Preparation and properties of silicon and sulfhydryl compound modified UV-curable WPUA coating

doi:10.16085/j.issn.1000-6613.2021-1413

Abstract

Abstract:

Use hydroxy-terminated silicone oil (HS) and pentaerythritol tetra-3-mercaptopropionate (PETMP) to modify UV-curable waterborne polyurethane acrylate (WPUA) successively, and explored the addition amount of HS and PETMP influence on the properties of the coating film. The structures of the products before and after modification were characterized by FTIR, the particle size of emulsion was tested, and the morphology and coating cross section of emulsion were analyzed by TEM and SEM. The mechanical properties, hydrophobicity, heat resistance and corrosion resistance of the coating were evaluated by adhesion, hardness, flexibility, impact resistance, contact angle, comprehensive thermal analysis, electrochemical impedance spectroscopy and polarization curve. The results showed that when the addition of HS and PETMP were 3% and 5%, respectively, the hardness of UV cured WPUA coating modified by silicon/sulfhydryl composite increased from HB to 3H, the adhesion increased from level 3 to level 1, the flexibility was 0.5mm, the impact resistance was 50cm, the contact angle increased from 68.5° to 90.5°, the water absorption rate decreased from 18.78% to 6.94%, and the thermal stability of the coating was significantly enhanced. The coating impedance increased from 1.86×10⁶Ω·cm² to 6.45×10⁷Ω·cm², E_coor positively moved from -1.069V to -0.4215V, I_coor reduced from 2.12×10^-8A/cm² to 8.11×10^-10A/cm² with an annual corrosion rate of 0.0242mm. The introduction of appropriate amounts of HS and PETMP significantly improved the overall performance of the coating.

Key words: polyurethane acrylate, emulsions, UV curing, silicon/sulfhydryl modification, water resistance, composites

摘要：

采用端羟基硅油（HS）、季戊四醇四-3-巯基丙酸酯（PETMP）先后改性紫外光固化水性聚氨酯丙烯酸酯（WPUA），探究了HS及PETMP添加量对涂膜性能的影响。FTIR表征了改性前、后产物的结构；测试了乳液粒径，并利用TEM和SEM对乳液形貌和涂层断面进行了分析。通过涂膜附着力、硬度、柔韧性、抗冲击、接触角、综合热分析、电化学阻抗谱及极化曲线等测试评价涂层的机械性能、疏水性、耐热性及防腐性能。结果表明：当HS及PETMP添加量分别为3%、5%时，硅/巯基复合改性的紫外光固化WPUA涂层相对于改性前，硬度由HB提升为3H，附着力由3级提升到1级，柔韧性为0.5mm，耐冲击为50cm，接触角由68.5°提升到90.5°，吸水率由18.78%降低为6.94%；涂层的热稳定性显著增强；涂层阻抗由1.86×10⁶Ω·cm²增大到6.45×10⁷Ω·cm²，E_coor由 -1.069V正移到-0.4215V，I_coor由2.12×10^-8A/cm²减小到8.11×10^-10A/cm²，年腐蚀速率为0.0242mm。表明HS及PETMP的引入显著提升了涂层的综合性能。

关键词: 聚氨酯丙烯酸酯, 乳液, 紫外光固化, 硅/巯基改性, 耐水性, 复合材料

CLC Number:

TQ630.7

HU Yaoyao, WEI Ming, LI Boshen, DONG Yuelin, DONG Qunfeng, LIU Chuanqi. Preparation and properties of silicon and sulfhydryl compound modified UV-curable WPUA coating[J]. Chemical Industry and Engineering Progress, 2022, 41(6): 3186-3193.

胡瑶瑶, 魏铭, 李博申, 董月林, 董群峰, 刘传奇. 硅/巯基复合改性光固化WPUA涂料制备及其性能[J]. 化工进展, 2022, 41(6): 3186-3193.

Figures/Tables 15

References 22

1	WANG S P, WU Y G, DAI J Y, et al. Making organic coatings greener: renewable resource, solvent-free synthesis, UV curing and repairability[J]. European Polymer Journal, 2020, 123: 109439.
2	DENG L, TANG L Y, QU J Q. Synthesis and photopolymerization of novel UV-curable macro-photoinitiators[J]. Progress in Organic Coatings, 2020, 141: 105546.
3	LI X W, LIU Z, HONG P, et al. Synthesis of organic and inorganic hybrid nanoparticles as multifunctional photoinitiator and its application in UV-curable epoxy acrylate-based coating systems[J]. Progress in Organic Coatings, 2020, 141: 105565.
4	KOU Y, WANG J Y, LYU M, et al. Preparation and evaluation of epoxy methacrylate UV-curable coatings containing phthalazinone[J]. Polymer International, 2010, 59(1): 107-111.
5	郭浩, 甄焕珍, 李翠红, 等. 紫外光固化水性涂料研究进展[J]. 信息记录材料, 2021, 22(4): 1-3.
	GUO Hao, ZHEN Huanzhen, LI Cuihong, et al. Research progress of UV curable waterborne coatings[J]. Information Recording Materials, 2021, 22(4): 1-3.
6	姜健, 王小东, 石雅琳. 环氧改性聚氨酯丙烯酸酯树脂的合成及性能研究[C]//中国聚氨酯工业协会第19次年会, 上海, 2018: 512-514.
	JIANG Jian, WANG Xiaodong, SHI Yalin. Synthesis and properties of epoxy modified polyurethane acrylate resin[C]// Proceedings of the 19th Annual conference of China Polyurethane Industry Association, Shanghai, 2018: 512-514.
7	QIU F X, XU H P, WANG Y Y, et al. Preparation, characterization and properties of UV-curable waterborne polyurethane acrylate/SiO₂ coating[J]. Journal of Coatings Technology and Research, 2012, 9(5): 503-514.
8	WEI D D, HUANG X M, ZENG J J, et al. Facile synthesis of a castor oil-based hyperbranched acrylate oligomer and its application in UV-curable coatings[J]. Journal of Applied Polymer Science, 2020, 137(36): 49054.
9	LEE Y J, LA Y J, JEON O S, et al. Effects of boron nitride nanotube content on waterborne polyurethane-acrylate composite coating materials[J]. RSC Advances, 2021, 11(21): 12748-12756.
10	KUKANJA D, GOLOB J, ZUPANČIČ-VALANT A, et al. The structure and properties of acrylic-polyurethane hybrid emulsions and comparison with physical blends[J]. Journal of Applied Polymer Science, 2000, 78(1): 67-80.
11	张求学. 超支化水性聚氨酯/丙烯酸酯复合乳液的制备和性能研究[D]. 长春: 长春工业大学, 2019.
	ZHANG Qiuxue. Preparation and properties of hyperbranched waterborne polyurethane/acrylate hybrid emulsions[D]. Changchun: Changchun University of Technology, 2019.
12	BHAGAT S D, CHATTERJEE J, CHEN B H, et al. High refractive index polymers based on thiol-ene cross-linking using polarizable inorganic/organic monomers[J]. Macromolecules, 2012, 45(3): 1174-1181.
13	TIAN Y Z, WANG Q, WANG K, et al. From biomass resources to functional materials: a fluorescent thermosetting material based on resveratrol via thiol-ene click chemistry[J]. European Polymer Journal, 2020, 123: 109416.
14	DAI J Y, MA S Q, ZHU L X, et al. UV-thermal dual cured anti-bacterial thiol-ene networks with superior performance from renewable resources[J]. Polymer, 2017, 108: 215-222.
15	GUZMÁN D, RAMIS X, FERNÁNDEZ-FRANCOS X, et al. Preparation of click thiol-ene/thiol-epoxy thermosets by controlled photo/thermal dual curing sequence[J]. RSC Advances, 2015, 5(123): 101623-101633.
16	RESETCO C, HENDRIKS B, BADI N, et al. Thiol-ene chemistry for polymer coatings and surface modification-building in sustainability and performance[J]. Materials Horizons, 2017, 4(6): 1041-1053.
17	LUO X M, ZHANG P, LIU R, et al. Preparation and physical properties of functionalized graphene/waterborne polyurethane UV-curing composites by click chemistry[J]. Polymer International, 2016, 65(4): 415-422.
18	JIAO X J, LIU J L, JIN J, et al. UV-cured transparent silicone materials with high tensile strength prepared from hyperbranched silicon-containing polymers and polyurethane-acrylates[J]. ACS Omega, 2021, 6(4): 2890-2898.
19	晏文康, 万里鹰. 基于两种双硫键自修复聚氨酯制备及性能[J]. 工程塑料应用, 2021, 49(2): 34-39.
	YAN Wenkang, WAN Liying. Preparation and performance of self-healing polyurethane based on two kind of disulfide bonds[J]. Engineering Plastics Application, 2021, 49(2): 34-39.
20	LEI H B, HE D L, GUO Y N, et al. Synthesis and characterization of UV-absorbing fluorine-silicone acrylic resin polymer[J]. Applied Surface Science, 2018, 442: 71-77.
21	叶桐, 魏铭, 刘晓芳, 等.磷酸酯反应型乳化剂在叔丙乳液中的应用及防腐性能[J]. 化工进展, 2021, 40(8): 4413-4420.
	YE Tong, WEI Ming, LIU Xiaofang, et al. Application of phosphate reactive emulsifier in vinyl versatate-acrylate emulsion and its anticorrosive property[J]. Chemical Industry and Engineering Progress, 2021, 40(8): 4413-4420.
22	姚久提, 魏铭, 刘晓芳, 等.氟硅改性无溶剂环氧涂料的制备与性能[J].化工进展, 2021, 40(8): 4421-4427.
	YAO jiuti, WEI Ming, LIU Xiaofang, et al. Preparation and properties of fluorosilicone modified solventless epoxy coatings [J]. Chemical Industry and Engineering Progress, 2021, 40(8): 4421-4427.

样品	IPDI /mol	PEG400 /mol	BDO /mol	DMPA /mol	2-HEA /mol	w(HS) /%	w(PETMP) /%
WPUA	0.1	0.041	0.032	0.01	0.045	0	0
1%-HSWPUA	0.1	0.041	0.032	0.01	0.045	1	0
2%-HSWPUA	0.1	0.041	0.032	0.01	0.045	2	0
3%-HSWPUA	0.1	0.041	0.032	0.01	0.045	3	0
4%-HSWPUA	0.1	0.041	0.032	0.01	0.045	4	0
5%-HSWPUA	0.1	0.041	0.032	0.01	0.045	5	0
2.5%-PHSWPUA	0.1	0.041	0.032	0.01	0.045	3	2.5
5%-PHSWPUA	0.1	0.041	0.032	0.01	0.045	3	5
7.5%-PHSWPUA	0.1	0.041	0.032	0.01	0.045	3	7.5
10%PHSWPUA	0.1	0.041	0.032	0.01	0.045	3	10

样品	IPDI /mol	PEG400 /mol	BDO /mol	DMPA /mol	2-HEA /mol	w(HS) /%	w(PETMP) /%
WPUA	0.1	0.041	0.032	0.01	0.045	0	0
1%-HSWPUA	0.1	0.041	0.032	0.01	0.045	1	0
2%-HSWPUA	0.1	0.041	0.032	0.01	0.045	2	0
3%-HSWPUA	0.1	0.041	0.032	0.01	0.045	3	0
4%-HSWPUA	0.1	0.041	0.032	0.01	0.045	4	0
5%-HSWPUA	0.1	0.041	0.032	0.01	0.045	5	0
2.5%-PHSWPUA	0.1	0.041	0.032	0.01	0.045	3	2.5
5%-PHSWPUA	0.1	0.041	0.032	0.01	0.045	3	5
7.5%-PHSWPUA	0.1	0.041	0.032	0.01	0.045	3	7.5
10%PHSWPUA	0.1	0.041	0.032	0.01	0.045	3	10

样品	离心稳定性 /级	冻融稳定性	吸水率 /%	耐水性（168h）	乳液外观
WPUA	1	通过	18.78	严重锈蚀	透明泛蓝
1%-HSWPUA	1	通过	16.33	严重锈蚀	透明泛蓝
2%-HSWPUA	1	通过	12.64	严重锈蚀	透明泛蓝
3%-HSWPUA	1	通过	8.56	中度锈蚀	透明泛蓝
4%-HSWPUA	1	通过	8.93	中度锈蚀	乳白泛蓝
5%-HSWPUA	1	通过	8.47	中度锈蚀	透明泛蓝
2.5%-PHSWPUA	1	通过	8.13	轻度锈蚀	透明泛蓝
5%-PHSWPUA	1	通过	7.88	轻度锈蚀	透明泛蓝
7.5%-PHSWPUA	1	通过	6.94	轻度发白	透明泛蓝
10%-PHSWPUA	1	通过	8.21	中度锈蚀	乳白泛蓝

样品	离心稳定性 /级	冻融稳定性	吸水率 /%	耐水性（168h）	乳液外观
WPUA	1	通过	18.78	严重锈蚀	透明泛蓝
1%-HSWPUA	1	通过	16.33	严重锈蚀	透明泛蓝
2%-HSWPUA	1	通过	12.64	严重锈蚀	透明泛蓝
3%-HSWPUA	1	通过	8.56	中度锈蚀	透明泛蓝
4%-HSWPUA	1	通过	8.93	中度锈蚀	乳白泛蓝
5%-HSWPUA	1	通过	8.47	中度锈蚀	透明泛蓝
2.5%-PHSWPUA	1	通过	8.13	轻度锈蚀	透明泛蓝
5%-PHSWPUA	1	通过	7.88	轻度锈蚀	透明泛蓝
7.5%-PHSWPUA	1	通过	6.94	轻度发白	透明泛蓝
10%-PHSWPUA	1	通过	8.21	中度锈蚀	乳白泛蓝

样品	T_10%/℃	T_50%/℃	T_max/℃
WPUA	225.4	327.3	345.5
3%-HSWPUA	260.3	342.2	347.2
7.5%-PHSWPUA	280.5	352.2	353.8