Aliphatic hyperbranched poly(ester amine)s with terminal acrylate groups were synthesized by Michael addition reaction between pizine and trimethylol propanetriacrylate (TMPTA) under various molar ratios, and their structures were characterized by 1H NMR,GPC and DSC analysis.The multi peaks within δ 4.04～4.18 (RCH 2OCOR′) in the 1H NMR spectra were analyzed and the peaks at δ 4.15, δ 4 06～4 07 and δ 4.04 can be assigned to terminal ( T ),linear ( L ) and dendritic units ( D ),respectively.Based on 1H NMR spectra,the degree of branching ( DB) for these polymers were calculated by using both the Fréchet method and the Frey method.With the molar ratio between pizine and TMPTA increased to 1/1,the terminate units decreased,both of the dendritic and linear units increased,while M n and M w/ M n became large and the T g value became high,accordingly.Moreover,cured films were obtained through UV radiation of the polymers.The gel contents for the films decreased with increasing the molar ratio between pizine and TMPTA,which may account for the changes of their mechanical properties.
Hyperbranched poly(ester-amine) (PEAC) with terminal acrylate groups aggregated into micelles in acidic methanol-water mixed solutions at a volume ratio 1∶100,and the micellar size became large with increasing the solution pH value.Self-assembled films were successfully formed from hyperbranched polyester (PMPP) with terminal aromatic carboxylic acid groups and PEAC by layer-by-layer dipping and the process was affected by the pH value of PEAC solutions.With PEAC as the outlayer,further reaction of the self-assembled film based on acrylate groups was investigated.The film was irradiated by UV light and washed by ionizing water.The cured film fell off the substrate seriously due to the highly branched architecture of PEAC and the polymerization of acrylate groups.In addition, the self-assembled film was immersed in aqueous p-phenylenediamine solution for 72?h.Regular spherical particles in diameter of 200?nm were observed on the film surface, which was due to the strong arene-arene interaction of benzene rings introduced into the film surface through Michael addition between acrylate groups and amino groups in p-phenylenediamine.
