封闭型无溶剂聚氨酯的研究进展

doi:10.11896/cldb.18110087

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Abstract The use of traditional solvent polyurethane (PU) is likely to cause environmental pollution, which hinders the wide application of PU in functional films, finishes, foaming materials and the like. Blocked solvent-free polyurethane (SFPU), with its advantages of green, environmental protection, low energy consumption, high stability and simple operation, has become a research hotspot in the field of PU in recent years. In particular, SFPU with controllable activity can achieve efficient sealing and unsealing, which promotes the further development of PU materials.
However, due to the difference in the type and structure of the blocking agent, the blocked SFPU prepolymer formed has large deflagration temperature fluctuation and easy yellowing. In addition, the escape of the small molecule blocking agent during deblocking destroys the regularity of the product structure, reducing its mechanical properties. Therefore, in recent years, in addition to studying the effect of monomer on the physicochemical properties of blocked SFPU, the researchers have been trying on the selection of sealants, and have achieved relevant results, which effectively reduce the stability of blocked SFPU materials. It unblocks the temperature. At present, the blocked SFPU can achieve complete deblocking at 120 ℃.
The commonly used blocking agents are mainly alcohols, phenols, terpenes, amines and amides, active methylenes, pyrazoles and triazoles, bisulfites and the like. Among these blocking agents, the blocking agent for the alcohol structure is the earliest, the blocked prepolymer has a lo-wer activity and a higher deblocking temperature, giving the material excellent stability; although the anthraquinone blocking agent is lower. The release of the active isocyanate group at the deblocking temperature facilitates the re-extraction of the exposed isocyanate group and the chain extender, but the yellowing resistance is poor; the less toxic pyrazole and triazole sealer have nitrogen The structure of the five-membered ring is not easy to yellow. The blocked SFPU was initially prepared by a method of directly blocking the isocyanate monomer, but the method has a poor effect of extending the chain and a low film forming property. In recent years, the research work has adopted the method of sealing SFPU prepolymer, that is, synthesizing SFPU prepolymer first, and further blocking the prepolymer, ensuring high molecular weight and good film formation of the blocked SFPU.
In this paper, the research progress of blocked PU is reviewed, including three types of traditional blocked solvent PU, blocked WPU and blocked SFPU. The types and synthesis of blocked PU, common blocking agent and blocked-unblocking are discussed. Reaction mechanism, factors influencing the deblocking temperature, and methods for determining the deblocking temperature. The mechanism of blocked deblocking is divided into elimination-addition mechanism and nucleophilic substitution mechanism; the factors affecting the deblocking temperature are the structure of isocyanate, the structure of the blocking agent, the reaction medium and the catalyst. At the end of this paper, the advantages and disadvantages of the current blocked SFPU are summarized. It is pointed out that solving the three difficulties of blocking agent release, high deblocking temperature and high viscosity when unsealing is the key to be solved in the application process of this technology.

Key words： blocked solvent-free polyurethane deblocking temperature blocking agent influencing factors

Published: 30 September 2019

CLC number:

TQ311

Fund:This work was financially supported by the National High-tech R&D Program of China (863 Program) (2015AA033903).

About author:: Shuai Liu, received his B.S. degree from Shaanxi University of Science and Technology in 2016.He is currently pursuing his MA.Eng at the College of Bioresour-ces Chemical and Materials Engineering, Shaanxi University of Science and Technology under the supervision of Prof. Xingyuan Ma. His research has focused on blocked solvent-free polyurethane.
Xingyuan Ma, doctor of engineering, professor at College of Bioresources Chemical and Materials Enginee-ring, Shaanxi University of Science and Technology, supervisor for postgraduates, Dean of Nonwoven Mate-rials and Engineering Department. He is also the editor of professional magazines such as China Leather, West Leather and Leather and Chemicals. He has been engaged in the teaching and research of leather and synthetic leather for more than 20 years. He has been engaged in the teaching and research of leather and synthetic leather for more than 20 years. He has obtained more than 40 national invention patents, published more than 50 papers in foreign languages and core journals, and completed 5 professional works. As the project leader or main accomplisher, he has completed 2 national 863 projects, 2 special funds projects of the National Ministry of Science and Technology, 1 National Natural Science Foundation project, 2 National SME Innovation Fund Projects, and 1 Key Project of Science and Technology Research of the Ministry of Education, 1 industrial research projects of the Science and Technology Department of Shaanxi Pro-vince, 1 major project of Fujian Province.

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LIU Shuai,MA Xingyuan. Research Progress of Blocked Solvent-free Polyurethane[J]. Materials Reports, 2019, 33(23): 3892-3899.

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http://www.mater-rep.com/EN/10.11896/cldb.18110087 OR http://www.mater-rep.com/EN/Y2019/V33/I23/3892

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