端羟基P(GA-b-AMCMO)共聚醚的合成与性能

Synthesis and properties of hydroxy-terminated glycidyl azide-b-(3-azidomethyl-3-cyanoethoxylmethyloxetane) copolymers

以1,3,5-三羟乙基异氰脲酸酯(THEIC)为起始剂,三氟化硼乙醚(BF3.OEt2)为催化剂,经环氧氯丙烷开环聚合和叠氮化取代等反应,首先制成带有氮杂环结构的数均相对分子质量(Mn)为2 500～3 000的三官能度叠氮缩水甘油醚(TGAP),然后以TGAP为大分子起始剂,引发3-叠氮甲基-3-氰乙氧基甲基氧丁环(AMCMO)进行开环聚合制备出一种新型叠氮粘合剂P(GA-b-AMCMO)。采用红外、核磁共振(1H-NMR和13C-NMR)和凝胶渗透色谱(GPC)对P(GA-b-AMCMO)的分子结构、组成和Mn进行了表征。考察了催化剂用量及投料比等因素对聚合反应的影响,确定了该体系下最优物料比为nBF3.OEt2/nAMCMO/nTGAP=1.5/13～14/1。P(GA-b-AMCMO)的Mn、羟值测试结果均表明在该优化条件下聚合较为可控,产品官能度f≥2.80,Mn达到5 000且与相应理论值均较为接近。混溶性实验表明其与硝酸酯增塑剂的混溶性较GAP有较大幅度提高。应用研究表明,P(GA-b-AMCMO)基推进剂高温拉伸强度较好(0.69～0.86 MPa/50℃),约为GAP基推进剂的2～3倍。

Trifunctionalized glycidyl aside polymer（ TGAP, M, = 2 500 - 3 000） containing nitrogen heterocyclic ring was syn-thesized by cationic ring-opening polymerization of epoxy chloropropane and subsequent azidation with NaN3 , using trihydroxyethyl isocyanuricate（THEIC） as initiator and BF3·OEt2 as catalyst. A novel azide binder glycidyl azide-b-（3-azidomethyl-3-eyanoethox- ylmethyl oxetane） eopolymer（ P（GA-b-AMCMO） ） was synthesized by polymerization of 3-azidomethyl-3-eyanoethoxylmethyl oxet-ane （AMCMO） , using TGAP as a macromolecular initiator, and its structure was characterized by FTIR, 1H-NMR, 13 C-NMR and GPC. The effect of molar ratios of the catalyst, AMCMO and TGAP on the polymerization was investigated. The optimized molar ra- tio was nat.3. OEt2/nAMCMo/nTGAP = 1.5/13 - 14/1. Both functionality（f≥2.70） and Mn （ ≥5 000） of the synthesized polymers P （GA-b-AMCMO） under optimized conditions are close to the corresponding theoretical value, which indicated that the polymeriza- tion reaction was controllable in this appropriate polymerization condition. The compatibility test indicated that P（ GA-b-AMCMO ） had better compatibility with nitrate ester plastieizers than GAP. The applied tests showed that the mechanical strength（50℃） of the propellants based on P（GA-b-AMCMO） were 0.69 -0.86 MPa, which is approximately twice or three times as much as that based on GAP.