环三磷腈基三臂氯化聚醚粘合剂的合成与热性能

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

以六氯环三磷腈、对羟基苯甲醛、苯酚钠和环氧氯丙烷（ 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，合成出环三磷腈基三臂氯化聚醚TCPCP。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TCPCP的结构进行了表征。重点研究了以1，3，5-三（4-羟甲基苯氧基）-1′，3′，5′-三（苯氧基）环三磷腈（PN-3OH）为起始剂、ECH为聚合单体、三氟化硼乙醚络合物（ BF3·Et2 O）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）＝1∶1，引发反应温度为20～25℃，聚合反应温度为0℃。并对产物TCPCP进行了热性能研究，结果表明，TCPCP的玻璃化转变温度（ Tg ）为-43．66℃，800℃时的残焦量为4．89％。

Three armed polyepichlorohydrin adhesive based on cyclotriphosphazene （ TCPCP ） was prepared by nucleophilic substitution, reduction and cationic ring opening polymerization reaction in sequence using hexachlorocyclotriphosphazene, p-hydroxybenzaldehyde, sodium phenate and epichlorohydrin（ECH） as raw materials.The products were 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-3OH） ,ECH and BF3 ·Et2 O was investigated. The optimized process conditions were：the mixture of toluene and 1,2-dichloroethane（ V（ toluene）：V（ 1,2-dichloroethane）=1 ∶ 3） used as reaction reagent,n （BF3·Et2O） ∶ n（-OH）=1 ∶ 1, initiation reaction temperature was 20-25℃, polymerization temperature was 0℃.The thermal properties of TCPCP were also studied.The results show that the glass state temperature is -43.66 ℃ and the char yield at 800℃is 4.89%.