Preparation and properties of rosin based fluorescent waterborne polyurethane

doi:10.16085/j.issn.1000-6613.2022-0112

Abstract

Abstract:

Rosin-based fluorescent waterborne polyurethane emulsion (FWPU) with good stability was successfully prepared using isophorone diisocyanate (IPDI), ester (RAG) of acrylic rosin adduct and 2-hydroxyethyl methacrylate as raw materials, dihydroxymethyl propyl acid (DMPA) as hydrophilic chain extender and 5,7-dihydroxy-4-methyl coumarin (DHMC) as fluorescent chain extender. The structure of FWPU was characterized by ¹H NMR, Infrared spectrum and UV-visible spectroscopy, and the effects of the amount of DHMC and quenching agent 1,4-hydroquinone (HQ) on the fluorescence performance of FWPU were discussed. The UV protection performance (UPF) of polyurethane film was tested. The results showed that DHMC was successfully linked onto the polyurethane main chain. With the increase of the dosage of DHMC, the fluorescence intensity of FWPU increased gradually, and the maximum fluorescence intensity was 5002 when the dosage was 1%. Compared with DHMC, the fluorescence intensity of FWPU increased significantly. The fluorescence quenching effect of HQ on FWPU was obvious. With the addition of DHMC, the UPF value of polyurethane increased from 6.86 to 12.27, and the UV protection performance was improved as well as the water resistance.

Key words: rosin ester, waterborne polyurethane, fluorescent intensity, UV protection performance

摘要：

以异佛尔酮二异氰酸酯（IPDI）、丙烯酸松香加成物与甲基丙烯酸2-羟乙酯酯化物（RAG）为原料，二羟甲基丙酸（DMPA）为亲水扩链剂，5,7-二羟基-4-甲基香豆素（DHMC）为荧光扩链剂，成功制备了稳定性好的松香基荧光水性聚氨酯乳液（FWPU）。采用核磁共振氢谱、红外光谱、紫外光谱等对FWPU进行了结构表征，探讨了DHMC用量、猝灭剂1,4-对苯二酚（HQ）对FWPU荧光性能的影响，测试了聚氨酯膜的紫外防护性能。结果表明，DHMC成功接枝到聚氨酯主链上，随着其用量的增加，FWPU的荧光强度逐渐增大，用量为1%时荧光强度最大（达5002）；相比于DHMC，FWPU的荧光强度明显增大；HQ对FWPU荧光猝灭效果明显。加入DHMC，聚氨酯的紫外线防护系数从6.86增加到12.27，紫外防护性能得到改善，耐水性也有一定的提高。

关键词: 松香酯化物, 水性聚氨酯, 荧光强度, 紫外防护性能

CLC Number:

TQ323.8

YAN Chengfei, YU Caili, ZHANG Fa’ai. Preparation and properties of rosin based fluorescent waterborne polyurethane[J]. Chemical Industry and Engineering Progress, 2022, 41(11): 6061-6067.

严成飞, 余彩莉, 张发爱. 松香基荧光水性聚氨酯的制备及性能[J]. 化工进展, 2022, 41(11): 6061-6067.

Figures/Tables 10

References 18

1	柴春鹏, 赵佳, 侯靖辉, 等. 含一种蒽醌结构红色水性聚氨酯的制备及表征[J]. 北京理工大学学报, 2021, 41(4): 432-438.
	CHAI Chunpeng, ZHAO Jia, HOU Jinghui, et al. Preparation and characterization of red waterborne polyurethane with an anthraquinone structure[J]. Transactions of Beijing Institute of Technology, 2021, 41(4): 432-438.
2	TIAN Saiqi, CHEN Yinyan, ZHU Yifan, et al. A fluorescent polyurethane with covalently cross-linked rhodamine derivatives[J]. Polymers, 2020, 12(9): 1989.
3	解芝茜, 王继印, 陶灿, 等. 水性聚氨酯荧光材料的制备及其荧光性能[J]. 功能高分子学报, 2014, 27(4): 426-431.
	XIE Zhiqian, WANG Jiyin, TAO Can, et al. Synthesis and fluorescence properties of waterborne polyurethane fluorescent materials[J]. Journal of Functional Polymers, 2014, 27(4): 426-431.
4	JIN Qingjun, HU Yang, SHEN Jie, et al. A novel 1,8-naphthalimide green fluorescent dye and its corresponding intrinsically fluorescent polyurethane latexes[J]. Journal of Coatings Technology and Research, 2017, 14(3): 571-582.
5	金青君, 徐旻, 黄馨仪, 等. 萘酰亚胺类荧光染料及共聚型荧光聚氨酯乳液的合成与性能[J]. 物理化学学报, 2015, 31(5): 989-997.
	JIN Qingjun, XU Min, HUANG Xinyi, et al. Synthesis and properties of naphthalimide fluorescent dye and covalent fluorescent polyurethane emulsion[J]. Acta Physico-Chimica Sinica, 2015, 31(5): 989-997.
6	ZAMANI E, YAHYAEI H, KHOSRAVI A, et al. Synthesis and characterization of a novel self-colored fluorescent polycarbonate urethane based on the 1, 8-naphthalimide group[J]. Journal of Macromolecular Science, Part B, 2019, 58(9): 772-781.
7	KUMAR R, YADAV R, KOLHE M A, et al. 8-Hydroxypyrene-1,3,6-trisulfonic acid trisodium salt (HPTS) based high fluorescent, pH stimuli waterborne polyurethane coatings[J]. Polymer, 2018, 136: 157-165.
8	HU Xianhai, LIU Xiang, LIU Manli, et al. A waterborne polyurethane-based polymeric dye with covalently linked disperse red 11[J]. Reactive and Functional Polymers, 2018, 132: 1-8.
9	TENORIO-ALFONSO A, SÁNCHEZ M C, FRANCO J M. A review of the sustainable approaches in the production of bio-based polyurethanes and their applications in the adhesive field[J]. Journal of Polymers and the Environment, 2020, 28(3): 749-774.
10	许建本, 余彩莉, 边峰, 等. 丙烯酸松香加成物与GMA酯化物的合成与表征[J]. 生物质化学工程, 2017, 51(4): 47-52.
	XU Jianben, YU Caili, BIAN Feng, et al. Synthesis and characterization of ester of acrylic rosin adduct and GMA[J]. Biomass Chemical Engineering, 2017, 51(4): 47-52.
11	WANG Xiangmei, LI Qian. A new method for preparing low viscosity and high solid content waterborne polyurethane—Phase inversion research[J]. Progress in Organic Coatings, 2019, 131: 285-290.
12	HUANG Hui, XU Min, GAO Yuan, et al. Water-soluble fluorescent conjugated polymer-enzyme hybrid system for the determination of both hydroquinone and hydrogen peroxide[J]. Talanta, 2011, 86: 164-169.
13	崔岳玲, 程衍铭, 孙稚源. 纺织品的珍珠纳米整理及紫外线防护性能测试[J]. 上海纺织科技, 2012, 40(9): 59-60, 62.
	CUI Yueling, CHENG Yanming, SUN Zhiyuan. Pearl nano-finishing on textiles and anti-ultraviolet performance test[J]. Shanghai Textile Science & Technology, 2012, 40(9): 59-60, 62.
14	HOU Aiqin, CHEN Zhuo, ZHENG Changwu, et al. Multi-functional fluorescence cellulose composites based on a modified amphiphilic waterborne polyurethane by covalent suspension of the triazine groups[J]. Progress in Organic Coatings, 2021, 158: 106386.
15	张光华, 刘丹, 王帆, 等. 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.
	ZHANG Guanghua, LIU Dan, WANG Fan, et al. 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.
16	PILEHKOUHI M, SHAKI H, KHOSRAVI A, et al. Synthesis and characterization of a fluorescent water-borne polyurethane based on a novel naphthalimide dye[J]. Journal of Macromolecular Science, Part B, 2018, 57(2): 151-167.
17	李朦, 强西怀, 薛强. 香豆素衍生物基荧光型水性聚氨酯的制备及性能[J]. 化工进展, 2015, 34(11): 4001-4005, 4013.
	LI Meng, QIANG Xihuai, XUE Qiang. Synthesis and properties of AFC-based waterborne polyurethane[J]. Chemical Industry and Engineering Progress, 2015, 34(11): 4001-4005, 4013.
18	罗汝楠, 赵胜男, 范敏, 等. 分散染料颜色对涤纶织物紫外线防护性能的影响[J]. 纺织科技进展, 2017(8): 33-36.
	LUO Runan, ZHAO Shengnan, FAN Min, et al. Effect of disperse dye color on UV protection performance of polyester fabric[J]. Progress in Textile Science & Technology, 2017(8): 33-36.

样品	UPF	T（UVA）/%	T（UVB）/%
FWPU0	6.86	15.29	12.34
FWPU0.2	10.85	9.03	9.52
FWPU0.4	11.08	8.90	9.20
FWPU0.6	11.51	8.58	8.65
FWPU0.8	12.23	8.00	8.51
FWPU1.0	12.27	7.74	7.99

样品	UPF	T（UVA）/%	T（UVB）/%
FWPU0	6.86	15.29	12.34
FWPU0.2	10.85	9.03	9.52
FWPU0.4	11.08	8.90	9.20
FWPU0.6	11.51	8.58	8.65
FWPU0.8	12.23	8.00	8.51
FWPU1.0	12.27	7.74	7.99

[1]	LU Shaofeng, CUI Shanshan, SHI Wenzhao, LI Susong, XIE Yan, YANG Qiancheng. Preparation and properties of cross-linked waterborne polyurethane solid-solid phase change material [J]. Chemical Industry and Engineering Progress, 2022, 41(5): 2574-2581.
[2]	LI Ting, DU Shaohui, CUI Jinfeng, WANG Yanghui, LI Hulin, GUO Runlan, WANG Peng, WANG Zhenjun, GUO Junhong, YANG Baoping. Preparation and properties of waterborne polyurethane paper sizing agents with phosphorus-boron hybrid prepolymer blocks [J]. Chemical Industry and Engineering Progress, 2022, 41(10): 5549-5557.
[3]	Dandan LI, Jihuai TAN, Dinggen HU, Jianbin CHEN, Zhulan LIU, Yunfeng CAO. Recent development of waterborne polyurethane as surface sizing agent: preparation, modification and application [J]. Chemical Industry and Engineering Progress, 2021, 40(1): 366-377.
[4]	Xiaojuan LAI,Yinyin ZHANG,Jiahui LIU,Lei WANG. Preparation and properties of surface modified GO modified amine-free waterborne polyurethane-acrylate emulsion [J]. Chemical Industry and Engineering Progress, 2020, 39(4): 1389-1395.
[5]	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.
[6]	ZHAO Yanna, JI Dingxi. Preparation and properties of nano CeO₂/waterborne polyurethane composites [J]. Chemical Industry and Engineering Progress, 2017, 36(12): 4501-4507.
[7]	LI Meng, QIANG Xihuai, XUE Qiang. Synthesis and properties of AFC-based waterborne polyurethane [J]. Chemical Industry and Engineering Progree, 2015, 34(11): 4001-4005,4013.
[8]	LI Meng, QIANG Xihuai, ZHANG Hui, YAN Zhe. Synthesis and characterization of PAE-based cationic waterborne polyurethane [J]. Chemical Industry and Engineering Progree, 2015, 34(1): 193-197,218.
[9]	WANG Yin, FU Heqing, YAN Caibin, YU Rongmin, XIA Jianrong. Research progress of waterborne polyurethane modified by nanomaterials [J]. Chemical Industry and Engineering Progree, 2015, 34(02): 463-469.
[10]	WANG Xuechuan，REN Jing，QIANG Taotao. Research progress in waterborne polyurethane hydrophilic chain extender [J]. Chemical Industry and Engineering Progree, 2014, 33(02): 432-438.
[11]	DENG Wei，HUANG Hong，FU Heqing. Progress of modification of waterborne polyurethane adhesive [J]. Chemical Industry and Engineering Progree, 2011, 30(6): 1341-.
[12]	YANG Yan，SHEN Yiding，LAI Xiaojuan，WANG Lei. Synthesis and characterization of waterborne polyurethane modified by glucose [J]. Chemical Industry and Engineering Progree, 2011, 30(2): 386-.
[13]	YAN Caibin，FU Heqing. Research progress of modification technology for waterborne polyurethane [J]. Chemical Industry and Engineering Progree, 2011, 30(12): 2658-.
[14]	ZHAO Caixia，ZOU Guoxiang，LI Jinchun. Preparation and characterization of waterborne polyurethane/polyvinyl alcohol composite [J]. Chemical Industry and Engineering Progree, 2011, 30(10): 2271-.
[15]	XU Xu，SHANG Shibin，SONG Zhanqian. Synthesis and properties of fumaropimaric acid-type waterborne polyurethane [J]. Chemical Industry and Engineering Progree, 2010, 29(6): 1102-.