Monomer-activated Copolymerization of Ethylene Oxide and Epichlorohydrin: <italic style="font-style: italic">In Situ</italic> Kinetics Evidences Tapered Block Copolymer Formation

Ann-Kathrin Danner; Daniel Leibig; Lea-Marie Vogt; Holger Frey

doi:10.1007/s10118-019-2296-y

Your Location：

Home >

Browse articles >

Monomer-activated Copolymerization of Ethylene Oxide and Epichlorohydrin: In Situ Kinetics Evidences Tapered Block Copolymer Formation

ARTICLE | Updated：2021-02-18

- Monomer-activated Copolymerization of Ethylene Oxide and Epichlorohydrin: In Situ Kinetics Evidences Tapered Block Copolymer Formation
- Monomer-activated Copolymerization of Ethylene Oxide and Epichlorohydrin: In Situ Kinetics Evidences Tapered Block Copolymer Formation
- Chinese Journal of Polymer Science 2019年37卷第9期页码：912-918
- Affiliations：
  
  a.Institute of Organic Chemistry, Johannes Gutenberg-Universität Mainz, Duesbergweg 10-14, 55128 Mainz, Germany
  b.Graduate School Materials Science in Mainz, Staudinger Weg 9, 55128 Mainz, Germany
- Author bio：
  
  hfrey@uni-mainz.de
- Funds：
  
  A. Danner is a recipient of a DFG-funded position through the Excellence Initiative by the Graduate School Materials Science in Mainz (GSC 266). The authors thank Dr. Johannes C. Liermann and Nadine Schenk for technical assistance during in situ NMR kinetics measurements as well as Maria Mueller and Monika Schmelzer for DSC and SEC measurements. Jan Blankenburg is acknowledged for help with the evaluation of in situ NMR data.
- DOI：10.1007/s10118-019-2296-y
  中图分类号：
- 收稿：2019-04-12，
  
  修回：2019-5-16，
  
  录用：2019-5-16，
  
  网络首发：2019-07-04，
  
  纸质出版：2019-09
- Accepted：
Scan QR Code
Citation: Danner, A. K.; Leibig, D.; Vogt, L. M.; Frey, H. Monomer-activated copolymerization of ethylene oxide and epichlorohydrin: In situ kinetics evidences tapered block copolymer formation. Chinese J. Polym. Sci. 2019, 37, 912–918

Ann-Kathrin Danner, Daniel Leibig, Lea-Marie Vogt, et al. Monomer-activated Copolymerization of Ethylene Oxide and Epichlorohydrin: In Situ Kinetics Evidences Tapered Block Copolymer Formation[J]. Chinese Journal of Polymer Science, 2019, 37(9): 912-918. DOI: 10.1007/s10118-019-2296-y.
Citation: Danner, A. K.; Leibig, D.; Vogt, L. M.; Frey, H. Monomer-activated copolymerization of ethylene oxide and epichlorohydrin: In situ kinetics evidences tapered block copolymer formation. Chinese J. Polym. Sci. 2019, 37, 912–918 DOI： 10.1007/s10118-019-2296-y.

Ann-Kathrin Danner, Daniel Leibig, Lea-Marie Vogt, et al. Monomer-activated Copolymerization of Ethylene Oxide and Epichlorohydrin: In Situ Kinetics Evidences Tapered Block Copolymer Formation[J]. Chinese Journal of Polymer Science, 2019, 37(9): 912-918. DOI: 10.1007/s10118-019-2296-y. DOI：

摘要

Abstract

The monomer-activated anionic ring-opening copolymerization (AROP) of ethylene oxide (EO) and epichlorohydrin (ECH) using tetraoctylammonium bromide as an initiator and triisobutylaluminum (

-Bu

Al) as an activator was studied. The properties of the copolymers as well as the microstructure have been analyzed in detail

via

in situ

NMR kinetics study. The statistical copolymers exhibited molecular weights ranging from 2350 g·mol

–1

to 38000 g·mol

–1

(measured by SEC

PEG-standards) and moderate dispersities of 1.27–1.44. The thermal property tests revealed both a glass transition and melting for all copolymers

supporting a block-like nature. Applying

in situ

NMR kinetic measurements

the reactivity ratios of EO and ECH were determined to be strongly disparate

i.e

= 9.2 and

ECH

= 0.10. This shows that the simple one-pot statistical anionic copolymerization of EO and ECH

via

the monomer-activated AROP resulted in the formation of strongly tapered

block-like structures. Furthermore

post-polymerization functionalization of the reactive chloromethyl groups by nucleophilic displacement was investigated for the copolymers. Copolymerization of EO and ECH offers a broad platform for further functionalization and therefore the possibility to prepare a variety of multifunctional PEGs.

关键词

Keywords

references

Frey, H.; Haag, R . Dendritic polyglycerol: A new versatile biocompatible material . Rev. Molecular Biotechnol. , 2002 . 90 257 - 267 . DOI: 10.1016/S1389-0352(01)00063-0 http://doi.org/10.1016/S1389-0352(01)00063-0 .

Kainthan, R. K.; Janzen, J.; Levin, E.; Devine, D. V.; Brooks, D. E . Biocompatibility testing of branched and linear polyglycidol . Biomacromolecules , 2006 . 7 703 - 709 . DOI: 10.1021/bm0504882 http://doi.org/10.1021/bm0504882 .

Thomas, A.; Müller, S. S.; Frey, H . Beyond poly(ethylene glycol): Linear polyglycerol as a multifunctional polyether for biomedical and pharmaceutical applications . Biomacromolecules , 2014 . 15 1935 - 1954 . DOI: 10.1021/bm5002608 http://doi.org/10.1021/bm5002608 .

Weinhart, M.; Grunwald, I.; Wyszogrodzka, M.; Gaetjen, L.; Hartwig, A.; Haag, R . Linear poly(methyl glycerol) and linear polyglycerol as potent protein and cell resistant alternatives to poly(ethylene glycol) . Chem. Asian J. , 2010 . 5 1992 - 2000 . DOI: 10.1002/asia.201000127 http://doi.org/10.1002/asia.201000127 .

Gosecki, M.; Gadzinowski, M.; Gosecka, M.; Basinska, T.; Slomkowski, S . Polyglycidol, its derivatives, and polyglycidol-containing copolymers—Synthesis and medical applications . Polymers , 2016 . 8 227 DOI: 10.3390/polym8060227 http://doi.org/10.3390/polym8060227 .

Calderón, M.; Quadir, M. A.; Sharma, S. K.; Haag, R . Dendritic polyglycerols for biomedical applications . Adv. Mater. , 2010 . 22 190 - 218 . DOI: 10.1002/adma.v22:2 http://doi.org/10.1002/adma.v22:2 .

Carlotti, S.; Labbé, A.; Rejsek, V.; Doutaz, S.; Gervais, M.; Deffieux, A . Living/controlled anionic polymerization and copolymerization of epichlorohydrin with tetraoctylammonium bromide-triisobutylaluminum initiating systems . Macromolecules , 2008 . 41 7058 - 7062 . DOI: 10.1021/ma801422c http://doi.org/10.1021/ma801422c .

Biedron, T.; Kubisa, P.; Penczek, S . Polyepichlorohydrin diols free of cyclics: Synthesis and characterization . J. Polym. Sci., Part A: Polym. Chem. , 1991 . 29 619 - 628 . .

Vandenberg, E. J . Organometallic catalysts for polymerizing monosubstituted epoxides . J. Polym. Sci. , 1960 . 47 486 - 489 . DOI: 10.1002/pol.1960.1204714947 http://doi.org/10.1002/pol.1960.1204714947 .

Xie, H. Q.; Guo, J. S.; Yu, G. Q.; Zu, J . Ring-opening polymerization of epichlorohydrin and its copolymerization with other alkylene oxides by quaternary catalyst system . J. Appl. Polym. Sci. , 2001 . 80 2446 - 2454 . DOI: 10.1002/(ISSN)1097-4628 http://doi.org/10.1002/(ISSN)1097-4628 .

Wu, J.; Shen, Z . Rare earth coordination catalysts for the polymerization of alkylene oxides I. Polymerization of epichlorohydrin . Polym. J. , 1990 . 22 326 - 330 . DOI: 10.1295/polymj.22.326 http://doi.org/10.1295/polymj.22.326 .

Hsieh, H. L . Polymerization of alkylene oxides with trialkylaluminum, metal acetylacetonates, and water . J. Appl. Polym. Sci. , 1971 . 15 2425 - 2438 . DOI: 10.1002/app.1971.070151009 http://doi.org/10.1002/app.1971.070151009 .

Kuntz, I.; Kroll, W. R . Polymerization of epoxides with dialkylaluminum acetylacetonate catalyst systems . J. Polym. Sci., Part A: Polym. Chem. , 1970 . 8 1601 - 1621 . DOI: 10.1002/pol.1970.150080701 http://doi.org/10.1002/pol.1970.150080701 .

Yagci, Y.; Serhatli, I. E.; Kubisa, P.; Biedron, T . Synthesis of block copolymers by combination of an activated monomer and free radical polymerization mechanism . Macromolecules , 1993 . 26 2397 - 2399 . DOI: 10.1021/ma00062a001 http://doi.org/10.1021/ma00062a001 .

Xie, H. Q.; Pan, S. B.; Guo, J. S . Ring-opening copolymerization of epoxy-terminated polystyrene macromer with epichlorohydrin and study on properties of the copolymers . Eur. Polym. J. , 2003 . 39 715 - 724 . DOI: 10.1016/S0014-3057(02)00277-X http://doi.org/10.1016/S0014-3057(02)00277-X .

Royappa, A. T . On the copolymerization of epichlorohydrin and glycidol . J. Appl. Polym. Sci. , 1997 . 65 1897 - 1904 . DOI: 10.1002/(ISSN)1097-4628 http://doi.org/10.1002/(ISSN)1097-4628 .

Majid, M. A.; George, M. H.; Barrie, J. A . Living anionic synthesis and characterization of poly(epichlorohydrin- g -styrene) copolymers . Polymer , 1981 . 22 1104 - 1111 . DOI: 10.1016/0032-3861(81)90300-1 http://doi.org/10.1016/0032-3861(81)90300-1 .

Kohjiya, S.; Horiuchi, T.; Miura, K.; Kitagawa, M.; Sakashita, T.; Matoba, Y.; Ikeda, Y . Polymer solid electrolyte from amorphous poly[epichlorohydrin- co -(ethylene oxide)]/lithium perchlorate complex . Polym. Int. , 2000 . 49 197 - 202 . DOI: 10.1002/(ISSN)1097-0126 http://doi.org/10.1002/(ISSN)1097-0126 .

Kuntz, I.; Cozewith, C.; Oakley, H. T.; Via, G.; White, H. T.; Wilchinsky, Z. W . Epoxide copolymerization with the dialkylaluminum acetylacetonate-dialkylzinc-water catalyst system . Macromolecules , 1971 . 4 4 - 10 . DOI: 10.1021/ma60019a002 http://doi.org/10.1021/ma60019a002 .

Gervais, M.; Brocas, A. L.; Cendejas, G.; Deffieux, A.; Carlotti, S . Synthesis of linear high molar mass glycidol-based polymers by monomer-activated anionic polymerization . Macromolecules , 2010 . 43 1778 - 1784 . DOI: 10.1021/ma902286a http://doi.org/10.1021/ma902286a .

Gervais, M.; Brocas, A. L.; Cendejas, G.; Deffieux, A.; Carlotti, S . Linear high molar mass polyglycidol and its direct α -azido functionalization . Macromol. Symp. , 2011 . 308 101 - 111 . DOI: 10.1002/masy.v308.1 http://doi.org/10.1002/masy.v308.1 .

Billouard, C.; Carlotti, S.; Desbois, P.; Deffieux, A . " Controlled” high-speed anionic polymerization of propylene oxide initiated by alkali metal alkoxide/trialkylaluminum systems . Macromolecules , 2004 . 37 4038 - 4043 . DOI: 10.1021/ma035768t http://doi.org/10.1021/ma035768t .

Labbé, A.; Carlotti, S.; Billouard, C.; Desbois, P.; Deffieux, A . Controlled high-speed anionic polymerization of propylene oxide initiated by onium salts in the presence of triisobutylaluminum . Macromolecules , 2007 . 40 7842 - 7847 . DOI: 10.1021/ma070288d http://doi.org/10.1021/ma070288d .

Rejsek, V.; Sauvanier, D.; Billouard, C.; Desbois, P.; Deffieux, A.; Carlotti, S . Controlled anionic homo- and copolymerization of ethylene oxide and propylene oxide by monomer activation . Macromolecules , 2007 . 40 6510 - 6514 . DOI: 10.1021/ma070450c http://doi.org/10.1021/ma070450c .

Müller, S. S.; Moers, C.; Frey, H . A challenging comonomer pair: Copolymerization of ethylene oxide and glycidyl methyl ether to thermoresponsive polyethers . Macromolecules , 2014 . 47 5492 - 5500 . DOI: 10.1021/ma501280k http://doi.org/10.1021/ma501280k .

Heinen, S.; Rackow, S.; Schäfer, A.; Weinhart, M . A perfect match: Fast and truly random copolymerization of glycidyl ether monomers to thermoresponsive copolymers . Macromolecules , 2017 . 50 44 - 53 . DOI: 10.1021/acs.macromol.6b01904 http://doi.org/10.1021/acs.macromol.6b01904 .

Gervais, M.; Labbé, A.; Carlotti, S.; Deffieux, A . Direct synthesis of α -azido, ω -hydroxypolyethers by monomer-activated anionic polymerization . Macromolecules , 2009 . 42 2395 - 2400 . DOI: 10.1021/ma802063s http://doi.org/10.1021/ma802063s .

Rodriguez, C. G.; Ferrier, R. C.; Helenic, A.; Lynd, N. A . Ring-opening polymerization of epoxides: Facile pathway to functional polyethers via a versatile organoaluminum initiator . Macromolecules , 2017 . 50 3121 - 3130 . DOI: 10.1021/acs.macromol.7b00196 http://doi.org/10.1021/acs.macromol.7b00196 .

Lundberg, P.; Lee, B. F.; van den Berg, S. A.; Pressly, E. D.; Lee, A.; Hawker, C. J.; Lynd, N. A . Poly(ethylene oxide)- co -(methylene ethylene oxide): A hydrolytically-degradable poly(ethylene oxide) platform . ACS Macro Lett. , 2012 . 1 1240 - 1243 . DOI: 10.1021/mz300477t http://doi.org/10.1021/mz300477t .

Meyer, J.; Keul, H.; Möller, M . Poly(glycidyl amine) and copolymers with glycidol and glycidyl amine repeating units: Synthesis and characterization . Macromolecules , 2011 . 44 4082 - 4091 . DOI: 10.1021/ma200757v http://doi.org/10.1021/ma200757v .

Brocas, A. L.; Cendejas, G.; Caillol, S.; Deffieux, A.; Carlotti, S . Controlled synthesis of polyepichlorohydrin with pendant cyclic carbonate functions for isocyanate-free polyurethane networks . J. Polym. Sci., Part A: Polym. Chem. , 2011 . 49 2677 - 2684 . DOI: 10.1002/pola.24699 http://doi.org/10.1002/pola.24699 .

Hu, H.; Yuan, W.; Lu, L.; Zhao, H.; Jia, Z.; Baker, G. L . Low glass transition temperature polymer electrolyte prepared from ionic liquid grafted polyethylene oxide . J. Polym. Sci., Part A: Polym. Chem. , 2014 . 52 2104 - 2110 . DOI: 10.1002/pola.v52.15 http://doi.org/10.1002/pola.v52.15 .

Deng, M; Guo, F.; Liao, D.; Hou, Z.; Li, Y . Aluminium-catalyzed terpolymerization of furfuryl glycidyl ether with epichlorohydrin and ethylene oxide: Synthesis of thermoreversible polyepichlorohydrin elastomers with furan/maleimide covalent crosslinks. Polym . Chem. , 2018 . 9 98 - 107 . .

Deng, M; Guo, F.; Li, Y.; Hou, Z . Synthesis of alkynyl-functionalized linear and star polyethers by aluminium-catalyzed copolymerization of glycidyl 3-butynyl ether with epichlorohydrin and ethylene oxide. Polym . Chem. , 2019 . 10 1110 - 1118 . .

Chipara, M. I.; Barb, D.; Notingher, P. V.; Georgescu, L.; Sarbu, T . Spin probe investigation of molecular motions in polyepichlorohydrin: 1 . Polymer , 1996 . 37 707 - 712 . DOI: 10.1016/0032-3861(96)83160-0 http://doi.org/10.1016/0032-3861(96)83160-0 .

Mandelkern, L . The crystallization of flexible polymer molecules . Chem. Rev. , 1956 . 56 903 - 958 . DOI: 10.1021/cr50011a001 http://doi.org/10.1021/cr50011a001 .

Herzberger, J.; Leibig, D.; Liermann, J. C.; Frey, H . Conventional oxyanionic versus monomer-activated anionic copolymerization of ethylene oxide with glycidyl ethers: Striking differences in reactivity ratios . ACS Macro Lett. , 2016 . 5 1206 - 1211 . DOI: 10.1021/acsmacrolett.6b00701 http://doi.org/10.1021/acsmacrolett.6b00701 .

Blankenburg, J.; Wagner, M.; Frey, H . Well-defined multi-amino-functional and stimuli-responsive poly(propylene oxide) by crown ether assisted anionic ring-opening polymerization . Macromolecules , 2017 . 50 8885 - 8893 . DOI: 10.1021/acs.macromol.7b01324 http://doi.org/10.1021/acs.macromol.7b01324 .

Obermeier, B.; Wurm, F.; Mangold, C.; Frey, H . Multifunctional poly(ethylene glycol)s . Angew. Chem. Int. Ed. , 2011 . 50 7988 - 7997 . DOI: 10.1002/anie.v50.35 http://doi.org/10.1002/anie.v50.35 .

Clayden, J.; Greeves, N.; Warren, S. G. Organic chemistry , 2. ed.; Oxford Univ. Press, Oxford, 2012 .

Tang, T.; Fan, X.; Jin, Y.; Wang, G . Synthesis and characterization of graft copolymers with poly(epichlorohydrin- co -ethylene oxide) as backbone by combination of ring-opening polymerization with living anionic polymerization . Polymer , 2014 . 55 3680 - 3687 . DOI: 10.1016/j.polymer.2014.05.066 http://doi.org/10.1016/j.polymer.2014.05.066 .

浏览量

523

Downloads

CSCD

文章被引用时，请邮件提醒。

Submit

工具集

关联资源

Flexible Gradient Poly(ether-ester) from the Copolymerization of Epoxides and ε-Caprolactone Mediated by a Hetero-bimetallic Complex

Mechanism-inspired Design of Heterodinuclear Catalysts for Copolymerization of Epoxide and Lactone

Recent Progress on COS-derived Polymers

Chemoselective Ring-opening Copolymerization of CO2-based Lactones towards Functional Polyesters

High Pressure Synthesis for Gold-backboned Polymer

Monomer-activated Copolymerization of Ethylene Oxide and Epichlorohydrin: In Situ Kinetics Evidences Tapered Block Copolymer Formation

Monomer-activated Copolymerization of Ethylene Oxide and Epichlorohydrin: In Situ Kinetics Evidences Tapered Block Copolymer Formation

DOI：10.1007/s10118-019-2296-y

摘要

Abstract

关键词

Keywords

references