环三磷腈基六臂氯化聚醚粘合剂的合成与热性能

摘要

Polyepichlorohydrin adhesive based on cyclotriphosphazene(HCPCP) was prepared by reaction of nucleophilic sub-stitution,reduction and cationic ring opening polymerization in sequence with hexachlorocyclotriphosphazene,p-hydroxybenzaldehyde and epichlorohydrin( ECH) as raw materials. The product was structurally characterized by FT-IR,NMR,elemental analysis and va-por pressure osmometry(VPO). The cationic ring opening polymerization reaction of Hexakis[p-(hydroxymethyl)phenoxy]cyclot-riphosphazene(PN-6OH),ECH and BF3·Et2O was investigated. The optimized process conditions were: the mixture of toluene and 1,2-dichloroethane(V(toluene):V(1,2-dichloroethane)=1 ∶ 3) was used as reaction reagent,n(BF3·Et2O): n(-OH)=6 ∶ 1,initiation reaction temperature was 40~50℃,polymerization temperature was 0~5℃. The thermal properties of HCPCP were also studied. The results show that the glass state temperature was -37.98℃ and the char yield at 800℃ was 24.38%.%以六氯环三磷腈、对羟基苯甲醛和环氧氯丙烷（ ECH）为原料，依次经亲核取代反应、还原反应和阳离子开环聚合反应合成出环三磷腈基六臂氯化聚醚HCPCP。利用红外光谱、核磁共振、元素分析和蒸汽渗透压法（ VPO）对所得中间体及HCPCP的结构进行了表征。重点研究了以PN-6OH为起始剂、ECH为聚合单体、三氟化硼乙醚络合物（BF3·Et2O）为催化剂的阳离子开环聚合反应，确定了最佳反应条件：以甲苯和1，2-二氯乙烷的混合溶剂（ V（甲苯）∶ V（1，2-二氯乙烷）＝1∶3）为反应溶剂，n（BF3·Et2O）∶ n（-OH）＝6∶1，引发反应温度为40～50℃，聚合反应温度为0～5℃，并对产物HCPCP进行了热性能研究，结果表明，HCPCP的玻璃化转变温度Tg＝-37．98℃，800℃时的残焦量为24．38％。