Research on the Blocking Reaction Kinetics and Mechanism of Aqueous Polyurethane Micelles Blocked by 2,4,6-Trichlorophenol

Abstract

The blocked terminal-isocyanate (NCO) aqueous polyurethane micelles were prepared by using the 2,6-hexamethylene diisocyanate (HDI), polyethylene glycol (PEG), dimethylol propionic acid (DMPA), and 2,4,6-trichlorophenol (TCP) as blocking agent. This paper was focused on the kinetics research of the TCP blocking terminal-NCO of pre-polymer, which occurred during the preparation process of TCP blocked aqueous polyurethane micelles. The kinetics parameters were obtained in the absence and presence of dibutyl tin dilaurate (DBTDL) as catalyst, respectively. Furthermore, the mechanism for TCP blocking terminal-NCO of pre-polymer was explored. The results showed that the blocking reaction was second order reaction, and the reaction activation energy was 43.890 KJ/mol without catalyst. In the presence of DBTDL, the blocking reaction activation energy was reduced to 34.412 KJ/mol, and the reaction rate was improved significantly. In addition, TCP blocking terminal-NCO of pre-polymer could be ascribed to the nucleophilic addition between nucleophilic phenolic hydroxyl of TCP and the carbon atom of -NCO group.

Keywords:

• Aqueous polyurethane micelles
• reaction rate constant
• activation energy
• isocyanate
• 2,4,6-trichlorophenol
• blocking

Funding

This work was supported by the Fundamental Research Funds for the Central Universities (DL12EB02-01), the National Natural Science Foundation of China (31000270 and 31270609) and the Youths Science Foundation of Heilongjiang Province of China (QC2011C010).