含悬垂双键的可降解支化聚合物的合成与表征  

Synthesis and Characterization of Degradable Branched Polymers with Pendant Vinyl Bonds

作　　者：杨宏军[1] 柏涛[1] 刘荣兴[1] 薛小强[1] 黄文艳[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,江苏省光伏科学与工程协同创新中心,常州213164

出　　处：《高分子学报》2016年第3期330-336,共7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

摘　　要：以氢化钾与苯甲醇的羟基反应形成氧阴离子,引发ε-己内酯（ε-CL）和甲基丙烯酸缩水甘油酯（GMA）的共聚反应,一步法制备带悬垂双键和端羟基的可降解支化聚合物.并将制备的聚合物与甲苯二异氰酸酯反应得到可降解聚氨酯薄膜.通过核磁（^1H-NMR、13C-NMR）、三检测体积排阻色谱仪（TD-SEC）、示差扫描量热仪（DSC）、热失重分析仪（TGA）和扫描电镜（SEM）对聚合物的结构和性能进行测试和表征.结果表明,氧阴离子能成功引发ε-CL和GMA的共聚反应,得到含大量悬垂双键的可降解支化共聚物.增加GMA的用量,共聚物的支化度从0.06增加到0.14,重均分子量从6.70×1^03增加到1.19×10^5,结晶度从47.6%降至非晶态.核磁结果表明共聚物中最多含有67%的悬垂双键.SEM结果表明通过15天的酶促降解,由该支化聚合物制备的聚氨酯薄膜表面变得非常粗糙,发生明显降解.Biodegradable vinyl functional branched copolymers were successfully synthesized by the oxyanionic copolymerization of ε-caprolactone（ ε-CL） and glycidyl methacrylate（ GMA）. Potassium hydride（ KH） and benzyl alcohol（ BA） were employed as the initiators. The structures and properties of the resulted copolymers were studied in detail by Flourier transform infrared spectroscopy（ FTIR）,size exclusion chromatography（ SEC）,nuclear magnetic resonance spectroscopy（ NMR）,differential scanning calorimetry（ DSC）,thermogravimetric analysis（ TGA） and scanning electron microscopy（ SEC）. The results showed that oxyanions displayed high activity for the copolymerization of ε-CL and GMA,resulting degradable copolymers with pendant vinyl groups in one step. Increasing the GMA/ε-CL feed ratio,the weight-average molecular weight of the copolymers increased from 6. 70 × 10^3 to 1. 19 × 10^5,the degree of branching increased from 0. 06 to 0. 14,but the degree of crystallinity decreased from 47. 6% to 0. The NMR results suggested that the copolymer retained up to 67% pendant vinyl groups,which could further be tailored via the thiol-ene click reaction. Due to the large amount of hydroxyl groups,the resulted copolymers could react with toluene-2,4-diisocyanate,forming a degradable polyurethane film. The SEC result showed that the surface of the polyurethane film became very rough after immersing in a lipase buffer solution for 15 days.

关 键 词：支化聚合物 悬垂双键 甲基丙烯酸缩水甘油酯 Ε-己内酯 

分 类 号：O631.3[理学—高分子化学]