Effects of Different Polyols with Functions on the Properties of Polyester Polyol-Based Polyurethane Coatings

Polyester-based polyurethane coatings were widely used in automotive, industrial, construction, and plastics industries due to their excellent mechanical properties, adhesion, and relatively outstanding oil and chemical resistance. In these coatings, the type and ratio of polyester and isocyanate curing agents influenced the cohesion energy, hydrogen bonding, crystallinity, crosslinking density, molecular weight, and morphology of the polyurethane at the microscopic level, thereby affecting the macroscopic mechanical properties, electrical performance, and environmental resistance of the material. However, there was limited systematic research on the effect of crosslinking density on the properties of polyester-based polyurethanes. In this study, an HTP-1 system was composed of neopentyl glycol (NPG) and phthalic anhydride (PA), and an HTP-2 system was composed of neopentyl glycol (NPG), hexahydrophthalic anhydride (HHPA), and adipic acid (AA). A series of polyesters (HTPs) were synthesized by adding polyols with different functional groups and adjusting their proportions in the system. The synthesized polyester was characterized using FT-IR, GPC, and DSC, and then cured with polyisocyanate curing agent N3390 to prepare the coating. The following properties of the films were evaluated: adhesion, impact resistance, pencil hardness, gloss, flexibility, oil resistance, and weather resistance. The results showed that in the HTP-1 system, the introduction of dipentaerythritol resulted in a polyester with a broad molecular weight distribution at high hydroxyl values, with a maximum PDI of 12.66 and a glass transition temperature (Tg) reaching 40.19 °C. The polyesters prepared by introducing three types of multifunctional polyols into the HTP-1 system exhibited good impact resistance, adhesion, and hardness. At low hydroxyl values, the coatings demonstrated good flexibility, but due to the lower crosslinking density, the oil resistance was poor. As the hydroxyl value increased, flexibility decreased, while oil resistance improved. In the HTP-2 system, coatings prepared with three different multifunctional polyols showed good impact resistance, flexibility, and hardness at low hydroxyl values but poor adhesion and oil resistance. As the hydroxyl value increased, adhesion improved from grade 1 to grade 0, and oil resistance improved for coatings prepared with trimethylolpropane and ditrimethylolpropane. However, the oil resistance of coatings prepared with dipentaerythritol decreased. Regarding weather resistance, the HTP-1-series resins primarily exhibited the cleavage of -CH2 groups, while the HTP-2-series resins showed the cleavage of C-N bonds. Overall, the HTP-2 series resins demonstrated better weather resistance. In the high-hydroxyl-value HTP-2 system, the incorporation of trimethylolpropane or ditrimethylolpropane has been shown to produce coatings that achieve a balance among mechanical properties, flexibility, and oil resistance. This finding provides valuable insights for the design and development of high-performance polyester-based polyurethane coatings.