Preparation and properties of nanoparticle composite coumarin fluorescent emulsion for papermaking

doi:10.11949/0438-1157.20190752

Abstract

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

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

CLC Number:

TQ 610.495

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.

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.

Figures/Tables 14

Fig.1 Preparation route of modified nanoparticles

Fig.2 Chemical reaction for coumarin fluorescent monomer

Fig.3 Preparation route of nanoparticle composite fluorescent emulsion

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

Fig.5 Infrared spectra of fluorescent emulsion

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

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

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

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

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

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

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°

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

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

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