有机胍催化法可控合成聚乳酸-聚丁二酸丁二醇酯多嵌段共聚物研究

丁申莹; 徐云龙; 丁马林; 张延凯; 李立衡; 李弘; 张全兴

doi:10.11777/j.issn1000-3304.2019.19041

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有机胍催化法可控合成聚乳酸-聚丁二酸丁二醇酯多嵌段共聚物研究

研究论文 | 更新时间：2021-01-26

- 有机胍催化法可控合成聚乳酸-聚丁二酸丁二醇酯多嵌段共聚物研究
- Controlled Synthesis of a Multi-block Copolymer Poly(L-lactic acid)-co-Poly(butylene succinate) with Creatinine-based Guanidine Catalysts
- 高分子学报 2019年50卷第8期页码：816-825
- 作者机构：
  
  1.国家有机毒物污染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
- 作者简介：
  
  E-mail: hongli@nankai.edu.cn
  E-mail: zhqx@nju.edu.cn
- 基金信息：
  
  国家自然科学基金面上项目(基金号 21074057)和环保部重大水专项(项目号 2014ZX07204-005-3，2015ZX07204-007-2，2017ZX07602-001-4)资助()
- DOI：10.11777/j.issn1000-3304.2019.19041
  中图分类号：
- 纸质出版日期：2019-8，
  
  网络出版日期：2019-4-30，
  
  收稿日期：2019-2-26，
  
  修回日期：2019-3-24，
扫描看全文
丁申莹, 徐云龙, 丁马林, 张延凯, 李立衡, 李弘, 张全兴. 有机胍催化法可控合成聚乳酸-聚丁二酸丁二醇酯多嵌段共聚物研究[J]. 高分子学报, 2019,50(8):816-825.

Shen-ying Ding, Yun-long Xu, Ma-lin Ding, Yan-kai Zhang, Li-heng Li, Hong Li, Quan-xing Zhang. Controlled Synthesis of a Multi-block Copolymer Poly(L-lactic acid)-co-Poly(butylene succinate) with Creatinine-based Guanidine Catalysts[J]. Acta Polymerica Sinica, 2019,50(8):816-825.
丁申莹, 徐云龙, 丁马林, 张延凯, 李立衡, 李弘, 张全兴. 有机胍催化法可控合成聚乳酸-聚丁二酸丁二醇酯多嵌段共聚物研究[J]. 高分子学报, 2019,50(8):816-825. DOI： 10.11777/j.issn1000-3304.2019.19041.

Shen-ying Ding, Yun-long Xu, Ma-lin Ding, Yan-kai Zhang, Li-heng Li, Hong Li, Quan-xing Zhang. Controlled Synthesis of a Multi-block Copolymer Poly(L-lactic acid)-co-Poly(butylene succinate) with Creatinine-based Guanidine Catalysts[J]. Acta Polymerica Sinica, 2019,50(8):816-825. DOI： 10.11777/j.issn1000-3304.2019.19041.

摘要

以4种生物质肌酐(CR)系有机胍化合物及辛酸亚锡(Sn(Oct)

)为催化剂首先合成了寡聚L-乳酸(OPLLA)及寡聚丁二酸丁二醇酯(OPBS) 2种大分子单体，继而经熔融嵌段共缩聚(bc-MP)合成了一种中分子量(MMW)多嵌段共聚物(mb(PLLA-PBS)). 实验结果证明4种有机胍的催化性能均优于Sn(Oct)

．4种有机胍催化剂中以醋酸肌酐胍(CRA)催化性能最优，氢核磁共振谱(

H-NMR)分析证明所合成MMW-mb(PLLA-PBS)分子中二嵌段摩尔组成比(

OPLLA

OPBS

= 89.3/10.7)非常接近设计值(

$$ \

f\!_{{\rm OPLLA}_0}/f\!_{{\rm OPBS}_0 }$$

http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=13612228&type=

= 90/10)，聚合物分子量(

= 28.6 kDa)、产率(82.02%)、力学性能(拉伸强度TS = 21.81 MPa，断裂伸长率BE = 49.24%)、热稳定性(起始分解温度，

= 270 °C)等均优于用Sn(Oct)

催化聚合结果. 这一优良性能嵌段共聚物可用作PLLA-PBS共混的增容剂. 利用CRA催化bc-MP反应还合成了一种高分子量(

= 114.0 kDa)的多嵌段共聚物(HMW-mb(PLA-PBS))，其拉伸强度(TS = 50.67 MPa)接近PLLA (TS = 54.10 MPa)，断裂伸长率(BE = 60.66%)较PLLA提高15倍. 热重分析(TGA)证明，其起始热分解温度(

= 272 °C)较聚L-乳酸(PLLA)高22 °C.

H-NMR结构分析指出其分子中二嵌段摩尔组成比值(

OPLLA

OPBS

= 89.7/10.3)极接近设计值(

$$\

f\!_{{\rm OPLLA}_0} $$

http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=13612231&type=

$$ \

f\!_{{\rm OPBS}_0}$$

http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=13612233&type=

= 90/10). 上述实验结果证明，以无毒有机胍催化剂CRA实现了MMW-mb(PLLA-PBS)及HMW-mb(PLLA-PBS)的组成可控合成. 在实验研究的基础上推断了大分子单体bc-MP反应的机理.

Abstract

Medium molecular weight multi-block copolymers of poly(L-lactic acid) (PLLA) and poly(butylene succinate) (PBS)

MMW-mb(PLLA-PBS)s

were controlled-synthesized

via

melt block copolycondensation (bc-MP) of two macromonomers

i.e.

oligo-PLLA (OPLLA) and oligo-PBS (OPBS) with four creatinine (CR)-based organic guanidine (OG) catalysts. The catalytic performance of the four OGs is far superior to that of Sn(Oct)

in terms of molecular weight (

= 14.2 – 28.6 kDa versus 12.9 kDa)

apparent yield of synthesized block copolymers (74.15% – 82.02%)

as well as the by-product (lactide

LA) yield (1.08% – 6.71% versus 20.7%). Among the OGs

creatinine acetate (CRA) shows the best catalytic performance.

H-NMR structural characterization of the MMW-mb(PLLA-PBS) synthesized with CRA indicates that the measured molar ratio of the two blocks

OPLLA

OPBS

of MMW-mb(PLLA-PBS) is 89.3/10.7

close to the designed value (

$$\

f\!_{\rm{OPLLA}_0} $$

http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=13612234&type=

$$ \

f\!_{\rm OPBS_0}$$

http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=13612235&type=

= 90/10). A high molecular weight (

= 114.0 kDa) block copolymer

HMW-mb(PLLA-PBS)

was synthesized

via

bc-MP of two macromonomers with CRA for the first time. The tensile strength of the block copolymer (50.67 MPa) is close to that of PLLA (54.10 MPa)

and the elongation at break of the copolymer (BE = 60.66%) is 15 times greater than that of PLLA. TGA analysis indicates that the original decomposition temperature (

= 272 °C) is 22 °C higher than that of PLLA. The molar ratio of two blocks

OPLLA

OPBS

(89.7/10.3) in HMW-mb(PLLA-PBS)

measured by

H-NMR

is very close to the designed value (90/10). This is the first controlled synthesis of multi-block copolymer of PLLA-PBS

via

bc-MP with a biogenic guanidine-based catalyst CRA. The mechanism of the bc-MP is proposed on the basis of experimental investigation.

关键词

有机胍嵌段共聚物聚L-乳酸聚丁二酸丁二醇酯熔融共缩聚

Keywords

Organic guanidineMulti-block copolymerPoly(L-lactic acid)Poly(butylene succinate)Melt copolycondensation

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