膦腈碱催化甲基丙烯酸烯丙酯与甲基丙烯酸甲酯的负离子共聚反应  

Anionic Copolymerization of Allyl Methacrylate and Methyl Methacrylate Catalyzed by Phosphazene Base

作　　者：杨宏军[1] 钱小磊[1] 黄文艳[1] 薛小强[1] 蒋必彪[1] 

机构地区：[1]江苏省材料表面科学与技术重点实验室常州大学材料科学与工程学院,常州213164

出　　处：《高分子学报》2015年第5期550-555,共6页Acta Polymerica Sinica

基　　金：国家自然科学青年基金(基金号21304010);江苏省自然科学青年基金(基金号SBK201342994);常州大学科技创新基金(基金号ZMF13020026)资助项目

摘　　要：室温下以膦腈碱(t-Bu P4)为催化剂,催化甲基丙烯酸烯丙酯(AMA)和甲基丙烯酸甲酯(MMA)进行负离子共聚反应.用核磁(1H-NMR、13C-NMR)、红外光谱(FTIR)、凝胶渗透色谱(GPC)、示差扫描量热仪(DSC)和热失重分析仪(TGA)等对聚合物结构和性能进行表征.结果发现,t-Bu P4能在室温下成功催化AMA与MMA的共聚反应,一步法合成结构可控的含悬垂双键共聚物.共聚反应中单体AMA和MMA的转化率均高于90%,且无交联或凝胶生成.通过NMR和FTIR对聚合物进行结构分析表明,AMA单体仅甲基丙烯酸酯双键参与聚合反应,烯丙基双键不参与聚合反应、无交联反应、环化反应等.聚合物中烯丙基结构单元的含量可通过体系中AMA/MMA的投料比调节.GPC结果表明所得共聚物分子量可控且分子量分布较窄.TGA和DSC结果表明,共聚物的热分解温度升高,玻璃化温度降低.The anionic copolymerization of allyl methacrylate （AMA） and methyl methacrylate （MMA） catalyzed by 1 -tert-butyl-4,4,4-tris （ dimethylamino ） -2,2-bis [ tris （ dimethylamino ） -phosphoranylidenamino ] - 2 A5,A5-catenadi-（phosphazene） （t-BuP4 ） was studied at room temperature. The structure and properties of the polymers have been characterized by nuclear magnetic resonance spectroscopy （NMR） ,Flourier transform infrared spectroscopy （FTIR）, gel permeation chromatography （GPC）, differential scanning calorimetry （DSC） and themogravimetric analysis （TGA）. The results showed that t-BuP4 displays high catalytic activity for the copolymerization of AMA with MMA, resulting linear copolymers with pendent allyl groups at back chains. Both the conversions of AMA and MMA could reach over 90% without considering the risk of gelation or erosslinking. NMR and FTIR results indicated that AMA incorporated into the copolymers by the reactions of methacrylate double bonds but not allyl groups. No cross-linking or cyclization reactions were observed during this polymerization system, which might be because the active centers catalyzed by t-BuP4 were not strong enough for the initiation of ally groups. The amount of pendant double bonds in the copolymers could be adjusted by changing AMA/MMA feed ratio. GPC results showed that the resultant copolymers have narrow polydispersity and good molecular weight control. TGA and DSC results showed that the decomposition temperatures for eopolymers increased with the increasing of AMA/MMA feed ratio, but the glass transition temperatures （T） were changed oppositely.

关 键 词：悬垂双键 甲基丙烯酸烯丙酯 甲基丙烯酸甲酯 

分 类 号：O631.5[理学—高分子化学]