基于非对称聚乳酸共混物调控多重立构复合晶：定量研究

郭明威; 黄黎明; 赵志锋

doi:10.11777/j.issn1000-3304.2023.23231

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基于非对称聚乳酸共混物调控多重立构复合晶：定量研究

研究论文 | 更新时间：2024-04-16

- 基于非对称聚乳酸共混物调控多重立构复合晶：定量研究
- Designed Multicomplexation Based on Asymmetric Polylactide Enantiomeric Blends: A Quantitative Study
- 高分子学报 2024年55卷第4期页码：473-484
- 作者机构：
  
  1.南京大学化学与化工学院南京 210023
  2.信阳艺术职业学院信阳 464000
  3.河北工业大学化工学院天津 310030
- 作者简介：
  
  E-mail: guomw199876@163.com; guomw@nju.edu.cn
- 基金信息：
- DOI：10.11777/j.issn1000-3304.2023.23231
  中图分类号：
- 纸质出版日期：2024-04-20，
  
  网络出版日期：2024-03-28，
  
  收稿日期：2023-09-19，
  
  修回日期：2023-10-26，
- 稿件说明：
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郭明威, 黄黎明, 赵志锋. 基于非对称聚乳酸共混物调控多重立构复合晶：定量研究. 高分子学报, 2024, 55(4), 473-484

Guo, M. W.; Huang, L. M.; Zhao, Z. F. Designed multicomplexation based on asymmetric polylactide enantiomeric blends: a quantitative study. Acta Polymerica Sinica, 2024, 55(4), 473-484
郭明威, 黄黎明, 赵志锋. 基于非对称聚乳酸共混物调控多重立构复合晶：定量研究. 高分子学报, 2024, 55(4), 473-484 DOI： 10.11777/j.issn1000-3304.2023.23231.

Guo, M. W.; Huang, L. M.; Zhao, Z. F. Designed multicomplexation based on asymmetric polylactide enantiomeric blends: a quantitative study. Acta Polymerica Sinica, 2024, 55(4), 473-484 DOI： 10.11777/j.issn1000-3304.2023.23231.

摘要

定量地探讨了非对称聚乳酸(PLA)外消旋共混物中，链长和摩尔比对立构复合(SC)结晶形成的关键贡献. 通过控制对映体链段差异与共混比例制备一系列聚乳酸外消旋共混物，结果发现在对映体平均聚合度(

https://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=57147425&type=

https://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=57147422&type=

4.06400013

2.70933342

) 60以内的对映体共混物中，2个对映体具有完全相同数量的相同链长时，形成的SC结晶更有序且具有更少的纠缠度或非晶区域. 另一方面，当2个对映体链长度不等时，长段的多余段可能在SC结晶表面保持无定形，或与其他短对映体复合，或多余链段间堆积形成同质(HC)结晶，这取决于链长的差异和共混比的双重作用：当链长差异不显著时(

，其中

为链段长度，

和

指聚乳酸构型)，由于

不超过2倍

，一个较长的链段不能容纳该系列中的2个短链，长段的多余段可能在SC结晶表面保持无定形. 虽然SC结晶和HC结晶之间存在竞争性结晶，但在适当的共混比下，前者优先；随着链长差异(

≥2

)的进一步扩大，较长的链中将有足够的空间容纳一个以上的短对映体链，此时，等比例非对称PLLA/PDLA共混物不能形成特别均匀的单一SC结晶，发现了HC结晶的迹象. 同时，在SC结晶表面的冗长片段可与另一个额外的对映体短链进一步相配对去形成多重SC结晶.

Abstract

To quantitatively explore the critical contributions of both molecular weights and blending ratios to the formation of stereocomplex (SC) crystallization in the poly(

-lactide)/poly(

-lactide) (PLLA/PDLA) enantiomeric blends. A series of PLLA/PDLA racemic blends were prepared by controlling the enantiomeric chain length differences and blending ratios

and it was found that in the enantiomeric blends with an enantiomeric chain length average degree of polymerization (

https://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=57147439&type=

https://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=57147435&type=

4.57200003

3.04800010

) about 60 or less

when the two enantiomers had exactly the same chain lengths with the same blending ratios

SCs were formed that were more ordered with less entanglement or the amorphous regions. On the other hand

when the two enantiomeric chain lengths are unequal

the excess segments of the longer ones could remain amorphous on the surface of the SC crystallization

or complex with the other shorter enantiomers

or tightly pack between the excess segments to form homocrystals (HCs)

depending on the dual effects of the difference in chain lengths and the blending ratios: when the difference in chain lengths is not significant (

where

is the chain segment length

and

refer to the poly(lactide) configuration)

since

does not exceed 2 times

(

)

a longer chain segment cannot accommodate the two shorter chains in the series

and the excess segments of the longer segments could stay amorphous on the SC crystallization surface. Although there is competitive crystallization between SC crystallization and HC crystallization

the former is preferred at appropriate blending ratios; when the difference in chain length (

≥2

) widens further

there will be enough space in the longer chain to accommodate more than one short enantiomeric chain

which means that the equal-ratio asymmetric PLLA/PDLA blends fail to form a particularly uniform single SC crystallization

and HC crystallization is found to be signs of HC crystallization. Meanwhile

the lengthy segments of the longer enantiomeric chains on the surface of the SCs could be further matched with another additional short enantiomeric chain to form multi-complexation.

关键词

聚乳酸立构复合晶共混比分子量对映体共混物

Keywords

PolylactideStereo-complexationBlending ratiosMolecular weightEnantiomeric blends

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