a.Department of Chemical and Biological Engineering, Korea University, Seoul 02841, Republic of Korea
b.Department of Chemical Engineering, Pusan National University, Pusan 46241, Republic of Korea
choe@pusan.ac.kr (Y.C.)
joona@korea.ac.kr (J.B.)
收稿:2021-05-19,
修回:2021-5-29,
录用:2021-5-31,
网络首发:2021-07-23,
纸质出版:2021-10-18
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Moon, J.; Huh, Y.; Kim, S.; Choe, Y.; Bang, J. Reactive core-shell bottlebrush copolymer as highly effective additive for epoxy toughening. Chinese J. Polym. Sci. 2021, 39, 1626–1633
Junsoo Moon, Yoon Huh, Seonghwan Kim, et al. Reactive Core-Shell Bottlebrush Copolymer as Highly Effective Additive for Epoxy Toughening[J]. Chinese Journal of Polymer Science, 2021, 39(12): 1626-1633.
Moon, J.; Huh, Y.; Kim, S.; Choe, Y.; Bang, J. Reactive core-shell bottlebrush copolymer as highly effective additive for epoxy toughening. Chinese J. Polym. Sci. 2021, 39, 1626–1633 DOI: 10.1007/s10118-021-2614-z.
Junsoo Moon, Yoon Huh, Seonghwan Kim, et al. Reactive Core-Shell Bottlebrush Copolymer as Highly Effective Additive for Epoxy Toughening[J]. Chinese Journal of Polymer Science, 2021, 39(12): 1626-1633. DOI: 10.1007/s10118-021-2614-z.
Herein
we designed a core-shell structured bottlebrush copolymer (BBP)
which is composed of rubbery poly(butyl acrylate) (PBA) core and an epoxy miscible/reactive poly(glycidyl methacrylate) (PGMA) shell
as an epoxy toughening agent. The PGMA shell allows BBP to be uniformly dispersed within the epoxy matrix and to react with the epoxy groups
while the rubbery PBA block simultaneously induced nanocavitation effect
leading to improvement of mechanical properties of the epoxy resin. The mechanical properties were measured by the adhesion performance test
and the tensile and fracture test using universal testing machine. When BBP additives were added to the epoxy resin
a significant improvement in the adhesion strength (2-fold increase) and fracture toughness (2-fold increase in
K
Ic
and 5-fold increase in
G
Ic
) compared to the neat epoxy was observed. In contrast
linear additives exhibited a decrease in adhesion strength and no improvement of fracture toughness over the neat epoxy. Such a difference in mechanical performance was investigated by comparing the morphologies and fracture surfaces of the epoxy resins containing linear and BBP additives
confirming that the nanocavitation effect and void formation play a key role in strengthening the BBP-modified epoxy resins.
Dillard, D. A. Advances in structural adhesive bonding . Elsevier: 2010 .
Hartshorn, S. R. Structural adhesives : chemistry and technology . Springer Science & amp; Business Media: 2012 .
Kinloch, A . Toughening epoxy adhesives to meet today's challenges . MRS Bull. , 2003 . 28 445 - 448 . DOI: 10.1557/mrs2003.126 http://doi.org/10.1557/mrs2003.126 .
Marques, J.; Barbosa, A.; da Silva, C.; Carbas, R.; da Silva, L . An overview of manufacturing functionally graded adhesives–Challenges and prospects . J. Adhes. , 2021 . 97 172 - 206 . DOI: 10.1080/00218464.2019.1646647 http://doi.org/10.1080/00218464.2019.1646647 .
Schmidt, R. G.; Bell, J. P. Epoxy adhesion to metals . Springer: 1986 Vol. 75, p 33−71.
Marouf, B. T.; Mai, Y. W.; Bagheri, R.; Pearson, R. A . Toughening of epoxy nanocomposites: nano and hybrid effects . Polym. Rev. , 2016 . 56 70 - 112 . DOI: 10.1080/15583724.2015.1086368 http://doi.org/10.1080/15583724.2015.1086368 .
Bagheri, R.; Marouf, B.; Pearson, R . Rubber-toughened epoxies: a critical review . Polym. Rev. , 2009 . 49 201 - 225 . DOI: 10.1080/15583720903048227 http://doi.org/10.1080/15583720903048227 .
Pruksawan, S.; Samitsu, S.; Fujii, Y.; Torikai, N.; Naito, M . Toughening effect of rodlike cellulose nanocrystals in epoxy adhesive . ACS Appl. Polym. Mater. , 2020 . 2 1234 - 1243 . DOI: 10.1021/acsapm.9b01102 http://doi.org/10.1021/acsapm.9b01102 .
Unnikrishnan, K.; Thachil, E. T . Toughening of epoxy resins . Des. Monomers Polym. , 2006 . 9 129 - 152 . DOI: 10.1163/156855506776382664 http://doi.org/10.1163/156855506776382664 .
Hsieh, T.; Kinloch, A.; Masania, K.; Lee, J. S.; Taylor, A.; Sprenger, S . The toughness of epoxy polymers and fibre composites modified with rubber microparticles and silica nanoparticles . J. Mater. Sci , 2010 . 45 1193 - 1210 . DOI: 10.1007/s10853-009-4064-9 http://doi.org/10.1007/s10853-009-4064-9 .
Liu, X. F.; Luo, X.; Liu, B. W.; Zhong, H. Y.; Guo, D. M.; Yang, R.; Chen, L.; Wang, Y. Z . Toughening epoxy resin using a liquid crystalline elastomer for versatile application . ACS Appl. Polym. Mater. , 2019 . 1 2291 - 2301 . DOI: 10.1021/acsapm.9b00319 http://doi.org/10.1021/acsapm.9b00319 .
Huang, Y.; Liu, W.; Jiang, Q.; Wei, Y.; Qiu, Y . Interlaminar fracture toughness of carbon-fiber-reinforced epoxy composites toughened by poly (phenylene oxide) particles . ACS Appl. Polym. Mater. , 2020 . 2 3114 - 3121 . DOI: 10.1021/acsapm.0c00285 http://doi.org/10.1021/acsapm.0c00285 .
Kinloch, A.; Shaw, S.; Tod, D.; Hunston, D . Deformation and fracture behaviour of a rubber-toughened epoxy: 1 . Microstructure and fracture studies. Polymer , 1983 . 24 1341 - 1354 . .
Sue, H. J . Study of rubber-modified brittle epoxy systems. Part II: Toughening mechanisms under mode-I fracture . Polym. Eng. Sci. , 1991 . 31 275 - 288 . .
Chen, T. K.; Jan, Y. H . Toughening mechanism for a rubber-toughened epoxy resin with rubber/matrix interfacial modification . J. Mater. Sci , 1991 . 26 5848 - 5858 . DOI: 10.1007/BF01130124 http://doi.org/10.1007/BF01130124 .
Dompas, D.; Groeninckx, G . Toughening behaviour of rubber-modified thermoplastic polymers involving very small rubber particles: 1. A criterion for internal rubber cavitation . Polymer , 1994 . 35 4743 - 4749 . .
Bucknall, C.; Paul, D . Notched impact behavior of polymer blends: Part 1: New model for particle size dependence . Polymer , 2009 . 50 5539 - 5548 . DOI: 10.1016/j.polymer.2009.09.059 http://doi.org/10.1016/j.polymer.2009.09.059 .
Bucknall, C.; Paul, D . Notched impact behaviour of polymer blends: Part 2: Dependence of critical particle size on rubber particle volume fraction . Polymer , 2013 . 54 320 - 329 . DOI: 10.1016/j.polymer.2012.11.019 http://doi.org/10.1016/j.polymer.2012.11.019 .
Lipic, P. M.; Bates, F. S.; Hillmyer, M. A . Nanostructured thermosets from self-assembled amphiphilic block copolymer/epoxy resin mixtures . J. Am. Chem. Soc. , 1998 . 120 8963 - 8970 . DOI: 10.1021/ja981544s http://doi.org/10.1021/ja981544s .
Grubbs, R. B.; Broz, M. E.; Dean, J. M.; Bates, F. S . Selectively epoxidized polyisoprene-polybutadiene block copolymers . Macromolecules , 2000 . 33 2308 - 2310 . DOI: 10.1021/ma992049z http://doi.org/10.1021/ma992049z .
Hillmyer, M. A.; Lipic, P. M.; Hajduk, D. A.; Almdal, K.; Bates, F. S . Self-assembly and polymerization of epoxy resin-amphiphilic block copolymer nanocomposites . J. Am. Chem. Soc. , 1997 . 119 2749 - 2750 . DOI: 10.1021/ja963622m http://doi.org/10.1021/ja963622m .
Grubbs, R. B.; Dean, J. M.; Bates, F. S . Methacrylic block copolymers through metal-mediated living free radical polymerization for modification of thermosetting epoxy . Macromolecules , 2001 . 34 8593 - 8595 . DOI: 10.1021/ma011270k http://doi.org/10.1021/ma011270k .
Pang, V.; Thompson, Z. J.; Joly, G. D.; Bates, F. S.; Francis, L. F . Adhesion strength of block copolymer toughened epoxy on aluminum . ACS Appl. Polym. Mater. , 2019 . 2 464 - 474 . DOI: 10.1021/acsabm.8b00662 http://doi.org/10.1021/acsabm.8b00662 .
Dean, J. M.; Verghese, N. E.; Pham, H. Q.; Bates, F. S . Nanostructure toughened epoxy resins . Macromolecules , 2003 . 36 9267 - 9270 . DOI: 10.1021/ma034807y http://doi.org/10.1021/ma034807y .
Parameswaranpillai, J.; Hameed, N.; Pionteck, J.; Woo, E. M. Handbook of epoxy blends . Springer: 2017 .
Li, T.; Heinzer, M. J.; Redline, E. M.; Zuo, F.; Bates, F. S.; Francis, L. F . Microstructure and performance of block copolymer modified epoxy coatings . Prog. Org. Coat. , 2014 . 77 1145 - 1154 . DOI: 10.1016/j.porgcoat.2014.03.015 http://doi.org/10.1016/j.porgcoat.2014.03.015 .
Thio, Y. S.; Wu, J.; Bates, F. S . Epoxy toughening using low molecular weight poly(hexylene oxide)-poly(ethylene oxide) diblock copolymers . Macromolecules , 2006 . 39 7187 - 7189 . DOI: 10.1021/ma052731v http://doi.org/10.1021/ma052731v .
Declet-Perez, C.; Francis, L. F.; Bates, F. S . Deformation processes in block copolymer toughened epoxies . Macromolecules , 2015 . 48 3672 - 3684 . DOI: 10.1021/acs.macromol.5b00243 http://doi.org/10.1021/acs.macromol.5b00243 .
Liu, J.; Thompson, Z. J.; Sue, H.-J.; Bates, F. S.; Hillmyer, M. A.; Dettloff, M.; Jacob, G.; Verghese, N.; Pham, H . Toughening of epoxies with block copolymer micelles of wormlike morphology . Macromolecules , 2010 . 43 7238 - 7243 . DOI: 10.1021/ma902471g http://doi.org/10.1021/ma902471g .
Wu, J.; Thio, Y. S.; Bates, F. S . Structure and properties of PBO–PEO diblock copolymer modified epoxy . J. Polym. Sci. Pt. B-Polym. Phys. , 2005 . 43 1950 - 1965 . DOI: 10.1002/polb.20488 http://doi.org/10.1002/polb.20488 .
Liu, J. D.; Sue, H.-J.; Thompson, Z. J.; Bates, F. S.; Dettloff, M.; Jacob, G.; Verghese, N.; Pham, H . Strain rate effect on toughening of nano-sized PEP–PEO block copolymer modified epoxy . Acta Mater. , 2009 . 57 2691 - 2701 . DOI: 10.1016/j.actamat.2009.02.023 http://doi.org/10.1016/j.actamat.2009.02.023 .
Qian, J. Y.; Pearson, R. A.; Dimonie, V. L.; El-Aasser, M. S . Synthesis and application of core–shell particles as toughening agents for epoxies . J. Appl. Polym. , 1995 . 58 439 - 448 . DOI: 10.1002/app.1995.070580222 http://doi.org/10.1002/app.1995.070580222 .
Bécu-Longuet, L.; Bonnet, A.; Pichot, C.; Sautereau, H.; Maazouz, A . Epoxy networks toughened by core-shell particles: influence of the particle structure and size on the rheological and mechanical properties . J. Appl. Polym. , 1999 . 72 849 - 858 . DOI: 10.1002/(SICI)1097-4628(19990509)72:6<849::AID-APP10>3.0.CO;2-R http://doi.org/10.1002/(SICI)1097-4628(19990509)72:6<849::AID-APP10>3.0.CO;2-R .
Ning, N.; Liu, W.; Hu, Q.; Zhang, L.; Jiang, Q.; Qiu, Y.; Wei, Y . Impressive epoxy toughening by a structure-engineered core/shell polymer nanoparticle . Compos. Sci. Technol. , 2020 . 199 108364 DOI: 10.1016/j.compscitech.2020.108364 http://doi.org/10.1016/j.compscitech.2020.108364 .
Fröhlich, J.; Kautz, H.; Thomann, R.; Frey, H.; Mülhaupt, R . Reactive core/shell type hyperbranched blockcopolyethers as new liquid rubbers for epoxy toughening . Polymer , 2004 . 45 2155 - 2164 . DOI: 10.1016/j.polymer.2004.01.065 http://doi.org/10.1016/j.polymer.2004.01.065 .
Luo, L.; Meng, Y.; Qiu, T.; Li, X . An epoxy-ended hyperbranched polymer as a new modifier for toughening and reinforcing in epoxy resin . J. Appl. Polym. , 2013 . 130 1064 - 1073 . DOI: 10.1002/app.39257 http://doi.org/10.1002/app.39257 .
Verduzco, R.; Li, X.; Pesek, S. L.; Stein, G. E . Structure, function, self-assembly, and applications of bottlebrush copolymers . Chem. Soc. Rev. , 2015 . 44 2405 - 2420 . DOI: 10.1039/C4CS00329B http://doi.org/10.1039/C4CS00329B .
Huang, K.; Rzayev, J . Well-defined organic nanotubes from multicomponent bottlebrush copolymers . J. Am. Chem. Soc. , 2009 . 131 6880 - 6885 . DOI: 10.1021/ja901936g http://doi.org/10.1021/ja901936g .
Kim, K. H.; Kim, M.; Moon, J.; Huh, J.; Bang, J . Bottlebrush copolymer as surface neutralizer for vertical alignment of block copolymer nanodomains in thin films . ACS Macro Lett. , 2021 . 10 346 - 353 . DOI: 10.1021/acsmacrolett.0c00879 http://doi.org/10.1021/acsmacrolett.0c00879 .
Kawamoto, K.; Zhong, M.; Gadelrab, K. R.; Cheng, L. C.; Ross, C. A.; Alexander-Katz, A.; Johnson, J. A . Graft-through synthesis and assembly of janus bottlebrush polymers from A-branch-B diblock macromonomers . J. Am. Chem. Soc. , 2016 . 138 11501 - 11504 . DOI: 10.1021/jacs.6b07670 http://doi.org/10.1021/jacs.6b07670 .
Vohidov, F.; Milling, L. E.; Chen, Q.; Zhang, W.; Bhagchandani, S.; Nguyen, H. V. T.; Irvine, D. J.; Johnson, J. A . ABC triblock bottlebrush copolymer-based injectable hydrogels: design, synthesis, and application to expanding the therapeutic index of cancer immunochemotherapy . Chem. Sci. , 2020 . 11 5974 - 5986 . DOI: 10.1039/D0SC02611E http://doi.org/10.1039/D0SC02611E .
Johnson, J. A.; Lu, Y. Y.; Burts, A. O.; Lim, Y. H.; Finn, M.; Koberstein, J. T.; Turro, N. J.; Tirrell, D. A.; Grubbs, R. H . Core-clickable PEG-branch-azide bivalent-bottle-brush polymers by ROMP: grafting-through and clicking-to . J. Am. Chem. Soc. , 2011 . 133 559 - 566 . DOI: 10.1021/ja108441d http://doi.org/10.1021/ja108441d .
Sowers, M. A.; McCombs, J. R.; Wang, Y.; Paletta, J. T.; Morton, S. W.; Dreaden, E. C.; Boska, M. D.; Ottaviani, M. F.; Hammond, P. T.; Rajca, A . Redox-responsive branched-bottlebrush polymers for in vivo MRI and fluorescence imaging . Nat. Commun. , 2014 . 5 1 - 9 . .
Choi, J.; Kim, H.; Do, T.; Moon, J.; Choe, Y.; Kim, J. G.; Bang, J . Influence of residual impurities on ring-opening metathesis polymerization after copper (I)-catalyzed alkyne-azide cycloaddition click reaction . J. Polym. Sci., Part A: Polym. Chem. , 2019 . 57 726 - 737 . DOI: 10.1002/pola.29317 http://doi.org/10.1002/pola.29317 .
Radzinski, S. C.; Foster, J. C.; Matson, J. B . Preparation of bottlebrush polymers via a one-pot ring-opening polymerization (ROP) and ring-opening metathesis polymerization (ROMP) grafting-through strategy . Macromol. Rapid Commun. , 2016 . 37 616 - 621 . DOI: 10.1002/marc.201500672 http://doi.org/10.1002/marc.201500672 .
Cho, H. Y.; Krys, P.; Szcześniak, K.; Schroeder, H.; Park, S.; Jurga, S.; Buback, M.; Matyjaszewski, K . Synthesis of poly (OEOMA) using macromonomers via “grafting-through” ATRP . Macromolecules , 2015 . 48 6385 - 6395 . DOI: 10.1021/acs.macromol.5b01592 http://doi.org/10.1021/acs.macromol.5b01592 .
Morandi, G.; Mantovani, G.; Montembault, V.; Haddleton, D. M.; Fontaine, L . Synthesis of graft copolymers from α -oxanorbornenyl macromonomers . New J. Chem. , 2007 . 31 1826 - 1829 . DOI: 10.1039/b705245f http://doi.org/10.1039/b705245f .
Zhou, Q.; Liu, Q.; Song, N.; Yang, J.; Ni, L . Amphiphilic reactive poly (glycidyl methacrylate)-block-poly (dimethyl siloxane)-block-poly (glycidyl methacrylate) triblock copolymer for the controlling nanodomain morphology of epoxy thermosets . Eur. Polym. J. , 2019 . 120 109236 DOI: 10.1016/j.eurpolymj.2019.109236 http://doi.org/10.1016/j.eurpolymj.2019.109236 .
Tang, B.; Kong, M.; Yang, Q.; Huang, Y.; Li, G . Toward simultaneous toughening and reinforcing of trifunctional epoxies by low loading flexible reactive triblock copolymers . RSC Adv. , 2018 . 8 17380 - 17388 . DOI: 10.1039/C8RA01017J http://doi.org/10.1039/C8RA01017J .
Abbasi, M.; Faust, L.; Wilhelm, M . Comb and bottlebrush polymers with superior rheological and mechanical properties . Adv. Mater. , 2019 . 31 1806484 DOI: 10.1002/adma.201806484 http://doi.org/10.1002/adma.201806484 .
Tao, P.; Viswanath, A.; Li, Y.; Siegel, R. W.; Benicewicz, B. C.; Schadler, L. S . Bulk transparent epoxy nanocomposites filled with poly (glycidyl methacrylate) brush-grafted TiO 2 nanoparticles . Polymer , 2013 . 54 1639 - 1646 . DOI: 10.1016/j.polymer.2013.01.032 http://doi.org/10.1016/j.polymer.2013.01.032 .
Naguib, M.; Grassini, S.; Sangermano, M . Core/shell PBA/PMMA-PGMA nanoparticles to enhance the impact resistance of UV-cured epoxy systems . Macromol. Mater. Eng. , 2013 . 298 106 - 112 . DOI: 10.1002/mame.201200001 http://doi.org/10.1002/mame.201200001 .
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