Instituto de Macromoléculas, Universidade Federal do Rio de Janeiro, Centro de Tecnologia, Bloco J, Ilha do Fundão, 21945-970, Rio de Janeiro, RJ, Brazil.
J Colloid Interface Sci. 2011 Jun 15;358(2):338-46. doi: 10.1016/j.jcis.2011.03.030. Epub 2011 Mar 15.
Polybutadiene-block-epoxy prepolymer (DGEBA-b-PBNCO) copolymers with multi-branched topological structure were prepared by reacting isocyanate-multifunctionalized liquid polybutadiene (PBNCO) with DGEBA prepolymer and used to develop nanostructured rubber-modified epoxy thermosets cured with triethylene-tetramine (TETA) as the aliphatic amine. The nanoscopic structure was obtained with the addition of as high as 20 phr of rubber component and successfully demonstrated by transmission electron microscopy (TEM) and small-angle X-ray scattering (SAXS). The glass transition temperature of the rubber-modified epoxy networks was slightly higher than the neat epoxy system. In addition, a unique combination of outstanding toughness and increased modulus and T(g) was achieved in these modified systems, which was attributed to the peculiar morphology associated with a strong interfacial adhesion imparted by the reaction between the isocyanate and hydroxyl groups present in the PBNCO and epoxy resin, respectively. The effect of the PBNCO on the gelation time of the epoxy/TETA system was investigated by rheological techniques. The NCO-functionalized polybutadiene decreased the gelation time, indicating an accelerating effect on the curing process, probably because of the urethane groups formed by the reaction between PBNCO and the epoxy resin during the PB-b-ER block copolymer preparation.
多支化拓扑结构的聚丁二烯嵌段环氧树脂预聚物(DGEBA-b-PBNCO)通过异氰酸酯多功能化液体聚丁二烯(PBNCO)与 DGEBA 预聚物反应制备,并用于开发用三乙烯四胺(TETA)作为脂肪族胺固化的纳米结构化橡胶改性环氧树脂热固性塑料。通过添加高达 20 份的橡胶组分可获得纳米级结构,并通过透射电子显微镜(TEM)和小角 X 射线散射(SAXS)成功地证明了这一点。橡胶改性环氧树脂网络的玻璃化转变温度略高于纯环氧树脂体系。此外,在这些改性体系中实现了韧性和模量以及 T(g) 的独特组合,这归因于与 PBNCO 和环氧树脂中存在的异氰酸酯和羟基之间的反应赋予的强界面附着力相关的独特形态。通过流变技术研究了 PBNCO 对环氧树脂/TETA 体系凝胶时间的影响。NCO 官能化聚丁二烯降低了凝胶时间,表明对固化过程具有加速作用,这可能是因为 PBNCO 与环氧树脂在 PB-b-ER 嵌段共聚物制备过程中反应形成了氨基甲酸酯基团。