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首页> 外文期刊>International Journal of Biological Macromolecules: Structure, Function and Interactions >Ring-opening polymerisation of #beta#-butyrolactone catalysed by distannoxane complexes: study of the mechanism
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Ring-opening polymerisation of #beta#-butyrolactone catalysed by distannoxane complexes: study of the mechanism

机译：双锡氧烷络合物催化的＃beta＃-丁内酯开环聚合：机理的研究

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摘要

The mechanism of the ring-opening polymerisation of #beta#-butyrolactones was studied. The ring-opening polymerisation of BL catalysed by distanoxane complexes is of a living nature. The polymerisation of racemic BL gave predominantly syndiotactic P(3HB). The temperature effect on syndiospecifivity was used to determine the activation energy (#DELTA#E = E_(syndiotactic) - E_(isotactic)) for syndiotactic versus isotactic diad placement. The #DELTA#E value was obtained as -1.49 kcal/mol. The steric control leading to the observed syndiospecificity is due predominantly to diastereomeric interactions between the Sn-coordinated P(3HB) chain end. having a specific chain end stereochemistry, and the incoming BL enantiomeric monomers. The catalytic cycle derived from the mechanism of the polymerisation was proposed.
机译：研究了＃β＃-丁内酯的开环聚合机理。由二氧六环络合物催化的BL的开环聚合具有活性。外消旋BL的聚合主要产生间同P（3HB）。温度对间同立体选择性的影响用于确定间同二元对等位二元体位置的活化能（＃DELTA＃E = E_（同构）-E_（等规））。获得的＃DELTA＃E值为-1.49kcal / mol。导致观察到的间同特异性的空间控制主要归因于Sn配位的P（3HB）链末端之间的非对映异构相互作用。具有特定的链端立体化学和传入的BL对映体单体。提出了源自聚合机理的催化循环。

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