Synthesis of Flame-Retardant Rigid Polyurethane Foams The flame-retardant rigid PUFs were prepared by one-step and free-rise method with the chemical compositions showed in Table I. Distilled water, tin(II) bis(2-ethylhexanoate), silicone oil, and DMMP were used as the foaming agent, catalyst, stabi- lizer, and flame retardant, respectively. All of the materials, except PMDI, were mixed in a beaker with mechanical stirring at the speed of 1000 rpm. To confirm the completion of the reaction, excess PMDI (NCO/OH51.1 : 1, in molar ratio) was added into the beaker and stirred for 10 s.21 The mixture was immediately poured into an open mold (/ 60 3 100 mm3) to produce free-rise foam in 2–10 s. A series of reactions occurred while the foams were produced22: (1) the addition polymeriza- tion of PMDI and BHET (Scheme 2a); (2) the reaction of PMDI and water to generate the unstable intermediate carbamic acid, and the decomposition to amine and carbon dioxide (Scheme 2b), the mixture expanded dozens of times in several seconds; (3) the side reaction of amine and PMDI to generate biuret diisocyanate (Scheme 2c). Then, the foams were kept in an oven at 60C for 24 h, to complete the polymerization reac- tion. The test samples were cut from the cured foams and rubbed with fine emery papers.
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