDAB M K, BLOKK, PATELM K. Innovations in papermaking: an LCA of printing and writing paper from conventional and high yield pulp[J]. Science of the Total Environment, 2012, 439(1): 307-320.
2	ZHANGH, HUH, HEZ, et al. Highly substituted cationic starch as an anionic trash catcher for high-yield pulp[J]. Tappi Journal, 2009, 8(7): 31-36.
3	张光华, 徐海龙, 郭锦鸽, 等.具有荧光增白作用的新型返黄抑制剂的合成及性能[J]. 化工学报, 2012, 63（10）: 3358-3364.
	ZHANGGuanghua, XUHailong, GUOJinge, et al. Synthesis and properties of new yellowing inhibitor with fluorescent whitenin[J].CIESC Journal, 2012, 63(10): 3358-3364.
4	李朦, 强西怀, 张辉, 等. 脂肪胺聚氧乙烯醚（PAE）型阳离子水性聚氨酯乳液的制备和性能[J]. 化工进展, 2015, 34(1): 193-197.
	LIMeng, QIANGXihuai, ZHANGHui, et al. Synthesis and characterization of PAE-based cationic waterborne polyurethane[J]. Chemical Industry and Engineering Progress, 2015, 34(1): 193-197.
5	HUSSAINM, SHAMEYR, HINKSD, et a1. Synthesis of novel stilhene-alkoxysilane fluorescent brighteners, and their performance on cotton fiber as fluorescent brightening and ultraviolet absorbing agents[J]. Dyes and Pigments,2012, 92(3): 1231-1240.
6	SHARMAP, BROWNS, WALTERG, et a1. Nanoparticles for bioimaging[J]. Advances in Colloid＆Interface Science, 2006, 123/124/125/126: 471-485.
7	CHANY, ZIMMERJ, STROHM, et a1. Incorporation of luminescent nanocrystals into monodisperse core-shell silica microspheres[J]. Advanced Materials, 2004, 16(23/24): 2092-2097.
8	吕彤, 张光华, 郭明媛. 聚苯乙烯荧光乳液的制备及其性能研究[J]. 发光学报, 2018, 39(4): 466-474.
	LUTong, ZHANGGuanghua, GUOMingyuan. Preparation of polystyrene fluorescent emulsion and its properties[J]. Chinese Journal of Luminescence, 2018, 39(4): 466-474.
9	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.
	ZHENGHua, ZHANGGuanghua, XIANGRui. Synthesis and application of cationic coumarin fluorescent brighteners[J].China Pulp & Paper, 2015, 34(8): 13-17.
10	BARDAJEEG R, LIA Y, HALEYJ C, et al. Synehesis and photophysical properties of novel, functional fluorescent naphthalimide dyes[J]. Dyes and Pigment, 2008, 79(1): 24-32.
11	郭玉花, 李树材, 王高升, 等. 水性聚氨酯表面施胶剂的合成及其应用研究[J]. 中国造纸, 2011, 30(1): 10-14.
	GUOYuhua, LIShucai, WANGGaosheng, et al. Synthesis of waterborne polyurethane surface sizing agent and its effectson properties of papers[J]. China Pulp & Paper, 2011, 30(1): 10-14.

[1]	朱佳杰, 刘元伟, 沈江南, 高从堦. 4,4'-二叠氮二苯乙烯-2,2-二磺酸钠的应用及发展前景[J]. 化工进展, 2019, 38(04): 1804-1814.
[2]	苏钰涵, 滕欣余, 王博威, 林晨辉, 陈立功, 李阳, 闫喜龙. 光稳定型9,10-二苯乙烯基蒽类变色材料的合成及性能[J]. 化工进展, 2018, 37(01): 212-222.
[3]	高洪军, 陈世明, 金一丰, 糜泽峰. 二苯乙烯苯酚聚氧乙烯醚(10)的合成工艺[J]. 化工进展, 2017, 36(12): 4635-4640.
[4]	张军华1，国海光1，郇昌永1，姜莉2，沈强1. Pt/C催化加氢法制备DSD酸[J]. 化工进展, 2012, 31(09): 2070-2074.

用于高得率浆纸张增白的二苯乙烯型水性聚氨酯荧光乳液的合成及其性能

Synthesis and properties of stilbene type waterborne polyurethane emulsion with fluorescent for high yield pulp paper whitening

RichHTML

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

图/表 10

参考文献 11

相关文章 4

编辑推荐

Metrics

本文评价