用于水性车漆的受阻胺光稳定剂的合成及性能
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1.天津大学 化工学院;2.天津大学浙江研究院绍兴;3.天津功能精细化学品技术工程中心;4.绍兴兴欣新材料股份有限公司

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Synthesis of a hindered amine light stabilizer used in automotive varnishes
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1.School of Chemical Engineering and Technology, Tianjin University;2.School of Chemical Engineering and Technology, Tianjin University, Tianjin,;3.Institute of Shaoxing, Tianjin University, Zhejiang, Shaoxing, China;4.Tianjin Engineering Research Center of Functional Fine Chemicals, Tianjin, China;5.Shaoxing Xingxin New Materials Co., Ltd.,Shaoxing

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    摘要:

    阳光照射引发的光氧老化对汽车清漆涂层造成了损伤,如何提高涂层的抗老化性能成为研究的重点。在清漆涂料中添加受阻胺光稳定剂是延长汽车清漆寿命重要的方法。因此,设计并合成了一种新型受阻胺光稳定剂(HALS),以三聚氯氰和N-丁基氨基-2,2,6,6-四甲基哌啶为起始原料通过亲核取代反应得到中间体Ⅰ,再与己二胺哌啶反应生成中间体Ⅱ,最后水解,生成目标化合物TM-3。通过1H NMR、13C NMR证实了TM-3的结构。研究了其紫外吸收性能、热稳定性、光稳定性能和溶解性。结果表明,新型HALS TM-3在210nm处具有强烈的吸收;热稳定性能良好,在400℃以下能够保持热稳定,可以耐受较高的温度;由于其引入了亲水基团羟基,在含水的有机溶剂中比HALS 770具有更好的溶解性;比较TM-3和HALS 770在汽车清漆涂料中的光稳定性,在色差方面,加入TM-3的样品在模拟紫外光照射800 h后色差为6.01,而加入HALS 770的样品色差达到6.72;同样在光泽损失率方面,加入TM-3的样品在模拟紫外光照射800 h后光泽损失率为4.6%,而加入HALS 770的样品光泽损失率为6.7%。由此可知TM-3的光稳定效果优于HALS 770。新型受阻胺光稳定剂TM-3在汽车清漆涂层的耐老化方面具有潜在的商业应用前景。

    Abstract:

    The photo-oxidation caused by sunlight exposure has damaged the clear coat layer of the car. How to improve the anti-aging performance of the coating has become the focus of research. Adding hindered amine light stabilizer (HALS) to the clear coat paint is an important method to extend the life of the car clear coat. Therefore, a novel hindered amine light stabilizer (HALS) was designed and synthesized. Triphosgene and N-butylamino-2,2,6,6-tetramethylpiperidine were used as starting materials to obtain intermediate Ⅰ through nucleophilic substitution reaction, and then reacted with hexanediamine piperidine to generate intermediate Ⅱ, and finally hydrolyzed to obtain the target compound TM-3. The structure of TM-3 was confirmed by 1H NMR and 13C NMR. Its UV absorption performance, thermal stability, light stability and solubility were studied. The results show that the novel HALS TM-3 has strong absorption at 210nm; good thermal stability, it can maintain thermal stability below 400°C and can withstand higher temperatures; due to the introduction of hydrophilic hydroxyl group, it has better solubility in aqueous organic solvents than HALS 770; comparing TM-3 and HALS 770 in car clear coat paint, In terms of chromatic aberration, the sample with TM-3 added had a chromatic aberration of 6.01 after 800 h of simulated ultraviolet irradiation, while the sample with HALS 770 added had a chromatic aberration of 6.72; similarly, in terms of gloss loss rate, the sample with TM-3 added had a gloss loss rate of 4.6% after 800 h of simulated ultraviolet irradiation, while the sample with HALS 770 added had a gloss loss rate of 6.7%. It can be seen that TM-3 has better light stability than HALS 770. The novel hindered amine light stabilizer TM-3 has potential commercial application prospects in the aging resistance of car clear coat coating.

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赵雪钦,王博威,许文胜,沈华伟,陈立功,李阳.用于水性车漆的受阻胺光稳定剂的合成及性能[J].精细化工,2024,41(4):

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  • 收稿日期:2023-04-13
  • 最后修改日期:2023-05-16
  • 录用日期:2023-05-25
  • 在线发布日期: 2024-04-11
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