화학공학소재연구정보센터
Biomacromolecules, Vol.8, No.12, 3860-3870, 2007
Enhancing the functionality of biobased polyester coating resins through modification with citric acid
Citric acid (CA) was evaluated as a functionality-enhancing monomer in biobased polyesters suitable for coating applications. Model reactions of CA with several primary and secondary alcohols and diols, including the 1,4:3,6-dianhydrohexitols, revealed that titanium(IV) n-butoxide catalyzed esterification reactions involving these compounds proceed at relatively low temperatures, often via anhydride intermediates. Interestingly, the facile anhydride formation from CA at temperatures around CA's melting temperature (T-m = 153 degrees C) proved to be crucial in modifying sterically hindered secondary hydroxyl end groups. OH-functional polyesters were reacted with CA in the melt between 150 and 165 C, yielding slightly branched carboxylic acid functional materials with strongly enhanced functionality. The acid/epoxy curing reaction of the acid-functional polymers was simulated with a monofunctional glycidyl ether. Finally, the CA-modified polyesters were applied as coatings, using conventional cross-linking agents. The formulations showed rapid curing, resulting in chemically and mechanically stable coatings. These results demonstrate that citric acid can be applied in a new way, making use of its anhydride formation to functionalize OH-functional polyesters, which is an important new step toward fully biobased coating systems.