端羟基P(GA-b-AMMO)的合成与表征

Synthesis and Characterization of Hydroxy-terminated Glycidyl Azide-b-(3-azidomethyl-3-methyloxetane) Copolymers

以1,3,5-三羟乙基异氰脲酸酯(THEIC)为起始剂,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2500～3000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-甲基氧杂环丁烷(AMMO)进行开环聚合制备出一种新型叠氮粘合剂P(GA-b-AMMO)。采用红外、核磁共振(1H NM R和13C NM R)和凝胶渗透色谱(GPC)对P(GA-b-AMMO)的分子结构、组成和Mn进行了表征。考察了聚合温度及投料比等因素对聚合反应的影响,确定了该体系下聚合的优化条件为:n(BF3.OEt2)/n(TGAP)/n(AMMO)=1.35/1/12～16,聚合温度为0～3℃。P(GA-b-AM M O)的Mn、羟值(OH)测试结果均表明在该优化条件下聚合较为可控,产品总收率≥80.0%,官能度≥2.70,Mn达到4000～4400且与相应理论值均较为接近。力学性能测试表明与均聚醚T GAP相比,P(GA-b-AM M O)表现出较好的力学性能,以异氟尔酮二异氰酸酯(IPDI)为固化剂,其纯胶片常温力学强度为2.04 MPa,而常温延伸率可达261%,较低分子量的TGAP提高约2倍。

Trihydroxyethyl isocyanuricate（THEIC） using as initiator,trifunctionality glycidyl azide polymer（TGAP,Mn=2500~3000） with nitrogen heterocyclic ring structure was synthesized by cationic ring-opening polymerization of epichlorohydrin and azidation with NaN3.A novel azide binder glycidyl azide-b-（3-azidomethyl-3-methyl oxetane） copolymers（P（GA-b-AMMO）） were synthesized by polymerization of 3-azidomethyl-3-methyloxetane（AMMO）,using TGAP as a macromolecular initiator,and its structures were characterized by Flourier transform infrared spectroscopy（FTIR）,nuclear magnetic resonance（1H NMR and 13C NMR） and gel permeation chromatograph（GPC）.The effect of polymerization temperature and ratio of materials on the polymerization were investigated.The appropriate polymerization conditions were as fllow： n（BF3·OEt2）/n（TGAP）/n（AMMO）=1.35/1/12~16,the polymerization temperature was 0-3 ℃.The results show that the polymerization is controllable in this appropriate polymerization conditions.The total yield of polymers are above 80.0%,functionality ≥ 2.70 and Mn（4000~4400） are closed to theoretical value corresponding.The mechanical test indicated that P（GA-b-AMMO） had better mechanical property compared with TGAP homopolymer.The mechanical strength of P（GA-b-AMMO） /IPDI is 2.04 MPa.The elongation could reach 261%（20 ℃）,which is about three times as much as TGAP/IPDI.