NCO Pincer-type Indol-2-yl Rare-earth Complexes: Synthesis and Catalytic Performances in <italic style="font-style: italic">δ</italic>-Valerolactone Homo- and Co-polymerization with <italic style="font-style: italic">L</italic>-Lactide

HUANG Hua; YAN Bo-han; LIU Chen-cheng; PAN Rui; CHEN Li; LI Qing-hai; HUANG Ze-ming

doi:10.14028/j.cnki.1003-3726.2025.25.138

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NCO Pincer-type Indol-2-yl Rare-earth Complexes: Synthesis and Catalytic Performances in δ-Valerolactone Homo- and Co-polymerization with L-Lactide

更新时间：2025-09-23

- NCO Pincer-type Indol-2-yl Rare-earth Complexes: Synthesis and Catalytic Performances in δ-Valerolactone Homo- and Co-polymerization with L-Lactide
- Polymer Bulletin Vol. 38, Issue 10, Pages: 1525-1535(2025)
- 作者机构：
  
  安徽工程大学化学与环境工程学院，安徽省功能配合物材料化学与应用重点实验室，芜湖 241000
- 作者简介：
- 基金信息：
- DOI：10.14028/j.cnki.1003-3726.2025.25.138
  CLC：
- Received：07 May 2025，
  
  Accepted：09 June 2025，
  
  Published Online：01 September 2025，
  
  Published：20 October 2025
- 稿件说明：
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黄华, 颜伯翰, 刘晨程, 潘睿, 陈理, 李庆海, 黄泽明. NCO钳型吲哚-2-基稀土金属配合物的合成及其在δ-戊内酯均聚与L-丙交酯共聚中的催化性能. 高分子通报, 2025, 38(10), 1525–1535.

Huang, H.; Yan, B. H.; Liu, C. C.; Pan, R.; Chen, L.; Li, Q. H.; Huang, Z, M. NCO pincer-type indol-2-yl rare-earth complexes: synthesis and catalytic performances in δ-valerolactone homo- and co-polymerization with L-lactide. Polym. Bull. (in Chinese), 2025, 38(10), 1525–1535.
黄华, 颜伯翰, 刘晨程, 潘睿, 陈理, 李庆海, 黄泽明. NCO钳型吲哚-2-基稀土金属配合物的合成及其在δ-戊内酯均聚与L-丙交酯共聚中的催化性能. 高分子通报, 2025, 38(10), 1525–1535. DOI： 10.14028/j.cnki.1003-3726.2025.25.138.

Huang, H.; Yan, B. H.; Liu, C. C.; Pan, R.; Chen, L.; Li, Q. H.; Huang, Z, M. NCO pincer-type indol-2-yl rare-earth complexes: synthesis and catalytic performances in δ-valerolactone homo- and co-polymerization with L-lactide. Polym. Bull. (in Chinese), 2025, 38(10), 1525–1535. DOI： 10.14028/j.cnki.1003-3726.2025.25.138.

摘要

通过配体1-甲氧基乙基-3-二甲胺基亚甲基吲哚(H

= 1-(2-C

OCH

)-3-(Me

NCH

)-2-C

N，C

N = indol-2-yl)和三烷基稀土金属烃基化合物(RE(CH

SiMe

)

(THF)

)以1:1的摩尔比投料，在正己烷中反应0.5 h，可以合成双烷基稀土金属配合物(

NCO

)RE(CH

SiMe

)

(RE = Y (

)

Yb (

)

Lu (

))，当改变投料计量比为2:1时，正己烷中反应4 h可以合成单烷基稀土金属配合物(

NCO

)(

)RE(CH

SiMe

) (RE = Y (

)

Er (

)

Yb (

))。其中，配合物

和

可以与配体以1:1投料计量比在正己烷中反应1 h得到配合物

和

。配合物1中配体以钳型

NCO

的模式与稀土金属中心成键，配合物2中一个配体以钳型

NCO

的模式与稀土金属中心成键，另外一个配体以

模式与金属中心成键。两类配合物在催化

-戊内酯的开环聚合中表现优异(数均分子量

= 2.5×10

~6.3×10

多分散指数PDI = 1.33~1.79)。在催化

-戊内酯和

-丙交酯的开环共聚中，通过先聚合

-戊内酯，随后再加入

-丙交酯，实现

-丙交酯和

-戊内酯的开环共聚，得到嵌段共聚物。当使用“一锅法”投料进行共聚反应时，催化剂在极短的时间内引发

-丙交酯的聚合，随后通过酯交换实现与

-戊内酯的共聚，所得共聚物随机性(

)为0.33，介于完全无规共聚物和嵌段共聚物之间。

Abstract

The dialkyl complexes (

NCO

-L)RE(CH

SiMe

)

(RE = Y (

)

Yb (

)

Lu (

)) were isolated after 0.5 h at a 1:1 molar ratio of 1-methoxyethyl-3-dimethylaminomethylindole (H

= 1-(2-C

OCH

)-3-(Me

NCH

)-2-C

N = indol-2-yl) with RE(CH

SiMe

)

(THF)

in hexane. While the monoalkyl complexes (

NCO

)(

)RE(CH

SiMe

) (RE = Y (

)

Er (

)

Yb (

)) formed with a 2:1 ratio of H

: RE after 4 h in hexane. Notably

treatment dialkyl complexes

with ligand precursor H

at a 1:1 molar ratio quantitatively yielded the corresponding monoalkyl derivatives

respectively. The ligand coordinating with metal centers in a

NCO

mode in complexe

. While one ligand in complexe

bonds with central metal ions in a

NCO

mode and the other one bonds with the central metal ion in a

way. Both types of complexes exhibited remarkable catalytic activity for the ring-opening homopolymerization of

-valerolactone and block copolymerization of

-valerolactone with

-lactide (

= 2.5×10

−6.3×10

= 1.33−1.79). Complexes are highly active initiator for the block copolymerization of

-valerolactone and

-lactide by controlling to feed the monomer

-valerolactone first

followed by addition of

-lact

ide. When using the one-pot method for copolymerizatioN the catalyst rapidly initiates the polymerization of

-lactide within an extremely short period

followed by transesterification to achieve copolymerization with

-valerolactone. The resulting copolymer exhibits a randomness (

) of 0.33

which lies between a completely random copolymer and a block copolymer.

关键词

Keywords

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⁰

NCO Pincer-type Indol-2-yl Rare-earth Complexes: Synthesis and Catalytic Performances in δ-Valerolactone Homo- and Co-polymerization with L-Lactide

DOI：10.14028/j.cnki.1003-3726.2025.25.138

摘要

Abstract

关键词

Keywords

references