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以1,4-丁二醇/三氟化硼·乙醚为引发体系,通过阳离子开环共聚合方法合成了3,3’-双溴甲基环氧丁烷-3-溴甲基-3’-甲基环氧丁烷(BBMO-BrMMO)无规共聚物,采用13CNMR进行了结构表征.然后用微波法对BBMO-BrMMO无规共聚物进行大分子叠氮化反应,合成了3,3’-双叠氮甲基环氧丁烷-3-叠氮甲基-3’-甲基环氧丁烷(BAMO-AMMO)无规共聚物,并对叠氮化反应动力学进行了研究.结果表明,BBMO-BrMMO无规共聚物的共聚组成和微观序列分布可以通过调节单体的物质的量配比实现可控性.叠氮化反应速率由相转移催化剂四丁基溴化铵(TBAB)的用量控制,反应速率常数为k=48.85L/(mol·h)(TBAB=1%);k=51.95L/(mol·h)(TBAB=5%);k=62.72L/(mol·h)(TBAB=10%).微波法缩短了叠氮化反应时间,提高了合成过程的安全性,并且未改变共聚物的链结构.
3,3’-dibromomethyloxetane-3-bromomethyl-3 ’-butyric acid was synthesized by cationic ring-opening copolymerization using 1,4-butanediol / boron trifluoride diethyl ether as initiator. (BBMO-BrMMO) random copolymers were synthesized and characterized by 13CNMR. Then macromolecule azidation of BBMO-BrMMO random copolymer was carried out by microwave method to synthesize 3,3 ’ - bis-azidomethyloxetane-3-azidomethyl-3’-methyl-butylene oxide (BAMO-AMMO) random copolymers were synthesized and the kinetics of azidation reaction were studied. Results The results show that the copolymerization composition and microscopic sequence distribution of BBMO-BrMMO random copolymer can be controlled by adjusting the ratio of the monomers.The azidation reaction rate is controlled by the phase transfer catalyst TBAB, (TBAB = 1%); k = 51.95 L / (mol · h) (TBAB = 5%); k = 62.72 L / (mol · h) h) (TBAB = 10%). The microwave method shortens the azidation reaction time, improves the safety of the synthesis process, and does not change the chain structure of the copolymer.