高等学校化学学报
高等學校化學學報
고등학교화학학보
CHEMICAL JOURNAL OF CHINESE UNIVERSITIES
2014年
7期
1553-1558
,共6页
李伟%马艳%李远翔%范仲勇
李偉%馬豔%李遠翔%範仲勇
리위%마염%리원상%범중용
封端%开环聚合%立构嵌段聚乳酸%三枝化 PPO-PDLA-PLLA 嵌段共聚物%立构复合结晶
封耑%開環聚閤%立構嵌段聚乳痠%三枝化 PPO-PDLA-PLLA 嵌段共聚物%立構複閤結晶
봉단%개배취합%립구감단취유산%삼지화 PPO-PDLA-PLLA 감단공취물%립구복합결정
End capping%Ring-open polymerization%Stereoblock poly(lactic acid)%Three-arm PPO-PDLA-PLLA copolymer%Stereocomplex crystallite
以三枝化低不饱和度聚环氧丙烷(PPO)引发 D-丙交酯(D-LA)逐步开环聚合,合成了三枝化聚环氧丙烷-聚右旋乳酸(PPO-PDLA)共聚物。用辛酸亚锡 Sn(Oct)2与 PPO-PDLA 端羟基反应进行 Sn(Oct)封端,制备了三枝化 PPO-PDLA-Sn(Oct)预聚物。再于130℃下,以其作为大分子引发剂与 L-丙交酯(L-LA)开环聚合,合成了分子量>105的三枝化 PPO-PDLA-PLLA 嵌段共聚物。活性端基的引入,降低了聚合反应温度,从而降低了聚合中的酯交换或热降解反应发生的概率。实现了高分子量 PPO-PDLA-PLLA 嵌段共聚物的合成。结构测试结果表明,合成的嵌段共聚物具有分子结构易控及立构规整度高等特点。在结晶-熔融-再结晶重复热处理下,三枝化 PPO-PDLA-PLLA 嵌段共聚物仅发生立构复合聚乳酸结晶,且结晶能力稳定。
以三枝化低不飽和度聚環氧丙烷(PPO)引髮 D-丙交酯(D-LA)逐步開環聚閤,閤成瞭三枝化聚環氧丙烷-聚右鏇乳痠(PPO-PDLA)共聚物。用辛痠亞錫 Sn(Oct)2與 PPO-PDLA 耑羥基反應進行 Sn(Oct)封耑,製備瞭三枝化 PPO-PDLA-Sn(Oct)預聚物。再于130℃下,以其作為大分子引髮劑與 L-丙交酯(L-LA)開環聚閤,閤成瞭分子量>105的三枝化 PPO-PDLA-PLLA 嵌段共聚物。活性耑基的引入,降低瞭聚閤反應溫度,從而降低瞭聚閤中的酯交換或熱降解反應髮生的概率。實現瞭高分子量 PPO-PDLA-PLLA 嵌段共聚物的閤成。結構測試結果錶明,閤成的嵌段共聚物具有分子結構易控及立構規整度高等特點。在結晶-鎔融-再結晶重複熱處理下,三枝化 PPO-PDLA-PLLA 嵌段共聚物僅髮生立構複閤聚乳痠結晶,且結晶能力穩定。
이삼지화저불포화도취배양병완(PPO)인발 D-병교지(D-LA)축보개배취합,합성료삼지화취배양병완-취우선유산(PPO-PDLA)공취물。용신산아석 Sn(Oct)2여 PPO-PDLA 단간기반응진행 Sn(Oct)봉단,제비료삼지화 PPO-PDLA-Sn(Oct)예취물。재우130℃하,이기작위대분자인발제여 L-병교지(L-LA)개배취합,합성료분자량>105적삼지화 PPO-PDLA-PLLA 감단공취물。활성단기적인입,강저료취합반응온도,종이강저료취합중적지교환혹열강해반응발생적개솔。실현료고분자량 PPO-PDLA-PLLA 감단공취물적합성。결구측시결과표명,합성적감단공취물구유분자결구역공급립구규정도고등특점。재결정-용융-재결정중복열처리하,삼지화 PPO-PDLA-PLLA 감단공취물부발생립구복합취유산결정,차결정능력은정。
Three-arm poly(propylene oxide) (PPO) was used as a macroinitiator for the ring-opening poly-merization(ROP) of D-lactide to obtain three-arm poly( propylene oxide)-block-poly(D-lactic acid) ( PPO-PDLA). PPO-PDLA copolymer was then reacted with stannous octoate [Sn(Oct) 2 ] to obtain Sn(Oct) end-capped PPO-PDLA[PPO-PDLA-Sn(Oct)]. The PPO-PDLA-Sn(Oct) can be used as an efficient macroinitia-tor for the ROP of L-lactide to synthesize three-arm PPO-PDLA-PLLA at 130 ℃, which reduces the occurrence of hydrolysis and transesterification reaction. PPO-PDLA-PLLA copolymers with high molecular weight were synthesized by this novel and simple method. The results show that the composite of PPO-PDLA-PLLA can be easily tuned by controlling the feed ratio of L-lactide and D-lactide, and the stereoregularity of PPO-PDLA-PLLA is high. Moreover, the stereocomplexes of PPO-PDLA-PLLA can survive melting to reform the stereo-complex crystallites.