浏览全部资源
扫码关注微信
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NCO Pincer-type Indol-2-yl Rare-earth Complexes: Synthesis and Catalytic Performances in
δ -Valerolactone Homo- and Co-polymerization withL -Lactide- 高分子通报 2025年38卷第10期 页码：1525-1535
- 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：
zmhuang@mail.ahpu.edu.cn
- 基金信息：国家自然科学基金(22031001;U23A2079);安徽省科技厅科技创新平台重大科技项目(202305a12020018);安徽省教育厅高等学校科学研究项目重点项目(2023AH050901)
DOI：10.14028/j.cnki.1003-3726.2025.25.138
中图分类号：收稿日期：2025-05-07，
录用日期：2025-06-09，
网络出版日期：2025-09-01，
纸质出版日期：2025-10-20
- 稿件说明：
移动端阅览
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
L
L
= 1-(2-C
4
H
7
OCH
2
)-3-(Me
2
NCH
2
)-2-C
8
H
4
N，C
8
H
4
N = indol-2-yl)和三烷基稀土金属烃基化合物(RE(CH
2
SiMe
3
)
3
(THF)
2
)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(
κ
3
NCO
-
L
)RE(CH
2
SiMe
3
)
2
(RE = Y (
1a
)
Yb (
1b
)
Lu (
1c
))，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(
κ
3
NCO
-
L
)(
κ
2
NC
-
L
)RE(CH
2
SiMe
3
) (RE = Y (
2a
)
Er (
2b
)
Yb (
2c
))。其中，配合物
1a
和
1b
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
2a
和
2c
。配合物1中配体以钳型
κ
3
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
κ
3
NCO
的模式与稀土金属中心成键，另外一个配体以
κ
2
NC
模式与金属中心成键。两类配合物在催化
δ
-戊内酯的开环聚合中表现优异(数均分子量
M
n
= 2.5×10
4
~6.3×10
4
多分散指数PDI = 1.33~1.79)。在催化
δ
-戊内酯和
L
-丙交酯的开环共聚中，通过先聚合
δ
-戊内酯，随后再加入
L
-丙交酯，实现
L
-丙交酯和
δ
-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
L
-丙交酯的聚合，随后通过酯交换实现与
δ
-戊内酯的共聚，所得共聚物随机性(
R
)为0.33，介于完全无规共聚物和嵌段共聚物之间。
Abstract
The dialkyl complexes (
κ
3
NCO
-L)RE(CH
2
SiMe
3
)
2
(RE = Y (
1a
)
Yb (
1b
)
Lu (
1c
)) were isolated after 0.5 h at a 1:1 molar ratio of 1-methoxyethyl-3-dimethylaminomethylindole (H
L
L
= 1-(2-C
4
H
7
OCH
2
)-3-(Me
2
NCH
2
)-2-C
8
H
4
N
C
8
H
4
N = indol-2-yl) with RE(CH
2
SiMe
3
)
3
(THF)
2
in hexane. While the monoalkyl complexes (
κ
3
NCO
-
L
)(
κ
2
NC
-
L
)RE(CH
2
SiMe
3
) (RE = Y (
2a
)
Er (
2b
)
Yb (
2c
)) formed with a 2:1 ratio of H
L
: RE after 4 h in hexane. Notably
treatment dialkyl complexes
1a
or
1b
with ligand precursor H
L
at a 1:1 molar ratio quantitatively yielded the corresponding monoalkyl derivatives
2a
or
2c
respectively. The ligand coordinating with metal centers in a
κ
3
NCO
mode in complexe
1
. While one ligand in complexe
2
bonds with central metal ions in a
κ
3
NCO
mode and the other one bonds with the central metal ion in a
κ
2
NC
way. Both types of complexes exhibited remarkable catalytic activity for the ring-opening homopolymerization of
δ
-valerolactone and block copolymerization of
δ
-valerolactone with
L
-lactide (
M
n
= 2.5×10
4
−6.3×10
4
Ð
= 1.33−1.79). Complexes are highly active initiator for the block copolymerization of
δ
-valerolactone and
L
-lactide by controlling to feed the monomer
δ
-valerolactone first
followed by addition of
L
-lact
ide. When using the one-pot method for copolymerizatioN the catalyst rapidly initiates the polymerization of
L
-lactide within an extremely short period
followed by transesterification to achieve copolymerization with
δ
-valerolactone. The resulting copolymer exhibits a randomness (
R
) of 0.33
which lies between a completely random copolymer and a block copolymer.
关键词
Keywords
references
Ellis, L. D. ; Rorrer, N. A. ; Sullivan, K. P. ; Otto, M. ; McGeehan, J. E. ; Román-Leshkov, Y. ; Wierckx, N. ; Beckham, G. T . Chemical and biological catalysis for plastics recycling and upcycling . Nat. Catal. , 2021 , 4 ( 7 ), 539 – 556 .
Kwon, D . Three ways to solve the plastics pollution crisis . Nature , 2023 , 616 ( 7956 ), 234 – 237 .
Xie, X. X. ; Zhang, P. ; Li, X. H. ; Wang, Z. X. ; Qin, X. ; Shao, M. H. ; Zhang, L. Q. ; Zhou, W. D . Rational design of F-modified polyester electrolytes for sustainable all-solid-state lithium metal batteries . J. Am. Chem. Soc. , 2024 , 146 ( 9 ), 5940 – 5951 .
Tournier, V. ; Duquesne, S. ; Guillamot, F. ; Cramail, H. ; Taton, D. ; Marty, A. ; André, I . Enzymes' power for plastics degradation . Chem. Rev. , 2023 , 123 ( 9 ), 5612 – 5701 .
Shi, C. X. ; Quinn, E. C. ; Diment, W. T. ; Chen, E. Y . Recyclable and (bio)degradable polyesters in a circular plastics economy . Chem. Rev. , 2024 , 124 ( 7 ), 4393 – 4478 .
Aarsen, C. V. ; Liguori, A. ; Mattsson, R. ; Sipponen, M. H. ; Hakkarainen, M . Designed to degrade: tailoring polyesters for circularity . Chem Rev , 2024 , 124 ( 13 ), 8473 – 8515 .
Clark, R. A. ; Shaver, M. P . Depolymerization within a circular plastics system . Chem. Rev. , 2024 , 124 ( 5 ), 2617 – 2650 .
Li, M. Q. ; Luo, Z. X. ; Yu, X. Y. ; Tian, G. Q. ; Wu, G. ; Chen, S. C. ; Wang, Y. Z . Ring-opening polymerization of a seven-membered lactone toward a biocompatible, degradable, and recyclable semi-aromatic polyester . Macromolecules , 2023 , 56 ( 6 ), 2465 – 2475 .
季晨霖 , 介素云 , 李伯耿 . 苯并 𫫖 唑脲/TMBD催化L-丙交酯和 δ -戊内酯开环共聚 . 高分子学报 , 2022 , 53 ( 5 ), 488 – 496 .
Lu, X. L. ; Cai, W. ; Gao, Z. Y . Shape-memory behaviors of biodegradable poly( L -lactide- co - ε -caprolactone) copolymers . J. Appl. Polym. Sci. , 2008 , 108 ( 2 ), 1109 – 1115 .
Ouyang, H. ; Yuan, D. ; Nie, K. ; Zhang, Y. ; Yao, Y. M. ; Cui, D. M . Synthesis and characterization of dinuclear salan rare-earth metal complexes and their application in the homo- and copolymerization of cyclic esters . Inorg. Chem. , 2018 , 57 ( 15 ), 9028 – 9038 .
Shi, X. T. ; Jing, Z. X. ; Zhang, G. C . Crystallization and properties of poly(lactide)/poly(δ-valerolactone) alternating supramolecular copolymers adjusted by stereo complexation . ACS Omega , 2019 , 4 ( 6 ), 11145 – 11151 .
Santulli, F. ; Pappalardo, D. ; Lamberti, M. ; Amendola, A. ; Barba, C. ; Sessa, A. ; Tepedino, G. ; Mazzeo, M . Simple and efficient zinc catalysts for synthesis and chemical degradation of polyesters . ACS Sustainable Chem. Eng. , 2023 , 11 ( 43 ), 15699 – 15709 .
Fernández, J. ; Larrañaga, A. ; Etxeberria, A. ; Sarasua, J. R . Tensile behavior and dynamic mechanical analysis of novel poly(lactide/δ-valerolactone) statistical co-polymers . J. Mech. Behav. Biomed. Mater. , 2014 , 35 , 39 – 50 .
Tsutsumi, C. ; Manabe, S. ; Nakayama, S. ; Nakayama, Y. ; Shiono, T . Impregnation of poly( L -lactide-ran- δ -valerolactone) with essential bark oil using supercritical carbon dioxide . Sci. Rep. , 2019 , 9 ( 1 ), 16326 .
Fernández, J. ; Etxeberria, A. ; Sarasua, J. R . In vitro degradation of poly(lactide/ δ -valerolactone) copolymers . Polym. Degrad. Stab. , 2015 , 112 , 104 – 116 .
Huang, W. J. ; Wen, X. ; Zhou, J. ; Zhang, X. Z . Understanding the hydrolysis mechanism on segments and aggregate structures: corrosion-tailored poly(lactic acid) deriving copolymers with δ-valerolactone . Int. J. Biol. Macromol. , 2022 , 222 , 961 – 971 .
Feng, C. P. ; Mu, D. B. ; Zhu, X. H. ; Wang, Y. R. ; Yuan, D. ; Yao, Y. M . Synthesis of benzoxazine functionalized amine-bridged bis(phenolato) rare earth complexes and their application in ring-opening polymerization of rac-lactide . Chin. J. Chem. , 2022 , 40 ( 21 ), 2516 – 2524 .
Hu, G. J. ; Deng, Z. Y. ; Wang, Y. W. ; Yuan, D. ; Zhang, Y. ; Yao, Y. M . Synthesis of amine-bridged bis(phenolate) rare-earth metal alkoxides and their catalytic performance for the polymerization of trimethylene carbonate and L -lactide . J. Organomet. Chem. , 2024 , 1003 , 122941 .
Li, X. L. ; Clarke, R. W. ; An, H. Y. ; Gowda, R. R. ; Jiang, J. Y. ; Xu, T. Q. ; Chen, E. Y. X . Dual recycling of depolymerization catalyst and biodegradable polyester that markedly outperforms polyolefins . Angew. Chem. Int. Ed. , 2023 , 62 ( 26 ), e202303791 .
Zhao, Z. W. ; Tong, Y. ; Liu, C. C. ; Huang, Z. M. ; Wang, S. W. ; Wang, F. H . Difunctionalized indol-2-yl-ligated bimetallic rare-earth metal complexes: Synthesis, characterization and high activity towards polymerization of 2-vinylpyridine . New J. Chem. , 2024 , 48 ( 33 ), 14690 – 14696 .
Yi, X. L. ; Ji, X. ; Huang, Z. M. ; Wang, F. H. ; Li, P. H. ; Wang, S. W . Synthesis, characterization of indol-2-yl-based NCO pincer rare-earth metal alkyl complexes and their catalytic activity towards hydroboration of imines . J. Organomet. Chem. , 2024 , 1015 , 123215 .
Huang, Z. M. ; Wang, R. R. ; Sheng, T. ; Zhong, X. Y. ; Wang, S. W. ; Zhu, X. C. ; Yuan, Q. B. ; Wei, Y. ; Zhou, S. L . Transformation of the sp 2 carbanion to carbene with subsequent 1, 1-migratory insertion and nucleophilic substitution in rare-earth metal chemistry . Inorg. Chem. , 2021 , 60 ( 24 ), 18843 – 18853 .
Huang, Z. M. ; Wang, S. W. ; Zhu, X. C. ; Wei, Y. ; Yuan, Q. B. ; Zhou, S. L. ; Mu, X. L. ; Wang, H . Synthesis, characterization of rare-earth metal chlorides bearing indolyl-based NCN pincer ligand and their catalytic activity toward 1,4- cis polymerization of isoprene . Chin. J. Chem. , 2021 , 39 ( 12 ), 3360 – 3368 .
Zhu, S. ; Xu, W. X. ; Hong, D. J. ; Wu, W. K. ; Chai, F. X. ; Zhu, X. C. ; Zhou, S. L. ; Wang, S. W . Rare-earth metal complexes supported by 1, 3-functionalized indolyl-based ligands for efficient hydrosilylation of alkenes . Inorg. Chem. , 2023 , 62 ( 1 ), 381 – 391 .
Zhu, S. ; Wu, W. K. ; Hong, D. J. ; Chai, F. X. ; Huang, Z. M. ; Zhu, X. C. ; Zhou, S. L. ; Wang, S. W . Synthesis and reactivity of the rare-earth metal complexes bearing the indol-2-yl-based NCN pincer ligand . Inorg. Chem. , 2024 , 63 ( 32 ), 14860 – 14875 .
Hong, D. J. ; Rajeshkumar, T. ; Zhu, S. ; Huang, Z. M. ; Zhou, S. L. ; Zhu, X. C. ; Maron, L. ; Wang, S. W . Unusual selective reactivity of the rare-earth metal complexes bearing a ligand with multiple functionalities . Sci. China Chem. , 2023 , 66 ( 1 ), 117 – 126 .
Wu, W. K. ; Rajeshkumar, T. ; Hong, D. J. ; Zhu, S. ; Huang, Z. M. ; Chai, F. X. ; Wang, W. G. ; Yuan, Q. B. ; Wei, Y. ; Xie, Z. W. ; Maron, L. ; Wang, S. W . Rare-earth metal complexes bearing electrophilic carbon and strongly polarized metallacyclopropane moiety: synthesis and diverse reactivity toward small molecules . Inorg. Chem. , 2024 , 63 ( 39 ), 18365 – 18378 .
Wu, W. K. ; Rajeshkumar, T. ; Zhu, S. ; Chai, F. X. ; Hong, D. J. ; Huang, Z. M. ; Yuan, Q. B. ; Maron, L. ; Wang, S. W . Rare-earth metal complexes bearing electrophilic and nucleophilic carbon centres and their unique reactivity patterns towards pyridine derivatives . Chem. Sci. , 2024 , 15 ( 48 ), 20315 – 20327 .
Wang, X. R. ; Ji, X. ; Zhao, X. ; Huang, Z. M. ; Huang, J. S. ; Wang, F. H. ; Yan, B. H. ; Chu, C. H. ; Wang, S. W . Synthesis of rare-earth metal bisalkyl complexes supported by [1-(2- N -morpholinoethylene)-3-(4, 4-dimethyl-2-oxazolinyl) ] indolyl ligand and their application in the intermolecular hydrophosphination of aryl alkenes . Inorg. Chim. Acta , 2022 , 542 , 121096 .
Nomura, N. ; Taira, A. ; Tomioka, T. ; Okada, M . A catalytic approach for cationic living polymerization: Sc(OTf) 3 -catalyzed ring-opening polymerization of lactones . Macromolecules , 2000 , 33 ( 5 ), 1497 – 1499 .
Ravi, P. ; Gröb, T. ; Dehnicke, K. ; Greiner, A . Novel [Sm 2 I(NPPh 3 ) 5 (DME) ] initiator for the living ring-opening polymerization of ε -caprolactone and δ -valerolactone . Macromolecules , 2001 , 34 ( 25 ), 8649 – 8653 .
Fernández, J. ; Meaurio, E. ; Chaos, A. ; Etxeberria, A. ; Alonso-Varona, A. ; Sarasua, J. R . Synthesis and characterization of poly(l-lactide/ε-caprolactone) statis-tical copolymers with well resolved chain microstr-uctures . Polymer , 2013 , 54 ( 11 ), 2621 – 2631 .
Karam, J. P. ; Muscari, C. ; Montero-Menei, C. N . Combining adult stem cells and polymeric devices for tissue engineering in infarcted myocardium . Biomaterials , 2012 , 33 ( 23 ), 5683 – 5695 .
0
浏览量
0
下载量
0
CSCD
- 网络PDF下载
- Meta-XML下载
- BibTeX下载
- Endnote下载
- RefMan 下载
- NoteExpress下载
- NoteFirst下载
关联资源
相关文章
相关作者
相关机构
- 技术支持由北京北大方正电子有限公司提供 京ICP备09064830号-19
京公网安备11010802024621 - 本系统建议在Chrome、 IE9+ 以上版本浏览器阅读本站内容，360浏览器请切换至极速模式
- Cookies帮助我们提供服务并提供个性化体验。使用本网站，即表示您同意我们使用Cookies