PBAMO-GAP-PBAMO三嵌段共聚物的制备及表征

Preparation and Characterization of PBAMO-GAP-PBAMO Tri-Block Copolymer

以三氟化硼四氢呋喃络合物(BF_3·THF)为催化剂,用端羟基聚环氧氯丙烷(PECH)大分子引发3,3-双氯甲基氧杂环丁烷(BCMO)开环聚合得到三嵌段共聚醚,再经过叠氮化反应得到聚3,3-双叠氮甲基氧杂环丁烷-聚叠氮缩水甘油醚-聚3,3-双叠氮甲基氧杂环丁烷(PBAMO-GAP-PBAMO)三嵌段共聚物。采用红外光谱、核磁共振碳谱、凝胶渗透色谱和差示扫描量热分析等对产物的结构和性能进行了测试和表征。对聚合反应和叠氮化反应的条件进行了研究,结果表明,聚合反应时间为8 h、PECH与BCMO的质量比为1∶2,并以N,N-二甲基乙酰胺作叠氮化反应溶剂时,得到的聚合产物相对分子质量可达6242,叠氮取代率达98.2%;产物的玻璃化转变温度为-46.1℃,热分解温度为235. 1℃。

Poly (3,3-bis-azidomethyl)-glycidylazidopolymer-poly (3,3-bis-azidomethyl)(PBAMO-GAP-PBAMO) tri-block copolymer was synthesized via cationic ring opening polymerization,using polyepichlorohydrin as macromolecular initiator for the BCMO monomer,followed by azidation.The tri-block copolymer was characterized by FT-IR,^13C-NMR,GPC,DSC and so on.The conditions of polymerization and azidation were optimized.The Mn of the resulted tri-block copolymer was determined by GPC to be 6242when the reaction time is 8h and the mass ratio of PECH to PBCMO is 1:2.An azidation degree of 98.2%is obtained using dimethylacetamide(DMAC)as azidation solvent.The Tg of the tri-block copolymer is found to be -46.1℃,whereas the decomposition temperature is 235.1℃.