Abstract
Polyester and polyether are two key oxygenated polymers, and completely alternative sequence of poly(ester-alt-ether) could efficiently combine the advantages (including flexibility, degradability, etc.) of both segments. Currently, despite their copolymers could be synthesized from one-pot mixture of cyclic esters and epoxides, perfectly alternative microstructure is very challenging to realize and typically restricted to certain monomer pairs. Moving forward, synthesizing poly(ester-alt-ether) from commercially available and largescale monomers would be a significant advance. For example, successfully commercialized poly(glycolic acid) (PGA), which is not easily soluble in polymers due to its high crystallinity and is brittle and difficult to control the degradation cycle, would encounter a new paradigm if engineered into poly(ester-alt-ether). In this work, starting from the design of monomer with hybrid structures, we successfully synthesized a series of 1,4-dioxan-2-one containing different substituents based on glycolide (GA) and epoxides using commercially available Salen-Cr(III) and PPNCl catalytic systems. The new monomers underwent ring-opening polymerization (ROP) to form a series of poly(ester-alt-ether) with perfectly alternating glycolic acid and propylene glycol repeat units under catalytic system of thiourea/base. The poly(ester-alt-ether) have significantly lower glass-transition temperature than PGA. Additionally, the poly(ester-alt-ether) can be chemically recovered to monomer using Sn(Oct)2 or 1,8-diazabicyclo[5.4.0]undecane-7-ene (DBU) as a catalyst in solution, thus establishing a closed-loop life cycle. From monomers derived from GA and epoxides, this work furnishes a novel strategy for the synthesis of poly(ester-alt-ether) with chemical recyclability.
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References
Zhu, Y.; Romain, C.; Williams, C. K. Sustainable polymers from renewable resources. Nature 2016, 540, 354–362.
Haussler, M.; Eck, M.; Rothauer, D.; Mecking, S. Cloeed-loop recycling of polyethylene-like materials. Nature 2021, 590, 423–427.
Masutani, K.; Kimura, Y.; Li, S. M.; Hu, Y. F.; Müller, A. J.; Ávila, M.; Saenz, G.; Salazar, J.; Raquez, J. M.; Ramy-Ratiarison, R.; Murariu, M.; Dubois, P.; Ruellan, A.; Ducruet, V.; Domenek, S.; Peponi, L.; Mújica-García, A.; Kenny, J. M.; Bitinis, N.; Verdejo, R.; López-Manchado, M. A.; Lagarón, J. M.; Cabedo, L.; Zhou, Q.; Berglund, L. A.; Catalá, R.; López-Carballo, G.; Hernández-Muñoz, P.; Gavara, R.; Armentano, I.; Fortunati, E.; Mattioli, S.; Rescignano, N.; Fukushima, K.; Camino, G.; Fiori, S.; Peltzer, M. A.; Beltrán-Sanahuja, A. Poly(lactic acid) Science and Technology: Processing, Properties, Additives and Applications. The Royal Society of Chemistry: 2014.
Coulembier, O.; Martin-Vaca, B.; Bourisso, D.; Fastnacht, K. V.; Datta, P. P.; Kiesewetter, M. K.; Naumann, S.; Lecomte, P.; Jérôme, C.; Guillaume, S. M.; Fukushima, K.; Taton, D.; Siefker, D.; Zhang, D. H.; Wolf, T.; Wurm, F. R.; Zhao, W. C.; Zhang, Y. T.; Bossion, A.; Heifferon, K. V.; Zivic, N.; Long, T. E.; Sardon, H.; Ryan, M. D.; Pearson, R. M.; Miyake, G. M.; Jehanno, C.; Demarteau, J.; Dove, A. P. Organic Catalysis for Polymerisation. The Royal Society of Chemistry: 2018.
Li, J.; Stayshich, R. M.; Meyer, T. Y. Exploiting sequence to control the hydrolysis behavior of biodegradable PLGA copolymers. J. Am. Chem. Soc. 2011, 133, 6910–6913.
Lu, Y.; Swisher, J. H.; Meyer, T. Y.; Coates, G. W. Chirality-directed regioselectivity: an approach for the synthesis of alternating poly(lactic-co-glycolic acid). J. Am. Chem. Soc. 2021, 143, 4119–4124.
Diaz, C.; Ebrahimi, T.; Mehrkhodavandi, P. Cationic indium complexes for the copolymerization of functionalized epoxides with cyclic ethers and lactide. Chem. Commun. 2019, 55, 3347–3350.
Chwatko, M.; Lynd, N. A. Statistical copolymerization of epoxides and lactones to high molecular weight. Macromolecules 2017, 50, 2714–2723.
Liu, D.; Bielawski, C. W. Synthesis of degradable poly[(ethylene glycol)-co-(glycolic acid)] via the post-polymerization oxyfunctionalization of poly(ethylene glycol). Macromol. Rapid Commun. 2016, 37, 1587–1592.
Li, Z.; Tan, B. H.; Lin, T.; He, C. Recent advances in stereocomplexation of enantiomeric PLA-based copolymers and applications. Prog. Polym. Sci. 2016, 62, 22–72.
Stosser, T.; Sulley, G. S.; Gregory, G. L.; Williams, C. K. Easy access to oxygenated block polymers via switchable catalysis. Nat. Commun. 2019, 10, 2668.
Ren, W. M.; Wang, R. J.; Ren, B. H.; Gu, G. G.; Yue, T. J. Mechanism-inspired design of heterodinuclear catalysts for copolymerization of epoxide and lactone. Chinese J. Polym. Sci. 2020, 38, 950–957.
Kerr, R. W. F.; Williams, C. K. Zr(IV) Catalyst for the ring-opening copolymerization of anhydrides (A) with epoxides (B), oxetane (B), and tetrahydrofurans (C) to make ABB- and/or ABC-poly(ester-alt-ethers). J. Am. Chem. Soc. 2022, 144, 6882–6893.
Zhang, H.; Hu, S.; Zhao, J.; Zhang, G. Phosphazene-catalyzed alternating copolymerization of dihydrocoumarin and ethylene oxide: weaker is better. Macromolecules 2017, 50, 4198–4205.
Hu, S.; Dai, G.; Zhao, J.; Zhang, G. Ring-opening alternating copolymerization of epoxides and dihydrocoumarin catalyzed by a phosphazene superbase. Macromolecules 2016, 49, 4462–4472.
Jung, H. J.; Goonesinghe, C.; Mehrkhodavandi, P. Temperature triggered alternating copolymerization of epoxides and lactones via pre- sequenced spiroorthoester intermediates. Chem. Sci. 2022, 13, 3713–3718.
Van Zee, N. J.; Coates, G. W. Alternating copolymerization of dihydrocoumarin and epoxides catalyzed by chromium salen complexes: a new route to functional polyesters. Chem. Commun. 2014, 50, 6322–6325.
Ren, W. M.; Gao, H. J.; Yue, T. J. Flexible gradient poly(ether-ester) from the copolymerization of epoxides and ε-approlcctoee mediated by a hetero-bimetallic complex. Chinese J. Polym. Sci. 2021, 39, 1013–1019.
Nishida, H.; Yamashita, M.; Endo, T.; Tokiwa, Y. Equilibrium polymerization behavior of 1,4-dioxan-2-one in bulk. Macromolecules 2000, 33, 6982–6986.
Li, K.; Li, Z.; Duan, S.; Shen, Y.; Li, Z. Organobase/urea catalyzed ring opening polymerization of 3-methyl-1, 4-dioxan-2-one to prepare chemically recyclable poly(ether ester). J. Polym. Sci. 2021, 60, 3331–3340.
MacDonald, J. P.; Shaver, M. P. An aromatic/aliphatic polyester prepared via ring-opening polymerisation and its remarkably selective and cyclable depolymerisation to monomer. Polym. Chem. 2016, 7, 553–559.
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, 2465–2475.
Bechtold, K.; Hillmyer, M. A.; Tolman, W. B. Perfectly alternating copolymer of lactic acid and ethylene oxide as a plasticizing agent for polylactide. Macromolecules. 2021, 34, 8641–8648.
Li, Z.; Shen, Y.; Li, Z. Chemical upcycling of poly(3-hydroxybutyrate) into bicyclic ether-ester monomers toward value-added, degradable, and recyclable poly(ether ester). ACS. Sustainable Chem. Eng. 2022, 10, 8228–8238.
Li, Z.; Zhao, D.; Shen, Y.; Li, Z. Rhg-opening polymerization of enantiopure bicyclic ether-ester monomers toward closed-loop recyclable and crystalline stereoregular polyesters via chemical upcycling of bioplastic. Angew. Chem. Int. Ed. 2023, 22, e202302101.
Xu, J. B.; Chen, Y.; Xiao, W. H.; Zhang, J.; Bu, M. L.; Zhang, X. Q.; Lei, C. H.Studying the ring-opening polymerization of 1,5-dioxepan-2-one with organocatalysts. Polymers 2019, 11, 1642.
Tu, Y. M.; Wang, X. M.; Yang, X.; Fan, H. Z.; Gong, F. L.; Cai, Z. Z.; Zhu, J. B. Biobased high-performance aromatic-aliphatic polyesters with complete recyclability. J. Am. Chem. Soc. 2021, 143, 20591–20597.
Grablowitz, H.; Lendlein, A. Synthesis and characterization of α,ω-dihydroxy-telechelic oligo(p-dioxanone). J. Mater. Chem. 2007, 17, 4050–4056.
Fan, H. Z.; Yang, X.; Wu, Y. C.; Cao, Q.; Cai, Z. Z.; Zhu, J. B. Leveraging the monomer structure for high-performance chemically recyclable semiaromatic polyesters. Polym. Chem. 2023, 14, 747–753.
Hu, S.; Liu, L.; Li, H.; Pahovnik, D.; Hadjichristidis, N.; Zhou, X.; Zhao, J. Tuning the properties of ester-based degradable polymers by inserting epoxides into poly(t-caprolactone). Chem. Asian J. 2023, 18, e202201097.
Hu, S.; Zhao, J.; Zhang, G. Noncopolymerization approach to copolymers via concurrent transesterification and ring-opening reactions. ACS Macro Lett. 2016, 5, 40–44.
Balasanthiran, V.; Chatterjee, C.; Chisholm, M. H.; Harrold, N. D.; RajanBabu, T. V.; Warren, G. A. Coupling of propylene oxide and lactide at a porphyrin chromium(III) center. J. Am. Chem. Soc. 2015, 137, 1786–1789.
Liang, Z. Z.; Li, X.; Hu, C. Y.; Duan, R. L.; Wang, X. H.; Pang, X.; Chen, X. S. Copolymerization of PO/CO2 and lactide by a dinuclear salen-Cr(III) complex: gradient and random copolymers with modificable microstructure. Chinese J. Polym. Sci. 2022, 40, 1028–1033.
Datta, P. P.; Pothupitiya, J. U.; Kiesewetter, E. T.; Kiesewetter, M. K. Coupled equilibria in H-bond donating ring-opening polymerization: The effective catalyst-determined shift of a polymerization equilibrium. Eur. Polym. J. 2017, 95, 671–677.
Kazakov, O. I.; Kiesewetter, M. K. Cocatalyst binding effects in organocatalytic ring-opening polymerization of l-lactide. Macromolecules 2015, 48, 6121–6126.
Spink, S. S.; Kazakov, O. I.; Kiesewetter, E. T.; Kiesewetter, M. K. Rate accelerated organocatalytic ring-opening polymerization of l-lactide via the application of a bis(thiourea) H-bond donating cocatalyst. Macromolecules 2015, 48, 6127–6131.
Hewawasam, R. S.; Kalana, U. L. D. I.; Dharmaratne, N. U.; Wright, T. J.; Bannin, T. J.; Kiesewetter, E. T.; Kiesewetter, M. K. Bisurea and bisthiourea H-bonding organocatalysts for ring-opening polymerization: cues for the catalyst design. Macromolecules 2019, 52, 9232–9237.
Lin, L.; Han, D.; Qin, J.; Wang, S.; Xiao, M.; Sun, L.; Meng, Y. Nonstrained y-butyrolactone to high-molecular-weight poly(γ-butyrolactone): facile bulk polymerization using economical ureas/alkoxides. Macromolecules 2018, 51, 9317–9322.
Dharmaratne, N. U.; Pothupitiya, J. U.; Kiesewetter, M. K. The mechanistic duality of (thio)urea organocatalysts for ring-opening polymerization. Org. Biomol. Chem. 2019, 17, 3305–3313.
Zhang, X.; Jones, G. O.; Hedrick, J. L.; Waymouth, R. M. Fast and selective ring-opening polymerizations by alkoxides and thioureas. Nat. Chem. 2016, 8, 1047–1053.
Coates, G. W.; Getzler, Y. D. Y. L. Chemical recycling to monomer for an ideal, circular polymer economy. Nat. Rev. Mater. 2020, 5, 501–516.
Acknowledgments
This work was financially supported by the National Key R&D Program of China (No. 2021YFA1501700), the Science and Technology Development Plan of Jilin Province (Nos. 20230101042JC and 20210201059GX), the National Natural Science Foundation of China, Basic Science Center Program (No. 51988102), and the National Natural Science Foundation of China (Nos. 52203017 and 52073272).
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Preparation of Chemically Recyclable Poly(ether-alt-ester) by the Ring Opening Polymerization of Cyclic Monomers Synthesized by Coupling Glycolide and Epoxides
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Ren, F., Liang, ZZ., Niu, MX. et al. Preparation of Chemically Recyclable Poly(ether-alt-ester) by the Ring Opening Polymerization of Cyclic Monomers Synthesized by Coupling Glycolide and Epoxides. Chin J Polym Sci 42, 168–175 (2024). https://doi.org/10.1007/s10118-023-3040-1
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DOI: https://doi.org/10.1007/s10118-023-3040-1