环三磷腈基六臂氯化聚醚粘合剂的合成与热性能

Synthesis and thermal properties of six-armed polyepichlorohydrin adhesive based on cyclotriphosphazene

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%。

Polyepichlorohydrin adhesive based on cyclotriphosphazene（HCPCP） was prepared by reaction of nucleophilic substitution,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 vapor pressure osmometry（VPO）. The cationic ring opening polymerization reaction of Hexakis[p-（ hydroxymethyl） phenoxy]cyclotriphosphazene（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%.