有机胍催化法可控合成聚乳酸系环境友好材料  

Controlled Synthesis of PLA-series Environment-friendly Polymers with Guanidine Catalysts

作　　者：王子羽 何文文 徐云龙[1] 黄伟[1] 江伟[1] 李弘[1,2] 张全兴[1] Zi-yu Wang;Wen-wen He;Yun-long Xu;Wei Huang;Wei Jiang;Hong Li;Quan-xing Zhang(National Engineering Research Center for Organic Pollution Control and Resource Reuse,School of the Environment,Nanjing University,Nanjing 210023;Key Laboratory of Functional Polymer Materials of Education Ministry,Institute of Polymer Chemistry,Nankai University,Tianjin 300071)

机构地区：[1]国家有机毒物控制与资源化工程技术研究中心南京大学环境学院,南京210023 [2]吸附与分离功能高分子材料教育部重点实验室南开大学高分子化学研究所,天津300071

出　　处：《高分子学报》2018年第7期786-796,共11页Acta Polymerica Sinica

基　　金：国家自然科学基金面上项目;国际交流项目;环保部重大水专项(项目号2014ZX07204-005-3;2015ZX07204-007-2和2017ZX07602-001-4)资助

摘　　要：可控聚合反应是进行大分子结构设计及获得优异性能聚合物的重要手段.作者近年来设计合成/筛选了若干种无毒有机胍化合物作为催化剂/引发剂,实现了可控缩聚、开环聚合、解聚反应.以生物质有机胍肌酐(CR)为催化剂实现了L-/D-乳酸(LLa/DLa)的等规熔融缩聚(Iso-MP),高产率(85%)合成得到了高等规度聚L-/D-乳酸(PLLA、PDLA,Iso.>98%);以CR催化Iso-MP反应得的中分子量聚L-/D-乳酸(Mw=2.2×104,Iso.=98.2%)为原料经熔融-固相缩聚(MP-SSP)联用法合成得到高分子量、高等规度PLLA、PDLA(Mw=1.0×105,Iso.>98%),聚合物热分解温度(Td,i=324.3°C)较Sn Cl2·2H2O催化法合成聚合物高120°C;由CR催化LLa/DLa的Iso-MP及其后解聚反应合成得到了光学纯L-/D-丙交酯(LLA、DLA,e.e.100%),副产的聚合物残渣r-PLLA/r-PDLA经水解后循环用作LLA/DLA合成原料,光学纯LLA/DLA总产率达到98%.设计合成了数种位阻型有机胍羧酸盐(HBG·OAc、CRA、CRG、CRL、TBDA),表征了其分子结构,用以实现LLA的活性开环聚合.合成了单一光学构型的L-乳酸-L-丝氨酸吗啉二酮(3S,6S-BMMD),测定了其单晶分子结构并以CRA为引发剂进行了3S,6S-BMMD的活性开环聚合,聚合物经脱保护后合成得到双亲功能基化生物降解聚合物聚(L-乳酸-L-丝氨酸).采用1H-NMR、13C-NMR跟踪监测法表征了大分子物种的精细结构,推断了上述可控反应的机理.Controlled polymerization is of great significance for the tailoring of macromolecular structure and synthesis of polymers with excellent properties.Several non-toxic organic guanidinines were prepared/selected in our laboratory in recent years and used as the catalysts/initiators to realize controlled melt polycondensation（MP）,ring-opening polymerization（ROP）,and depolymerization（DEP）.Isotactic melt polycondensation（Iso-MP）of L-lactic acid/D-lactic acid（LLa/DLa）was carried out for the first time with biogenic creatinine（CR）catalyst and poly（L-lactic acid）/poly（D-lactic acid）（PLLA/PDLA）with high isotacticity（Iso.〉98%）was obtained;Combined MP with solid-state polycondensation（MP-SSP）of the medium molecular weight PLLA/PDLA（Mw=2.2×104Iso.=98.2%）,prepared by the Iso-MP with CR,was carried out,and high molecular weight PLLA/PDLA（Mw〉1.0×10^5）with high isotacticity（Iso.〉98%）was obtained.The initial decomposition temperatureof the synthesized PLLA reached up to 324.5°C,which was 120°C higher than that of PLLA synthesized by Sncatalyst;Optical pure（e.e.100%）L-lactide/D-lactide（OP-LLA/OP-DLA）were synthesized via IsoMP and the subsequent depolymerization（DEP）of LMW-PLLA/LMW-PDLA（Mw=8.0×10^2–9.0×10^2）with CR catalyst.The polymer residues（r-PLLA/r-PDLA）,produced accompanying with the lactides formation,were reused as the raw material for LLA/DLA synthesis after being hydrolyzed.The total yield of OP-LLA/OP-DLA reached up to 98%;Several sterically hindered guanidine carboxylates（HBG·OAc,CRA,CRG,CRL,TBDA）were synthesized and used to realize living ROP of LLA.An optical pure morpholine-2,5-dione（3S,6S-BMMD）,derived from LLa and L-serine,was synthesized.Living ROP of 3S,6S-BMMD was carried out with CRA catalyst for the first time.After debenzylation of the synthesized P（3S,6S-BMMD）,an amphiphillic copolymer P（LLa-coSer）was obtained,which is a useful support material in biomedical areas.The fine molecular structures and isot

关 键 词：有机胍 立构专一性缩聚 活性开环聚合 环境友好聚合物 

分 类 号：TQ317[化学工程—高聚物工业]