Polymerization Mechanism of Methyl Methacrylate Initiated by Ethyl Acetate/<italic style="font-style: italic">t</italic>-BuP<sub>4</sub>

De-Yong Xia; Qi-Min Jiang; Wen-Yan Huang; Hong-Jun Yang; Xiao-Qiang Xue; Li Jiang; Bi-Biao Jiang

doi:10.1007/s10118-019-2228-x

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Polymerization Mechanism of Methyl Methacrylate Initiated by Ethyl Acetate/t-BuP₄

ARTICLE | Updated：2021-02-18

- Polymerization Mechanism of Methyl Methacrylate Initiated by Ethyl Acetate/t-BuP₄
- Polymerization Mechanism of Methyl Methacrylate Initiated by Ethyl Acetate/t-BuP₄
- Chinese Journal of Polymer Science 2019年37卷第6期页码：598-603
- Affiliations：
  
  a.Jiangsu Key Laboratory of Environmentally Friendly Polymeric Materials, School of Materials Science and Engineering, Jiangsu Collaborative Innovation Center of Photovoltaic Science and Engineering, Changzhou University, Changzhou 213164, China
  b.Changzhou University Huaide College, Jingjiang 214500, China
- Author bio：
  
  jiangbibiao@cczu.edu.cn
- Funds：
  
  This work was finanically supported by the National Natural Science Foundation of China (No. 21474010) and the Priority Academic Program Development of Jiangsu Province.
- DOI：10.1007/s10118-019-2228-x
  中图分类号：
- 收稿：2018-12-11，
  
  修回：2019-1-8，
  
  录用：2019-1-21，
  
  网络首发：2019-02-26，
  
  纸质出版：2019-06
- Accepted：
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Citation: Xia, D. Y.; Jiang, Q. M.; Huang, W. Y.; Yang, H. J.; Xue, X. Q.; Jiang, L.; Jiang, B. B. Polymerization mechanism of methyl methacrylate initiated by ethyl acetate/t-BuP₄. Chinese J. Polym. Sci. 2019, 37, 598–603 DOI: 10.1007/s10118-019-2228-x.

De-Yong Xia, Qi-Min Jiang, Wen-Yan Huang, et al. Polymerization Mechanism of Methyl Methacrylate Initiated by Ethyl Acetate/t-BuP₄[J]. Chinese Journal of Polymer Science, 2019, 37(6): 598-603. DOI: 10.1007/s10118-019-2228-x.
Citation: Xia, D. Y.; Jiang, Q. M.; Huang, W. Y.; Yang, H. J.; Xue, X. Q.; Jiang, L.; Jiang, B. B. Polymerization mechanism of methyl methacrylate initiated by ethyl acetate/t-BuP₄. Chinese J. Polym. Sci. 2019, 37, 598–603 DOI: 10.1007/s10118-019-2228-x. DOI：

De-Yong Xia, Qi-Min Jiang, Wen-Yan Huang, et al. Polymerization Mechanism of Methyl Methacrylate Initiated by Ethyl Acetate/t-BuP₄[J]. Chinese Journal of Polymer Science, 2019, 37(6): 598-603. DOI: 10.1007/s10118-019-2228-x. DOI：

摘要

Abstract

The anionic polymerization of methyl methacrylate (MMA) was carried out using phosphazene base

-BuP

and ethyl acetate (EA) as the catalyst and the initiator

respectively. Gas chromatography (GC)

size exclusion chromatography (SEC) measurements

and nuclear magnetic resonance (NMR) analyses were used to reveal the polymerization mechanism and to confirm the polymer structure. The results confirmed the proposed polymerization mechanism and the polymer structure

while the initiator efficiency was low. Meanwhile

the initiation by methoxy anion coming from hydrolysis of the ester bond in MMA was also observed. As a result

there is a marked deviation between the theoretical molecular weight and the measured molecular weight

and it is essential to carry out the polymerization at excessive dosage of

-BuP

for preparing polymers with narrow molecular weight distribution.

关键词

Keywords

references

Schwesinger, R.; Schlemper, H . Peralkylated polyaminophosphazenes-extremely strong, neutral nitrogen bases . Angew. Chem. Int. Ed. , 1987 . 26 1167 - 1169 . DOI: 10.1002/(ISSN)1521-3773 http://doi.org/10.1002/(ISSN)1521-3773 .

Schwesinger, R.; Willaredt, J.; Schlemper, H.; Keller, M.; Schmitt, D.; Fritz, H . Novel, very strong, uncharged auxiliary bases; design and synthesis of monomeric and polymer-bound triaminoiminophosphorane bases of broadly varied steric demand . Chem. Ber. , 1994 . 127 2435 - 2454 . DOI: 10.1002/(ISSN)1099-0682 http://doi.org/10.1002/(ISSN)1099-0682 .

Schwesinger, R.; Schlemper, H.; Hasenfratz, C.; Willaredt, J.; Dambacher, T.; Breuer, T.; Ottaway, C.; Fletschinger, M.; Boele, J.; Fritz, H.; Putzas, D.; Rotter, H. W.; Bordwell, F. G.; Satish, A. V.; Ji, G. Z.; Peters, E. M.; Peters, K.; Schnering, H. G. V.; Walz, L . Extremely strong, uncharged auxiliary bases; monomeric and polymer-supported polyaminophosphazenes (P 2 -P 5 ) . Liebigs Ann. , 1996 . 7 1055 - 1081 . .

Kaupmees, K.; Trummal, A.; Leito, I . Basicities of strong bases in water: A computational study . Croat. Chem. Acta , 2014 . 87 385 - 395 . DOI: 10.5562/cca2472 http://doi.org/10.5562/cca2472 .

Pietzonka, T.; Seebach, D . Alkylations of ( R , R )-2- t -butyl-6-methyl-1,3-dioxan-4-ones which are not possible with lithium amides may be achieved with a schwesinger P 4 Base . Chem. Ber. , 1991 . 124 1837 - 1843 . DOI: 10.1002/(ISSN)1099-0682 http://doi.org/10.1002/(ISSN)1099-0682 .

Pietzonka, T.; Seebach, D . N -Perbenzylation of oligopeptides with P 4 -phosphazene base; a new protecting-group technique for modification and solubilization of peptides in apolar organic solvents . Angew. Chem. Int. Ed. , 1992 . 31 1481 - 1482 . DOI: 10.1002/(ISSN)1521-3773 http://doi.org/10.1002/(ISSN)1521-3773 .

Pietzonka, T.; Seebach, D . The P 4 -phosphazene base as part of a new metal-free initiator system for the anionic polymerization of methyl methacrylate . Angew. Chem. Int. Ed. , 1993 . 32 716 - 717 . DOI: 10.1002/(ISSN)1521-3773 http://doi.org/10.1002/(ISSN)1521-3773 .

Isono, T . Synthesis of star- and figure-eight-shaped polyethers by t -Bu-P 4 -catalyzed ring-opening polymerization of butylene oxide . Macromolecules , 2013 . 46 3841 - 3849 . DOI: 10.1021/ma4006654 http://doi.org/10.1021/ma4006654 .

Song, Q. L.; Hu, S. Y.; Zhao, J. P.; Zhang, G. Z . Organocatalytic copolymerization of mixed type monomers . Chinese J. Polym. Sci. , 2017 . 35 581 - 601 . DOI: 10.1007/s10118-017-1925-6 http://doi.org/10.1007/s10118-017-1925-6 .

Kondo, Y. in Superbases for organic synthesis: Guanidines, amidines, phosphazenes and related organocatalysts , John Wiley & amp; Sons Ltd., 2009 , pp. 145–185.

Boileau, S.; Illy, N . Activation in anionic polymerization: Why phosphazene bases are very exciting promoters . Prog. Polym. Sci. , 2011 . 36 1132 - 1151 . DOI: 10.1016/j.progpolymsci.2011.05.005 http://doi.org/10.1016/j.progpolymsci.2011.05.005 .

Ottou, W. N.; Sardon, H.; Mecerreyes, D.; Vignolle, J.; Taton, D . Update and challenges in organo-mediated polymerization reactions . Prog. Polym. Sci. , 2016 . 56 64 - 115 . DOI: 10.1016/j.progpolymsci.2015.12.001 http://doi.org/10.1016/j.progpolymsci.2015.12.001 .

Hu, S. Y.; Zhao, J. P.; Zhang, G. Z.; Schlaad, H . Macromolecular architectures through organocatalysis . Prog. Polym. Sci. , 2017 . 74 34 - 77 . DOI: 10.1016/j.progpolymsci.2017.07.002 http://doi.org/10.1016/j.progpolymsci.2017.07.002 .

Hong, M.; Chen, E. Y. X . Towards truly sustainable polymers: A metal-free recyclable polyester from biorenewable non-strained γ -butyrolactone . Angew. Chem. Int. Ed. , 2016 . 55 4188 - 4193 . DOI: 10.1002/anie.201601092 http://doi.org/10.1002/anie.201601092 .

Hong, M.; Tang, X. Y.; Newell, B. S.; Chen, E. Y. X . " Nonstrained” γ -butyrolactone-based copolyesters: Copolymerization characteristics and composition-dependent (thermal, eutectic, cocrystallization, and degradation) properties . Macromolecules , 2017 . 50 8469 - 8479 . DOI: 10.1021/acs.macromol.7b02174 http://doi.org/10.1021/acs.macromol.7b02174 .

Song, Q. L.; Xia, Y. N.; Hu, S. Y.; Zhao, J. P.; Zhang, G. Z . Tuning the crystallinity and degradability of PCL by organocatalytic copolymerization with δ -hexalactone . Polymer , 2016 . 102 248 - 255 . DOI: 10.1016/j.polymer.2016.09.026 http://doi.org/10.1016/j.polymer.2016.09.026 .

Zhang, L.; Nederberg, F.; Messman, J. M.; Pratt, R. C.; Hedrick, J. L.; Wade, C. G . Organocatalytic stereoselective ring-opening polymerization of lactide with dimeric phosphazene bases . J. Am. Chem. Soc. , 2007 . 129 12610 - 12611 . DOI: 10.1021/ja074131c http://doi.org/10.1021/ja074131c .

Liu, J. J.; Chen, C.; Li, Z. J.; Wu, W. Z.; Zhi, X.; Zhang, Q. G.; Wu, H.; Wang, X.; Cui, S. D.; Guo, K . A squaramide and tertiary amine: An excellent hydrogen-bonding pair organocatalyst for living polymerization . Polym. Chem. , 2015 . 6 3754 - 3757 . DOI: 10.1039/C5PY00508F http://doi.org/10.1039/C5PY00508F .

Liu, S. F.; Ren, C. L.; Zhao, N.; Shen, Y.; Li, Z. B . Phosphazene bases as organocatalysts for ring-opening polymerization of cyclic esters . Macromol. Rapid Commun. , 2018 . 39 1800485 DOI: 10.1002/marc.v39.24 http://doi.org/10.1002/marc.v39.24 .

Li, Y. X.; Zhao, N.; Wei, C. Z.; Sun, A. B.; Liu, S. F.; Li, Z. B . Binary organocatalytic system for ring-opening polymerization of ε -caprolactone and δ -valerolactone: Synergetic effects for enhanced selectivity . Eur. Polym. J. , 2019 . 111 11 - 19 . DOI: 10.1016/j.eurpolymj.2018.12.012 http://doi.org/10.1016/j.eurpolymj.2018.12.012 .

Liu, S. F.; Li, H. K.; Zhao, N.; Li, Z. B . Stereoselective ring-opening polymerization of rac-lactide using organocatalytic cyclic trimeric phosphazene base . ACS Macro Lett. , 2018 . 7 624 - 628 . DOI: 10.1021/acsmacrolett.8b00353 http://doi.org/10.1021/acsmacrolett.8b00353 .

Dentzer, L.; Bray, C.; Noinville, S.; Illy, N.; Guégan, P . Phosphazene-promoted metal-free ring-opening polymerization of 1,2-epoxybutane initiated by secondary amides . Macromolecules , 2015 . 48 7755 - 7764 . DOI: 10.1021/acs.macromol.5b01638 http://doi.org/10.1021/acs.macromol.5b01638 .

Hassouna, L.; Illy, N.; Guégan, P . Phosphazene/triisobutylaluminum-promoted anionic ring-opening polymerization of 1,2-epoxybutane initiated by secondary carbamates . Polym. Chem. , 2017 . 8 4005 - 4013 . DOI: 10.1039/C7PY00675F http://doi.org/10.1039/C7PY00675F .

Zhang, H. X.; Hu, S. Y.; Zhao, J. P.; Zhang, G. Z . Phosphazene-catalyzed alternating copolymerization of dihydrocoumarin and ethylene oxide: Weaker is better . Macromolecules , 2017 . 50 4198 - 4205 . DOI: 10.1021/acs.macromol.7b00599 http://doi.org/10.1021/acs.macromol.7b00599 .

Zhang, J.; Liu, Q.; Ren, H. J.; Zhang, N. J.; Li, P. F.; Yang, K . Phosphoniums as catalysts for metal-free polymerization: Synthesis of well-defined poly(propylene oxide) . J. Mol. Struc. , 2017 . 1148 421 - 428 . DOI: 10.1016/j.molstruc.2017.05.094 http://doi.org/10.1016/j.molstruc.2017.05.094 .

Xia, Y. N.; Zhao, J. P . Macromolecular architectures based on organocatalytic ring-opening (co)polymerization of epoxides . Polymer , 2018 . 143 343 - 361 . DOI: 10.1016/j.polymer.2018.03.047 http://doi.org/10.1016/j.polymer.2018.03.047 .

Eßwein, B.; Molenberg, A.; Möller, M . Use of polyiminophosphazene bases for ring-opening polymerizations . Macromol. Symp. , 1996 . 107 331 - 340 . DOI: 10.1002/masy.v107.1 http://doi.org/10.1002/masy.v107.1 .

Molenberg, A.; Möller, M . A fast catalyst system for the ring-opening polymerization of cyclosiloxanes . Macromol. Rapid Commun. , 1995 . 16 449 - 453 . DOI: 10.1002/marc.1995.030160606 http://doi.org/10.1002/marc.1995.030160606 .

Pibre, G.; Chaumont, P.; Fleury, E.; Cassagnau, P . Ring-opening polymerization of decamethylcyclopentasiloxane initiated by a superbase: Kinetics and rheology . Polymer , 2008 . 49 234 - 240 . DOI: 10.1016/j.polymer.2007.11.017 http://doi.org/10.1016/j.polymer.2007.11.017 .

Dyke, M. E. V.; Clarson, S. J . Reaction kinetics for the anionic ring-opening polymerization of tetraphenyltetramethylcyclotetrasiloxane using a fast initiator system . J. Inorg. Organomet. Polym. , 1998 . 8 111 - 117 . DOI: 10.1023/A:1022487906770 http://doi.org/10.1023/A:1022487906770 .

Samuel, C.; Chalamet, Y.; Boisson, F.; Majesté, J.; Becquart, F.; Fleury, E . Highly efficient metal-free organic catalysts to design new environmentally friendly starch-based blends . J. Polym. Sci., Part A: Polym. Chem. , 2014 . 52 493 - 503 . DOI: 10.1002/pola.27022 http://doi.org/10.1002/pola.27022 .

Brignou, P.; Gil, M. P.; Casagrande, O.; Carpentier, J. F.; Guillaume, S. M . Polycarbonates derived from green acids: Ring-opening polymerization of seven-membered cyclic carbonates . Macromolecules , 2010 . 43 8007 - 8017 . DOI: 10.1021/ma1014098 http://doi.org/10.1021/ma1014098 .

Chen, J. L.; Li, M. S.; He, W. J.; Tao, Y. H.; Wang, X. H . Facile organocatalyzed synthesis of poly( ε -lysine) under mild conditions . Macromolecules , 2017 . 50 9128 - 9134 . DOI: 10.1021/acs.macromol.7b02331 http://doi.org/10.1021/acs.macromol.7b02331 .

Jr, W. M.; Campbell, G. C.; Davidson, F . Poly(aminophosphazene)s and protophosphatranes mimic classical strong anionic base catalysts in the anionic ring-opening polymerization of lactams . Macromolecules , 1996 . 29 6475 - 6480 . DOI: 10.1021/ma960659i http://doi.org/10.1021/ma960659i .

Börner, H. G.; Heitz, W . Anionic polymerization of butyl acrylate with metal free initiator systems containing [1- tert -butyl-4,4,4-tris(dimethylamino)-2,2-bis[tris(dimethylamino)-phosphor-anylidenamino]-2 λ 5 ,4 λ 5 -catenadi(phosphazene)] base (P 4 - tert -butyl-phosphazene base) . Macromol. Chem. Phys. , 1998 . 199 1815 - 1820 . .

Kakuchi, T.; Chen, Y.; Kitakado, J.; Mori, K.; Fuchise, K.; Satoh, T . Organic superbase as an efficient catalyst for group transfer polymerization of methyl methacrylate . Macromolecules , 2011 . 44 4641 - 4647 . DOI: 10.1021/ma200720p http://doi.org/10.1021/ma200720p .

Weideman, I.; Pfukwa, R.; Klumperman, B . Phosphazene base promoted anionic polymerization of n -butyraldehyde . Eur. Polym. J. , 2017 . 93 97 - 102 . DOI: 10.1016/j.eurpolymj.2017.05.034 http://doi.org/10.1016/j.eurpolymj.2017.05.034 .

Zhao, N.; Ren, C. L.; Li, H. K.; Li, Y. X.; Liu, S. F.; Li, Z. B . Selective ring-opening polymerization of non-strained γ -butyrolactone catalyzed by a cyclic trimeric phosphazene base . Angew. Chem. Int. Ed. , 2017 . 56 12987 - 12990 . DOI: 10.1002/anie.201707122 http://doi.org/10.1002/anie.201707122 .

Li, H. K.; Zhao, N.; Ren, C. L.; Liu, S. F.; Li, Z. B . Synthesis of linear and star poly( ε -caprolactone) with controlled and high molecular weights via cyclic trimeric phosphazene base catalyzed ring-opening polymerization . Polym. Chem. , 2017 . 8 7369 - 7374 . DOI: 10.1039/C7PY01673E http://doi.org/10.1039/C7PY01673E .

Wang, J.; Li, B. X.; Xin, D. H.; Hu, R. R.; Zhao, Z. J.; Qin, A. J.; Tang, B. Z . Superbase catalyzed regio-selective polyhydroalkoxylation of alkynes: A facile route towards functional poly(vinyl ether)s . Polym. Chem. , 2017 . 8 2713 - 2722 . DOI: 10.1039/C7PY00363C http://doi.org/10.1039/C7PY00363C .

Fevre, M . Tris(2,4,6-trimethoxyphenyl)phosphine (TTMPP) as potent organocatalyst for group transfer polymerization of alkyl (meth)acrylates . Macromolecules , 2012 . 45 7711 - 7718 . DOI: 10.1021/ma301412z http://doi.org/10.1021/ma301412z .

Wang, D.; Hadjichristidis, N . Allyl borates: A novel class of polyhomologation initiators . Chem. Commun. , 2017 . 53 1196 - 1199 . DOI: 10.1039/C6CC09047H http://doi.org/10.1039/C6CC09047H .

Lascelles, S. F.; Malet, F.; Mayada, R.; Billingham, N. C.; Armes, S. P . Latex syntheses using novel tertiary amine methacrylate-based macromonomers prepared by oxyanionic polymerization . Macromolecules , 1999 . 32 2462 - 2471 . DOI: 10.1021/ma981967e http://doi.org/10.1021/ma981967e .

Yang, H. J.; Xu, J. B.; Pispas, S.; Zhang, G . Hybrid copolymerization of ε -caprolactone and methyl methacrylate . Macromolecules , 2012 . 45 3312 - 3317 . DOI: 10.1021/ma300291q http://doi.org/10.1021/ma300291q .

Yang, H. J.; Bai, T.; Xue, X. Q.; Huang, W. Y.; Chen, J. H.; Qian, X. L.; Zhang, G. Z.; Jiang, B. B . A versatile strategy for synthesis of hyperbranched polymers with commercially available methacrylate inimer . RSC Adv. , 2015 . 5 60401 - 60408 . DOI: 10.1039/C5RA09851C http://doi.org/10.1039/C5RA09851C .

Yang, H. J.; Bai, T.; Xue, X. Q.; Huang, W. Y.; Chen, J. H.; Qian, X. L.; Zhang, G. Z.; Jiang, B. B . A simple route to vinyl-functionalized hyperbranched polymers: Self-condensing anionic copolymerization of allyl methacrylate and hydroxyethyl methacrylate . Polymer , 2015 . 72 63 - 68 . DOI: 10.1016/j.polymer.2015.06.048 http://doi.org/10.1016/j.polymer.2015.06.048 .

Zhang, Y. T.; Schmitt, M.; Falivene, L.; Caporaso, L.; Cavallo, L.; Chen, E. Y. X . Organocatalytic conjugate-addition polymerization of linear and cyclic acrylic monomers by N -heterocyclic carbenes: Mechanisms of chain initiation, propagation, and termination . J. Am. Chem. Soc. , 2013 . 135 17925 - 17942 . DOI: 10.1021/ja4088677 http://doi.org/10.1021/ja4088677 .

Odian, G. in Principles of Polymerization , 4 th Ed., John Wiley & amp; Sons, Hoboken, NJ, USA, 2004 .

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DOI：10.1007/s10118-019-2228-x

摘要

Abstract

关键词

Keywords

references

Polymerization Mechanism of Methyl Methacrylate Initiated by Ethyl Acetate/t-BuP₄

Polymerization Mechanism of Methyl Methacrylate Initiated by Ethyl Acetate/t-BuP₄