Four hyperbranched polyesters (HBPE) were synthesized by the unequal activity monomer method with trimellitic anhydride (TMA), trimethylolpropane (TMP), and tertiary glycidyl carbonate (E10P) as raw materials, N, N-dimethylacetamide (DMAC) as solvent, triphenylphosphine as catalyst, with yields of 97.6%, 95%, 95%, and 92%, respectively. Then, the hyperbranched polyester was cahracterized by IR, DSC, and TG. The IR results showed that the four products exhibited distinct sharp peaks between 1 720-1 770 cm-1, which were the stretching vibration peaks of carbonyl groups in ester groups. There were also distinct sharp peaks between 1 100-1 280 cm-1, which were the C—O—C stretching vibration peaks of ester groups, indicating that all four products contained a considerable amount of ester groups. G1,1 and G2,1 hyperbranched polyesters had very clear broad peaks between 2 500-3 400 cm-1, which were stretching vibration peaks of hydroxyl groups in carboxyl groups, indicating that G1,1 and G2,1 contained a large number of carboxyl groups. The peak area significantly decreased in G1,2 and G2,2 hyperbranched polyesters, indicating that the carboxyl content in the two products was very low. This suggested that in the generation process of G1,2 and G2,2, the carboxyl group disappeared and the reaction was basically complete. The DSC results showed that the glass transition temperatures of the four hyperbranched products G1,1, G1,2, G2,1, and G2,2 were -6.77 ℃, -8.45 ℃, -17.52 ℃, and -32.93 ℃, respectively, all below 0 ℃, indicating good low-temperature toughness and suitability as film-forming materials for coatings. The TG results showed that the initial thermal decomposition temperatures of the two generations of hydroxyl terminated polyesters were significantly higher than those of carboxyl terminated polyesters, at 228.8 ℃ and 243.0 ℃, respectively, making them suitable for preparing hyperbranched polymers with high-temperature resistance exceeding 200 ℃. On the basis of hydroxyl terminated hyperbranched polyester, waterborne hyperbranched polyurethane lotion was synthesized by introducing isophorone diisocyanate (IPDI), polyethylene glycol 600 (PEG600), and 2,2-dihydroxymethyl propionic acid (DMPA). On the basis of hydroxyl terminated hyperbranched polyester, epoxy E51 was introduced to synthesize waterborne hyperbranched epoxy lotion. Both lotion had good transparency. The particle size analysis results showed that the average particle size of the two lotion was less than 40 nm, and both had obvious bimodal distribution characteristics. The bimodal distribution was not only conducive to improving the solid content, but also conducive to maintaining good stability of lotion. GPC analysis results showed that the molecular weights of the two lotion were consistent with the theoretical calculation, and the Mn/Mw of the final products of waterborne polyurethane and waterborne hyperbranched epoxy was 1.939 and 1.170 respectively. The test results of the coating showed that the gloss of the water-based hyperbranched polyurethane coating was 98.2 GU, the adhesion was level 0 (grid cut method), the pencil hardness was 4H, and there were no cracks, peeling, or detachment on the surface after a 50 cm drop hammer impact. The glossiness of the water-based hyperbranched epoxy cured paint film was 80.4 GU, the pencil hardness was 3H, the adhesion was level 0 (grid cut method), and there was no damage after 50 cm drop hammer impact, indicating good comprehensive performance. In this experiment, industrial raw materials are used and the coating performance is also tested with industrial standards, which has certain industrial development potential. In addition to being widely promoted in the field of water-based coatings, it also has very bright application prospects in the fields of adhesives and thermosetting resins.
Key words
hyperbranched polyester /
polyurethane /
epoxy resin /
waterborne coating /
coating film
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Funding
Research Fund Project of Yunnan Provincial Department of Education Academy of Sciences (2021J0056); Research Foundation of Education Bureau of Hebei Province, China (ZD2021302); Central Guidance on Local Science Technology Development Fund of Hebei Province, China (226Z1007G); Teaching Research and Reform Project of North China Institute of Aerospace Engineering (JY-2024-37)
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