Performance Studies of Nano⁃GO⁃ZnO / CeO2 Composite Particles in Water⁃Based Polyurethane Coatings

doi:10.12422/j.issn.1006-396X.2024.01.009

Abstract

Abstract:

The modification of waterborne polyurethane(WPU) coating can be improved, and the nanocomposite particles can be added to WPU coating, and its mechanical properties and ultraviolet resistance can be improved.GO was synthesized by modified Hummers method, nano?ZnO/CeO₂ by copprecipitation, and nano?GO?ZnO/CeO₂ by in situ polymerization.It was also characterised by FT?IR,TEM,SEM,XRD,etc.,and the effect of nano?GO?ZnO/CeO₂ doping on the performance of WPU was explored.The results showed that nano?GO?ZnO/CeO₂ was composed of hybrid particles formed by ZnO and CeO₂ of cubic crystal fluorite structure on the GO surface. Compared with the pure WPU film,the fracture tensile strength and elongation at break of the WPU film with the addition of a mass fraction of 0.6% nano?GO?ZnO/CeO₂ increased by 43.1% and 47.0%.After 168 h of UV aging experiments,the modified membrane absorbed 15.4% of water,increased the tensile strength at break by 328.0% and the elongation at break by 39.0%.It shows that nano?GO?ZnO/CeO₂ can effectively improve the mechanical properties and UV aging resistance of WPU after film formation.

Key words: Graphene oxide, Zinc oxide, Cerium oxide, Waterborne polyurethane, UV shielding, Mechanical properties

摘要：

对水性聚氨酯（WPU）涂料进行改性可以实现其功能化改进，将纳米复合粒子添加至WPU涂料中，可提升其力学性能及抗紫外能力。采用改进的Hummers法制备了氧化石墨烯（GO），共沉淀法制备了nano?ZnO/CeO₂，原位聚合法合成了nano?GO?ZnO/CeO₂；对制备的样品进行FT?IR、XRD、TEM、SEM等表征，探究了nano?GO?ZnO/CeO₂的掺杂对WPU性能的影响。结果表明，nano?GO?ZnO/CeO₂是由六方纤碎矿结构的ZnO和立方晶型萤石结构的CeO₂形成的杂化粒子负载于GO表面组成的；与纯WPU膜相比，添加质量分数为0.6%的nano?GO?ZnO/CeO₂，WPU膜的断裂拉伸强度和断裂拉伸率分别提高了43.1%和47.0%；经过168 h的紫外光老化实验后，改性膜的吸水率为15.4%，断裂拉伸强度和断裂拉伸率分别提高了328.0%、39.0%。由此可知，nano?GO?ZnO/CeO₂可以有效提高WPU成膜后的力学性能和抗紫外老化性能。

关键词: 氧化石墨烯, 氧化锌, 氧化铈, 水性聚氨酯, 紫外屏蔽, 力学性能

CLC Number:

TQ636.3

Honglin LI, Yuling YAN, Lihua LI. Performance Studies of Nano⁃GO⁃ZnO / CeO₂ Composite Particles in Water⁃Based Polyurethane Coatings[J]. Journal of Petrochemical Universities, 2024, 37(1): 66-73.

黎泓麟, 闫玉玲, 李丽华. Nano⁃GO⁃ZnO/CeO₂在水性聚氨酯涂料中的性能研究[J]. 石油化工高等学校学报, 2024, 37(1): 66-73.

Figures/Tables 12

Fig.1 FT?IR spectra of GO

Fig.2 XRD patters of samples

Fig.3 XRD plot of composite nanoions before and after GO modification

Fig.4 SEM and TEM image of GO

Fig.5 SEM images of nano?GO?ZnO/CeO2 under different magnification

Fig.6 UV diffuse plot of the nanoparticles and WPU membranes with different zinc and cerium molar ratios

Table 1 UPF values of pure WPU membranes and modified WPU membranes with different n（Zn）/n（Ce）

膜	n（Zn）/n（Ce）	UPF
纯WPU膜	-	8.70
改性WPU膜	1∶1	14.38
	1∶2	14.06
	1∶3	15.91
	1∶4	14.58
	4∶1	14.62

Fig.7 Effect of different nanomaterials on the CTAB degradation rate

Fig.8 Effect of nano?GO?ZnO / CeO2 mass fractions on the absorbance and mechanical properties of WPU membranes

Fig.9 Effect of n(Zn)/n(Ce) on the water absorption and mechanical properties of WPU membrane before and after aging

Fig.10 Contact angle test plot of pure WPU membrane and modified WPU membrane

Fig.11 TG curves of pure WPU membranes and modified WPU membranes

References 21

1	YIN X，PANG H S，LUO Y J，et al.Eco⁃friendly functional two⁃component flame⁃retardant waterborne polyurethane coatings：A review［J］.Polymer Chemistry，2021，12（38）：5400⁃5411.
2	宋文迪.紫外光固化水性聚氨酯丙烯酸酯的制备及性能研究［D］.北京：北京化工大学，2018.
3	马中柱.功能化聚（醚⁃碳酸酯）和环碳酸酯的制备及其在水性聚氨酯中的应用［D］.杭州：浙江大学，2020.
4	黄慧华.多功能水性聚氨酯光学涂料的制备与性能研究［D］.广州：华南理工大学，2020.
5	王杰，杨明君，陈丽，等.UV固化水性含氟聚氨酯丙烯酸酯的制备与性能表征［J］.现代化工，2021，41（S1）：256⁃260.
	WANG J，YANG M J，CHEN L，et al.Preparation and performance characterization of UV⁃curable waterborne fluorine⁃containing polyurethane acrylate［J］.Modern Chemical Industry，2021，41（S1）：256⁃260.
6	WANG X Y，CUI Y，WANG Y N，et al.Preparation and characteristics of crosslinked fluorinated acrylate modified waterborne polyurethane for metal protection coating［J］.Progress in Organic Coatings，2021，158：106371.
7	AGNOL L D，DIAS F T G，ORNAGHI H L J R，et al.UV⁃curable waterborne polyurethane coatings：A state⁃of⁃the⁃art and recent advances review［J］.Progress in Organic Coatings，2021，154：106156.
8	章继龙.粉煤灰沸石分子筛负载氧化铈催化剂的制备及其催化燃烧二氯甲烷性能［J］.化工环保，2021，41（1）：91⁃97.
	ZHANG J L.Preparation of fly ash zeolite supported cerium oxide catalyst and its catalytic performance for combustion of dichloromethane［J］.Environmental Protection of Chemical Industry，2021，41（1）：91⁃97.
9	杨萍，李有喜，蔡武锋，等.双金属MOF⁃74（MgxNi_1- x）的制备及其对CO₂/N₂的吸附分离性能研究［J］.辽宁石油化工大学学报，2022，42（6）：1⁃7.
	YANG P，LI Y X，CAI W F，et al.Preparation of bimetallic MOF⁃74（MgxNi_1- x） and its adsorption and separation performance for CO₂/N₂［J］.Journal of Liaoning Petrochemical University，2022，42（6）：1⁃7.
10	陈佳慧，黎泓麟，杨紫坤，等.GO改性的铈基纳米复合光催化剂性能对比研究［J］.石油化工高等学校学报，2022，35（1）：63⁃67.
	CHEN J H，LI H L，YANG Z K，et al.Preparation of GO⁃modified cerium⁃based nano⁃composite photocatalyst and a comparative study on photocatalytic properties［J］.Journal of Petrochemical Universities，2022，35（1）：63⁃67.
11	LUO J，WANG J H，WEN S G，et al.Improved corrosion resistance based on APTES⁃grafted reduced sulfonated graphene/waterborne polyurethane coatings［J］.Journal of Coatings Technology and Research，2018，15（5）：1107⁃1115.
12	ZHANG S W，ZHANG D D，LI Z，et al.Polydopamine functional reduced graphene oxide for enhanced mechanical and electrical properties of waterborne polyurethane nanocomposites［J］.Journal of Coatings Technology and Research，2018，15（6）：1333⁃1341.
13	SUEN M C，GU J H，LEE H T，et al.In situ polymerisation and characteristic properties of the waterborne graphene oxide/poly（siloxane⁃urethane）s nanocomposites［J］.Polymer Bulletin，2017，74（12）：4921⁃4942.
14	LI P H，GUO W C，LU Z，et al.UV⁃responsive single⁃microcapsule self⁃healing material with enhanced UV⁃shielding SiO₂/ZnO hybrid shell for potential application in space coatings［J］.Progress in Organic Coatings，2021，151：106046.
15	LIZUNDIA E，RUIZ⁃RUBIO L，VILAS J L，et al.Poly（L⁃lactide）/zno nanocomposites as efficient UV⁃shielding coatings for packaging applications［J］.Journal of Applied Polymer Science，2016，133（2）：42426.
16	BALEN R，DA COSTA W V，DE LARA ANDRADE J，et al.Structural，thermal，optical properties and cytotoxicity of PMMA/ZnO fibers and films：Potential application in tissue engineering［J］.Applied Surface Science，2016，385：257⁃267.
17	DE LEON A C，ALONSO L，MANGADLAO J D，et al.Simultaneous reduction and functionalization of graphene oxide via ritter reaction［J］.ACS Applied Materials & Interfaces，2017，9（16）：14265⁃14272.
18	闫龙龙，厉晓英.改性石墨烯对液压油摩擦学性能的影响［J］.石油炼制与化工，2020，51（12）：76⁃81.
	YAN L L，LI X Y.Effect of modified graphene on tribological properties of hydraulic oil［J］.Petroleum Processing and Petrochemicals，2020，51（12）：76⁃81.
19	KIM H，LEE S.Evaluation of laundering durability of electro⁃conductive textile dip⁃coated on para aramid knit with graphene/waterborne polyurethane composite［J］.Fibers and Polymers，2018，19（11）：2351⁃2358.
20	POURHASHEM S，GHASEMY E，RASHIDI A，et al.A review on application of carbon nanostructures as nanofiller in corrosion⁃resistant organic coatings［J］.Journal of Coatings Technology and Research，2020，17（1）：19⁃55.
21	中华人民共和国国家质量监督检验检疫总局，中国国家标准化管理委员会.纺织品防紫外线性能的评定：GB/T 18830⁃2009［S］.北京：中国标准出版社，2010.

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[7]	Li Fengyan， Hu Yue， Zhao Jin， Zhao Tianbo. Crosslinking Modification Improves Mechanical Properties of Hydrophobic Fluorinated Acrylic Resin [J]. Journal of Petrochemical Universities, 2020, 33(2): 42-46.
[8]	Zhu Zhou,Zhan Guohua, Zhang Bin,Zhao Jian. Effect of GO on Viscosity Behavior of HPAM [J]. Journal of Petrochemical Universities, 2015, 28(4): 31-34.
[9]	LI Xiuping,DONG Hang,LI Chujia,et al. Preparation of HighPurityand White CeO₂ by ComplexPrecipitation  Method and Its Photocatalytic Activit [J]. Journal of Petrochemical Universities, 2013, 26(5): 15-18.
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[12]	LI Hui,LI Yu-jian. Effect of Technological Factors on OMMT/E-51 Composite Modification for Waterborne Polyurethane [J]. Journal of Petrochemical Universities, 2012, 25(1): 18-21.
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Performance Studies of Nano⁃GO⁃ZnO / CeO₂ Composite Particles in Water⁃Based Polyurethane Coatings

Nano⁃GO⁃ZnO/CeO₂在水性聚氨酯涂料中的性能研究

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References 21

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