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二硫键改性抗黄变水性聚氨酯的制备

Preparation of Yellowing-Resistant Waterborne Polyurethane Modified with Disulfide Bonds.

作者信息

Li Guorong, Duan Baorong, Leng Guorui, Liu Junjie, Zhang Tong, Lu Zhenwei, Wang Shanshan, Qu Jiale

机构信息

School of Pharmacy, Binzhou Medical University, Yantai 264003, China.

Research Center for Leather and Protein, College of Chemistry & Chemical Engineering, Yantai University, Yantai 264005, China.

出版信息

Molecules. 2024 May 2;29(9):2099. doi: 10.3390/molecules29092099.

Abstract

Waterborne polyurethane, renowned for its lightweight properties, excellent insulation capabilities, and corrosion resistance, has found extensive application in fields such as construction, automotive, leather, and thermal insulation. Nevertheless, during operational usage, waterborne polyurethane materials, akin to other polymeric substances, are susceptible to oxidative aging manifestations like yellowing, cracking, and diminished mechanical performance, significantly curtailing their utility. Consequently, the synthesis of yellowing-resistant polyurethane assumes pivotal significance. This study integrates dynamic reversible reactions into the synthesis process of polyurethane by introducing the dynamic reversible compound 2-hydroxyethyl disulfide as a chain extender, alongside the incorporation of a UV absorber to enhance the polyurethane's resistance to yellowing. When the disulfide bonds absorb heat, they undergo cleavage, yielding thiols that spontaneously recombine into disulfide bonds at ambient temperatures, allowing for the continuous breaking and reformation of disulfide bonds to absorb heat. Concurrently, in collaboration with the UV absorber, the detrimental effects of ultraviolet radiation on the polyurethane material are mitigated, thereby augmenting its resistance to yellowing. This study scrutinizes the positioning of UV absorber addition, the quantity of UV absorber, and the molar ratio of 1,4-butanediol to 2-hydroxyethyl disulfide, characterizing the functional groups of polyurethane through infrared and Raman spectroscopy. It is observed that the successful preparation of yellowing-resistant polyurethane is achieved, and evaluations on the modified polyurethane through color difference, tensile, and centrifugal tests reveal that the optimal yellowing resistance is attained by adding a UV absorber at a mass fraction of 1% to 3% prior to chain extension, resulting in a color change grade of 2, denoting slight discoloration. Simultaneously, the other properties of polyurethane exhibit relative stability. Notably, when the molar ratio of 1,4-butanediol to 2-hydroxyethyl disulfide is 3:2, the overall performance of the polyurethane remains stable, with exceptional yellowing resistance capabilities attaining a color change grade of 2.

摘要

水性聚氨酯以其轻质特性、出色的绝缘能力和耐腐蚀性而闻名,已在建筑、汽车、皮革和隔热等领域得到广泛应用。然而,在实际使用过程中,水性聚氨酯材料与其他聚合物物质一样,容易出现氧化老化现象,如变黄、开裂和机械性能下降,这显著限制了它们的实用性。因此,合成抗黄变聚氨酯具有至关重要的意义。本研究通过引入动态可逆化合物2-羟乙基二硫化物作为扩链剂,将动态可逆反应整合到聚氨酯的合成过程中,同时加入紫外线吸收剂以增强聚氨酯的抗黄变能力。当二硫键吸收热量时,它们会发生断裂,生成硫醇,硫醇在环境温度下会自发重新组合成二硫键,从而使二硫键能够持续断裂和重新形成以吸收热量。同时,与紫外线吸收剂协同作用,减轻了紫外线辐射对聚氨酯材料的有害影响,从而增强了其抗黄变能力。本研究考察了紫外线吸收剂添加的位置、紫外线吸收剂的用量以及1,4-丁二醇与2-羟乙基二硫化物的摩尔比,并通过红外光谱和拉曼光谱对聚氨酯的官能团进行了表征。结果表明,成功制备了抗黄变聚氨酯,通过色差、拉伸和离心测试对改性聚氨酯进行评估发现,在扩链前添加质量分数为1%至3%的紫外线吸收剂可达到最佳抗黄变效果,颜色变化等级为2,表示轻微变色。同时,聚氨酯的其他性能表现出相对稳定性。值得注意的是,当1,4-丁二醇与2-羟乙基二硫化物的摩尔比为3:2时,聚氨酯的整体性能保持稳定,具有出色的抗黄变能力,颜色变化等级为2。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/3894/11085269/0f1531e0f5bd/molecules-29-02099-g001.jpg

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