Study on Ring-opening Polymerization of Lactide Catalyzed by Guanidine Zinc Complexes

Jiao-yu Liu; Shuang Liu; Hong-yi Suo; Yu-sheng Qin

doi:10.11777/j.issn1000-3304.2023.23289

您当前的位置：

首页 >

文章列表页 >

Study on Ring-opening Polymerization of Lactide Catalyzed by Guanidine Zinc Complexes

更新时间：2024-04-23

- Study on Ring-opening Polymerization of Lactide Catalyzed by Guanidine Zinc Complexes
- Acta Polymerica Sinica Pages: 1-11(2024)
- 作者机构：
  
  烟台大学化学化工学院烟台 264005
- 作者简介：
  
  Yu-sheng Qin, E-mail: ysqin@ytu.edu.cn
- 基金信息：
- DOI：10.11777/j.issn1000-3304.2023.23289
  CLC：
- Published Online：19 April 2024，
  
  Received：20 December 2023，
  
  Accepted：26 January 2024
扫描看全文
刘娇玉, 刘爽, 索泓一, 秦玉升. 胍基锌配合物催化丙交酯开环聚合研究. 高分子学报, doi: 10.11777/j.issn1000-3304.2023.23289

Liu, J. Y.; Liu, S.; Suo, H. Y.; Qin, Y. S. Study on ring-opening polymerization of lactide catalyzed by guanidine zinc complexes. Acta Polymerica Sinica, doi: 10.11777/j.issn1000-3304.2023.23289
刘娇玉, 刘爽, 索泓一, 秦玉升. 胍基锌配合物催化丙交酯开环聚合研究. 高分子学报, doi: 10.11777/j.issn1000-3304.2023.23289 DOI：

Liu, J. Y.; Liu, S.; Suo, H. Y.; Qin, Y. S. Study on ring-opening polymerization of lactide catalyzed by guanidine zinc complexes. Acta Polymerica Sinica, doi: 10.11777/j.issn1000-3304.2023.23289 DOI：

摘要

发展绿色、高效的催化剂技术替代目前广泛应用的锡类催化剂一直是聚乳酸(PLA)及其相关催化剂技术研究领域的热点. 本研究设计合成了双核胍基锌配合物，该配合物以环氧化物作为共引发剂，可在模拟工业条件下以较高的活性(TOF = 7.50×10

~3.45×10

-1

)催化丙交酯开环聚合，且在极低的催化剂浓度条件仍可保持良好活性. 聚合所得产物的凝胶渗透色谱(GPC)曲线呈单峰窄分布(1.25~1.49)，分子量为6.2~34.3 kg/mol. 通过对低分子量聚合产物进行基质辅助激光解吸/电离飞行时间质谱(MALDI-TOF-MS)表征分析，证实所得聚合产物以环状聚乳酸(

-PLA)为主，并提出可能的成环机理. 此外，该双核胍基锌配合物具有较好的普适性，可实现

-己内酯(

-CL)和

-戊内酯(

-VL)等多种内酯单体的开环聚合.

Abstract

Poly(lactic acid) (PLA) is one of the most important biodegradable polymers

which has attracted much attention due to its renewable raw materials and excellent biodegradation properties. The quest to develop sustainable and high-performance catalytic technologies as alternatives to the tin catalysts

which are prevalent currently

is a hot topic in this field. Cyclic PLA

contrasting with the extensively produced linear PLA

has garnered significant attention due to its superior crystallinity

thermal stability

and low intrinsic viscosity

and it has been reported that the mixture of cyclic poly(lactic acid) and linear poly(lactic acid) has better hydrolysis resistance and thermal stability. This study reports the design and synthesis of a binuclear guanidine zinc complex

exhibiting exceptional activity (TOF = 7.50×10

-3.45×10

-1

) in catalyzing lactide ring-opening polymerization for the efficient production of cyclic poly(lactic acid) under simulated industrial conditions. Gel permeation chromatography (GPC) analysis revealed a narrow

unimodal distribution (1.25-1.49) of the obtained products

with a molecular weight range of 6.2-34.3 kg/mol. Matrix-assisted Laser Desorption Ionization Time-of-flight Mass Spectrometry (MALDI-TOF-MS) characterization of low molecular weight products confirmed the predominant presence of cyclic PLA

allowing for the proposal of a plausible ring formation mechanism. Moreover

the experiment demonstrated the binuclear guanidine zinc complex's effective catalytic action on a diverse range of lactone monomers

offering a novel avenue for the development of broad-spectrum catalytic systems within the realm of metal catalysis.

关键词

金属胍配合物丙交酯环状聚乳酸双核锌配合物

Keywords

Metal guanidine complexLactideCyclic poly(lactic acid)Binuclear zinc complex

references

Zhang X. Y.; Fevre M.; Jones G. O.; Waymouth R. M. Catalysis as an enabling science for sustainable polymers. Chem. Rev., 2018, 118(2), 839-885. doi:10.1021/acs.chemrev.7b00329http://dx.doi.org/10.1021/acs.chemrev.7b00329

安泽胜, 陈昶乐, 何军坡, 洪春雁, 李志波, 李子臣, 刘超, 吕小兵, 秦安军, 曲程科, 唐本忠, 陶友华, 宛新华, 王国伟, 王佳, 郑轲, 邹文凯. 中国高分子合成化学的研究与发展动态. 高分子学报, 2019, 50(10), 1083-1132. doi:10.11777/j.issn1000-3304.2019.19136http://dx.doi.org/10.11777/j.issn1000-3304.2019.19136

寇新慧, 沈勇, 李志波. 手性脲/有机碱二元体系协同催化外消旋丙交酯立构选择性开环聚合. 高分子学报, 2020, 51(10), 1121-1130. doi:10.11777/j.issn1000-3304.2020.20117http://dx.doi.org/10.11777/j.issn1000-3304.2020.20117

Mirkhalaf S. M.; Fagerström M. The mechanical behavior of polylactic acid (PLA) films: fabrication, experiments and modelling. Mech. Time Depend. Mater., 2021, 25(2), 119-131. doi:10.1590/0104-1428.1489http://dx.doi.org/10.1590/0104-1428.1489

Pachekoski W. M.; Dalmolin C.; Agnelli J. A. M. Biodegradable polymeric blends of PHB and PLA for film production. Polimeros, 2014, 24(4), 501-507. doi:10.1590/0104-1428.1489http://dx.doi.org/10.1590/0104-1428.1489

Gu J. C.; Xiao P.; Chen P.; Zhang L.; Wang H. L.; Dai L. W.; Song L. P.; Huang Y. J.; Zhang J. W.; Chen T. Functionalization of biodegradable PLA nonwoven fabric as superoleophilic and superhydrophobic material for efficient oil absorption and oil/water separation. ACS Appl. Mater. Interfaces, 2017, 9(7), 5968-5973. doi:10.1021/acsami.6b13547http://dx.doi.org/10.1021/acsami.6b13547

Shi J. W.; Zhang L.; Xiao P.; Huang Y. J.; Chen P.; Wang X. F.; Gu J. C.; Zhang J. W.; Chen T. Biodegradable PLA nonwoven fabric with controllable wettability for efficient water purification and photocatalysis degradation. ACS Sustain. Chem. Eng., 2018, 6(2), 2445-2452. doi:10.1021/acssuschemeng.7b03897http://dx.doi.org/10.1021/acssuschemeng.7b03897

Tümer E. H.; Erbil H. Y. Extrusion-based 3D printing applications of PLA composites: a review. Coatings, 2021, 11(4), 390. doi:10.3390/coatings11040390http://dx.doi.org/10.3390/coatings11040390

Ebrahimi F.; Ramezani Dana H. Polylactic acid (PLA) polymers: from properties to biomedical applications. Int. J. Polym. Mater. Polym. Biomater., 2022, 71(15), 1117-1130. doi:10.1080/00914037.2021.1944140http://dx.doi.org/10.1080/00914037.2021.1944140

Tanase C. E.; Spiridon I. PLA/chitosan/keratin composites for biomedical applications. Mat. Sci. Eng. C., 2014, 40, 242-247. doi:10.1016/j.msec.2014.03.054http://dx.doi.org/10.1016/j.msec.2014.03.054

Dechy-Cabaret O.; Martin-Vaca B.; Bourissou D. Controlled ring-opening polymerization of lactide and glycolide. ChemInform, 2005, 36(14), no. doi:10.1002/chin.200514262http://dx.doi.org/10.1002/chin.200514262

Schäfer P. M.; Herres-Pawlis S. Robust guanidine metal catalysts for the ring-opening polymerization of lactide under industrially relevant conditions. ChemPlusChem, 2020, 85(5), 1044-1052. doi:10.1002/cplu.202000252http://dx.doi.org/10.1002/cplu.202000252

Finne A.; Albertsson A. C. Controlled synthesis of star-shaped l-lactide polymers using new spirocyclic tin initiators. Biomacromolecules, 2002, 3(4), 684-690. doi:10.1021/bm020009ohttp://dx.doi.org/10.1021/bm020009o

dos Santos Vieira I.; Herres-Pawlis S. Lactide polymerisation with complexes of neutral N-donors—new strategies for robust catalysts. Eur. J. Inorg. Chem., 2012, 2012(5), 765-774. doi:10.1002/ejic.201101131http://dx.doi.org/10.1002/ejic.201101131

Fliedel C.; Vila-Viçosa D.; Calhorda M. J.; Dagorne S.; Avilés T. Dinuclear zinc—N-heterocyclic carbene complexes for either the controlled ring-opening polymerization of lactide or the controlled degradation of polylactide under mild conditions. ChemCatChem, 2014, 6(5), 1357-1367. doi:10.1002/cctc.201301015http://dx.doi.org/10.1002/cctc.201301015

Nylund P. V. S.; Monney B.; Weder C.; Albrecht M. N-Heterocyclic carbene iron complexes catalyze the ring-opening polymerization of lactide. Catal. Sci. Technol., 2022, 12(3), 996-1004. doi:10.1039/d1cy02143ehttp://dx.doi.org/10.1039/d1cy02143e

Harinath A.; Bhattacharjee J.; Sarkar A.; Panda T. K. Alkali metal complex-mediated ring-opening polymerization of rac-LA, ε-caprolactone, and δ-valerolactone. New J. Chem., 2019, 43(23), 8882-8891. doi:10.1039/c9nj01130ghttp://dx.doi.org/10.1039/c9nj01130g

Bhattacharjee J.; Harinath A.; Nayek H. P.; Sarkar A.; Panda T. K. Highly active and iso-selective catalysts for the ring-opening polymerization of cyclic esters using group 2 metal initiators. Chem. Eur. J., 2017, 23(39), 9319-9331. doi:10.1002/chem.201700672http://dx.doi.org/10.1002/chem.201700672

Liu J. J.; Zhang C.; Li Z. J.; Zhang L.; Xu J. X.; Wang H. X.; Xu S. Q.; Guo T. F.; Yang K.; Guo K. Dibutyl phosphate catalyzed commercial relevant ring-opening polymerizations to bio-based polyesters. Eur. Polym. J., 2019, 113, 197-207. doi:10.1016/j.eurpolymj.2019.01.057http://dx.doi.org/10.1016/j.eurpolymj.2019.01.057

Kan S. L.; Jin Y.; He X. J.; Chen J.; Wu H.; Ouyang P. K.; Guo K.; Li Z. J. Imidodiphosphoric acid as a bifunctional catalyst for the controlled ring-opening polymerization of δ-valerolactone and ε-caprolactone. Polym. Chem., 2013, 4(21), 5432-5439. doi:10.1039/c3py00667khttp://dx.doi.org/10.1039/c3py00667k

Chamberlain B. M.; Cheng M.; Moore D. R.; Ovitt T. M.; Lobkovsky E. B.; Coates G. W. Polymerization of lactide with zinc and magnesium β-diiminate complexes: stereocontrol and mechanism. J. Am. Chem. Soc., 2001, 123(14), 3229-3238. doi:10.1021/ja003851fhttp://dx.doi.org/10.1021/ja003851f

Wang Z. Y.; Xu G. Q.; Zhou L.; Lv C. D.; Yang R. L.; Dong B. Z.; Wang Q. G. Isoselective ring-opening polymerization of racemic lactide catalyzed by N-heterocyclic olefin/(thio)urea organocatalysts. Chinese J. Polym. Sci., 2021, 39(6), 709-715. doi:10.1007/s10118-021-2535-xhttps://doi.org/10.1007/s10118-021-2535-x

Fuchs M.; Schmitz S.; Schafer P. M.; Secker T.; Metz A.; Ksiazkiewicz A. N.; Pich A.; Kogerler P.; Monakhov K. Y.; Herres-Pawlis S. Mononuclear zinc(II) schiff base complexes as catalysts for the ring-opening polymerization of lactide. Eur. Polym. J., 2020, 122, 109302. doi:10.1016/j.eurpolymj.2019.109302http://dx.doi.org/10.1016/j.eurpolymj.2019.109302

Jones M. D.; Davidson M. G.; Keir C. G.; Hughes L. M.; Mahon M. F.; Apperley D. C. Zinc(II) homogeneous and heterogeneous species and their application for the ring-opening polymerisation of rac-lactide. Eur. J. Inorg. Chem., 2009, 2009(5), 635-642. doi:10.1002/ejic.200801049http://dx.doi.org/10.1002/ejic.200801049

Hu M. G.; Song X. F.; Wang F. G.; Zhang W. Z.; Ma W. H.; Han F. Z. Ring-opening polymerization of rac-lactide catalyzed by magnesium and zinc complexes supported by an NNO ligand. New J. Chem., 2022, 46(3), 1175-1181. doi:10.1039/d1nj05157ahttp://dx.doi.org/10.1039/d1nj05157a

Petrus R.; Lis T.; Kowaliński A. Use of heterometallic alkali metal-magnesium aryloxides in ring-opening polymerization of cyclic esters. Dalton Trans., 2022, 51(23), 9144-9158. doi:10.1016/j.mcat.2022.112480http://dx.doi.org/10.1016/j.mcat.2022.112480

Federica S.; Giuseppe G.; Marina L.; Consiglia T.; Mina M. Zinc and magnesium catalysts for the synthesis for PLA and its degradation: clues for catalyst design. Mol. Catal., 2022, 528: 112480. doi:10.1016/j.mcat.2022.112480http://dx.doi.org/10.1016/j.mcat.2022.112480

Marin P.; Tschan M. J. L.; Isnard F.; Robert C.; Haquette P.; Trivelli X.; Chamoreau L. M.; Guérineau V.; Del Rosal I.; Maron L.; Venditto V.; Thomas C. M. Polymerization of rac-lactide using achiral iron complexes: access to thermally stable stereo complexes. Angew. Chem. Int. Ed., 2019, 58(36), 12585-12589. doi:10.1002/anie.201903224http://dx.doi.org/10.1002/anie.201903224

Rittinghaus R. D.; Karabulut A.; Hoffmann A.; Herres-Pawlis S. Active in sleep: iron guanidine catalyst performs ROP on dormant side of ATRP. Angew. Chem. Int. Ed., 2021, 60(40), 21795-21800. doi:10.1002/anie.202109053http://dx.doi.org/10.1002/anie.202109053

Bruckmoser J.; Henschel D.; Vagin S.; Rieger B. Combining high activity with broad monomer scope: indium salan catalysts in the ring-opening polymerization of various cyclic esters. Catal. Sci. Technol., 2022, 12(10), 3295-3302. doi:10.1039/d2cy00436dhttp://dx.doi.org/10.1039/d2cy00436d

Thongkham S.; Monot J.; Martin-Vaca B.; Bourissou D. Simple In-based dual catalyst enables significant progress in ε-decalactone ring-opening (co)polymerization. Macromolecules, 2019, 52(21), 8103-8113. doi:10.1021/acs.macromol.9b01511http://dx.doi.org/10.1021/acs.macromol.9b01511

Cheng M.; Attygalle A. B.; Lobkovsky E. B.; Coates G. W. Single-site catalysts for ring-opening polymerization: synthesis of heterotactic poly(lactic acid) from rac-Lactide. J. Am. Chem. Soc., 1999, 121(49), 11583-11584. doi:10.1021/ja992678ohttp://dx.doi.org/10.1021/ja992678o

Chellali J. E.; Alverson A. K.; Robinson J. R. Zinc aryl/alkyl β-diketiminates: balancing accessibility and stability for high-activity ring-opening polymerization of rac-lactide. ACS Catal., 2022, 12(9), 5585-5594. doi:10.1021/acscatal.2c00858http://dx.doi.org/10.1021/acscatal.2c00858

Xia M. F.; Zhuo C. X.; Ma X. J.; Zhang X. H.; Sun H. M.; Zhai Q. G.; Zhang Y. D. Assembly of the active center of organophosphorus hydrolase in metal-organic frameworks via rational combination of functional ligands. Chem. Commun., 2017, 53(82), 11302-11305. doi:10.1039/c7cc06270bhttp://dx.doi.org/10.1039/c7cc06270b

Yu I.; Acosta-Ramírez A.; Mehrkhodavandi P. Mechanism of living lactide polymerization by dinuclear indium catalysts and its impact on isoselectivity. J. Am. Chem. Soc., 2012, 134(30), 12758-12773. doi:10.1021/ja3048046http://dx.doi.org/10.1021/ja3048046

Fang J.; Yu I.; Mehrkhodavandi P.; Maron L. Theoretical Investigation of lactide ring-opening polymerization induced by a dinuclear indium catalyst. Organometallics, 2013, 32(23), 6950-6956. doi:10.1021/om400399khttp://dx.doi.org/10.1021/om400399k

Soobrattee S.; Zhai X. F.; Nyamayaro K.; Diaz C.; Kelley P.; Ebrahimi T.; Mehrkhodavandi P. Dinucleating amino-phenolate platform for zinc catalysts: impact on lactide polymerization. Inorg. Chem., 2020, 59(8), 5546-5557. doi:10.1021/acs.inorgchem.0c00250http://dx.doi.org/10.1021/acs.inorgchem.0c00250

Thevenon A.; Romain C.; Bennington M. S.; White A. J. P.; Davidson H. J.; Brooker S.; Williams C. K. Dizinc lactide polymerization catalysts: hyperactivity by control of ligand conformation and metallic cooperativity. Angew. Chem. Int. Ed., 2016, 55(30), 8680-8685. doi:10.1002/anie.201602930http://dx.doi.org/10.1002/anie.201602930

Ghosh S.; Schulte Y.; Wölper C.; Tjaberings A.; Gröschel A. H.; Haberhauer G.; Schulz S. Cooperative effect in binuclear zinc catalysts in the ROP of lactide. Organometallics, 2022, 41(19), 2698-2708. doi:10.1021/acs.organomet.2c00333https://doi.org/10.1021/acs.organomet.2c00333

Kricheldorf H. R.; Weidner S. M.; Scheliga F. Ring-expansion polymerization (REP) of L-lactide with cyclic Tin(II) bisphenoxides. Eur. Polym. J., 2019, 116, 256-264. doi:10.1016/j.eurpolymj.2019.04.024http://dx.doi.org/10.1016/j.eurpolymj.2019.04.024

Haque F. M.; Grayson S. M. The synthesis, properties and potential applications of cyclic polymers. Nat. Chem., 2020, 12(5), 433-444. doi:10.1038/s41557-020-0440-5http://dx.doi.org/10.1038/s41557-020-0440-5

Culkin D. A.; Jeong W.; Csihony S.; Gomez E. D.; Balsara N. P.; Hedrick J. L.; Waymouth R. M. Zwitterionic polymerization of lactide to cyclic poly(lactide) by using N-heterocyclic carbene organocatalysts. Angew. Chem. Int. Ed., 2007, 46(15), 2627-2630. doi:10.1002/anie.200604740http://dx.doi.org/10.1002/anie.200604740

Baśko M.; Kubisa, P. Cationic polymerization of L,L-lactide. J. Polym. Sci. A. Polym. Chem., 2010, 48(12), 2650-2658. doi:10.1002/pola.24048https://doi.org/10.1002/pola.24048

Wild U.; Neuhäuser C.; Wiesner S.; Kaifer E.; Wadepohl H.; Himmel H. J. Redox-controlled hydrogen bonding: turning a superbase into a strong hydrogen-bond donor. Chem. Eur. J., 2014, 20(20), 5914-5925. doi:10.1002/chem.201304882http://dx.doi.org/10.1002/chem.201304882

Impemba S.; Della Monica F.; Grassi A.; Capacchione C.; Milione S. Cyclic polyester formation with an [OSSO]-type iron(III) catalyst. ChemSusChem, 2020, 13(1), 141-145. doi:10.1002/cssc.201902163http://dx.doi.org/10.1002/cssc.201902163

Suo H. Y.; Liu S.; Liu J. Y.; Zhang Z. S.; Qu R.; Gu Y. N.; Qin Y. S. Novel epoxide-promoted polymerization of lactides mediated by a zinc guanidine complex: a potential strategy for the tin-free PLA industry. Polym. Chem., 2023, 14(40), 4652-4658. doi:10.1039/d3py00890hhttp://dx.doi.org/10.1039/d3py00890h

Chen J. W.; Wu X. M.; Zhang L.; Duan Z. Y.; Liu B. Y. Ring-opening polymerization of ε-caprolactone mediated by a di-zinc complex bearing a macrocyclic thioether-phenolate[OSSO]-type ligand. Polym. Chem., 2022, 13(20), 2971-2979. doi:10.1039/d2py00115bhttp://dx.doi.org/10.1039/d2py00115b

Ghosh S.; Antharjanam P. K. S.; Chakraborty D. Magnesium complexes of the N, O polydentate scaffold: synthesis, structural characterization and polymerization studies. Polymer, 2015, 70, 38-51. doi:10.1016/j.polymer.2015.06.001http://dx.doi.org/10.1016/j.polymer.2015.06.001

马钰琨, 沈勇, 李志波. 高热稳定Lewis酸碱对催化L-丙交酯均聚及与乙交酯共聚的本体开环聚合研究. 高分子学报, 2022, 53(8), 923-932. doi:10.11777/j.issn1000-3304.2022.22042http://dx.doi.org/10.11777/j.issn1000-3304.2022.22042

Views

下载量

CSCD

Alert me when the article has been cited

提交

Tools

Publicity Resources

Bulk Ring-opening Polymerization of L-Lactide and Its Copolymerization with Glycolide Catalyzed by Highly Thermal Stable Lewis Pairs

Ring-opening Polymerization of Lactide by Bifunctional Organocatalyst at Ambient Conditions

SYNTHESIS AND CHARACTERIZATION OF OPTICALLY ACTIVE POLY(PHENYLACETYLENE) WITH POLYLACTIDE SIDE CHAINS

Related Author

Zhi-bo Li

Yong Shen

Yu-kun Ma

Jing-yi Wang

Bo-ping Liu

Rui-hua Cheng

Wei Liu

Li Wu

Related Institution

Key Laboratory of Biobased Polymer Materials, Shandong Provincial Education Department; College of Polymer Science and Engineering

College of Chemical Engineering, Qingdao University of Science and Technology

State Key Laboratory of Chemical Engineering, East China University of Science and Technology

College of Materials and Energy, South China Agricultural University

Polymer Materials Research Center, College of Materials Science and Chemical Engineering, Harbin Engineering University

Postal code：100190
Tel：010-62588927 Email：gfzxb@iccas.ac.cn
Technical support is provided by Beijing Founder electronics co., LTD 京ICP备05002797号-8 京公网安备11010802024621
It is recommended to read the content of this site in Chrome&IE9+. Please switch to extreme mode in browser 360.
Cookies We use cookies to help provide and enhance our service and tailor content. By continuing, you agree to the use of cookies.

⁰