摘要
以1,1,1-三溴甲基-1-羟甲基甲烷为原料,水和甲苯为反应介质,季铵盐为相转移催化剂,在NaOH作用下经关环反应合成3,3-双溴甲基氧杂环丁烷(BBMO)。以季铵盐为相转移催化剂,BBMO在水相介质中经叠氮基取代反应制备出3,3-双叠氮甲基氧杂环丁烷(BAMO)。BAMO经阳离子开环聚合可制备出数均分子量(Mn)为3000～4000的预聚物PBAMO。PBAMO经2,4-甲苯二异氰酸酯(2,4-TDI)与1,4-丁二醇(1,4-BDO)扩链即可制备出扩链的PBAMO(CE-PBAMO)。用红外、核磁、高效液相色谱、DSC、GPC等对单体、预聚物和CE-PBAMO的结构及相关物化性能进行了表征。结果表明,BBMO收率与纯度分别为81%和97.2%;BAMO收率与纯度分别为80.9%和98.37%;用相转移催化法制备BBMO和BAMO具有收率高、纯度高、安全性好等特点;所合成的CE-PBAMO的Mn为38933,可熔化溶解,20℃时拉伸强度高达12.7MPa,可作为高能热塑性粘合剂,用于具有3R概念新型可燃药筒的制备。
Using water and toluene as solvents,and quaternary ammonium salt as phase transfer catalyst,under the effect of NaOH,3,3-dibromomethyl oxetane（BBMO） was synthesized by the cylization of 1,1,1-tribromomethyl-1-hydroxymethyl methane.Using water as solvent,quaternary ammonium salt as phase transfer catalyst,3,3-diazido methyloxetane（BAMO） was obtained by the substitutation of BBMO with NaN3.The prepolymer of BAMO（PBAMO） was synthesized by the cationic polymerization of the monomer BAMO,and it had a number average molecular weight from 3000 to 4000.The chain-extended PBAMO（CE-PBAMO） was synthesized by the chain extended of the PBAMO with 2,4-toluene diisocyanate（2,4-TDI） and 1,4-butanediol（1,4-BDO）.The structure and physical chemical properties of BBMO,BAMO,PBAMO and CE-PBAMO were identified by FTIR,1H NMR,HPLC,DSC and GPC.The results show that the yield and purity of BBMO are 81% and 97.2%,and the yield and purity of BAMO are 80.9% and 98.37%;the synthesis of BBMO and BAMO by phase transfer catalysis possesses advantages of safety,high yield and high purity;the synthesized CE-PBAMO which has a number average molecular weight of 38933,can melt and dissolve,and its tensile strength is 12.7 MPa at 20 ℃,it can be used as high energy thermoplastic binder in the manufacture of the new type of combustible cartridge case which has concept of 3R（recycle,recover,reuse）.
出处
《含能材料》
EI
CAS
CSCD
北大核心
2010年第3期261-265,共5页
Chinese Journal of Energetic Materials
