Abstract
The emergence of vitrimer, a new class of polymer materials can address the problem of recyclability, reprocess ability and recyclability of thermosetting plastics. Rosin, a natural product, is an ideal raw material for the preparation of polymers in a more sustainable way. Nevertheless, due to the huge steric hindrance caused by the hydrogenated phenanthrene ring structure, the cross-link density of materials is frequently lowered. In this study, hydrogenated rosin was adopted for preparing hydrogenated rosin side-chain type diacids, which were reacted with mixed epoxy to obtain rosin side-chain type vitrimers. It was completely characterized by differential scanning calorimetry test, thermogravimetric analysis, shape memory test and self-healing test. The prepared vitrimers exhibited good self-healing properties, excellent heat resistance (Td = 352 °C) as well as high mechanical properties (tensile strength of 46.75 MPa). The tricyclic diterpene structure of rosin was introduced into the side chain in order to avoid the reduction of cross-link density resulting from the huge steric hindrance of the rigid tricyclic hydrophenylene skeleton. Vitrimers can undergo dynamic transesterification reaction without external catalysts due to the autocatalytic effect of tertiary amines from epoxy. Moreover, our work expanded the application field of rosin, increased the added value of rosin, and provided a novel method for preparing rosin-based vitrimers with ideal properties.
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References
Hirano K, Asami M. Phenolic resins-100 years of progress and their future. Reactive & Functional Polymers, 2013, 73(2): 256–269
Zheng J, Png Z M, Ng S H, Tham G X, Ye E, Goh S S, Loh X J, Li Z. Vitrimers: current research trends and their emerging applications. Materials Today, 2021, 51: 586–625
Chakma P, Konkolewicz D. Dynamic covalent bonds in polymeric materials. Angewandte Chemie International Edition, 2019, 58(29): 9682–9695
Montarnal D, Capelot M, Tournilhac F, Leibler L. Silica-like malleable materials from permanent organic networks. Science, 2011, 334(6058): 965–968
Porath L E, Evans C M. Importance of broad temperature windows and multiple rheological approaches for probing viscoelasticity and entropic elasticity in vitrimers. Macromolecules, 2021, 54(10): 4782–4791
Meng F, Saed M O, Terentjev E M. Elasticity and relaxation in full and partial vitrimer networks. Macromolecules, 2019, 52(19): 7423–7429
Lessard J J, Scheutz G M, Sung S H, Lantz K A, Epps T H III, Sumerlin B S. Block copolymer vitrimers. Journal of the American Chemical Society, 2020, 142(1): 283–289
Ling F, Liu Z, Chen M, Wang H, Zhu Y, Ma C, Wu J, Huang G. Compatibility driven self-strengthening during the radical-responsive remolding process of poly-isoprene vitrimers. Journal of Materials Chemistry A: Materials for Energy and Sustainability, 2019, 7(44): 25324–25332
Yu K, Xin A, Wang Q. Mechanics of self-healing polymer networks crosslinked by dynamic bonds. Journal of the Mechanics and Physics of Solids, 2018, 121: 409–431
Yu L, Zhu C, Sun X, Salter J, Wu H, Jin Y, Zhang W, Long R. Rapid fabrication of malleable fiber reinforced composites with vitrimer powder. ACS Applied Polymer Materials, 2019, 1(9): 2535–2542
Yang H, He C, Russell T P, Wang D. Epoxy-polyhedral oligomeric silsesquioxanes (POSS) nanocomposite vitrimers with high strength, toughness, and efficient relaxation. Giant, 2020, 4: 100035
Hubbard A M, Ren Y, Konkolewicz D, Sarvestani A, Picu C R, Kedziora G S, Roy A, Varshney V, Nepal D. Vitrimer transition temperature identification: coupling various thermomechanical methodologies. ACS Applied Polymer Materials, 2021, 3(4): 1756–1766
Liu T, Hao C, Shao L, Kuang W, Cosimbescu L, Simmons K L, Zhang J. Carbon fiber reinforced epoxy vitrimer: robust mechanical performance and facile hydrothermal decomposition in pure water. Macromolecular Rapid Communications, 2021, 42(3): e2000458
Kassem S, Adam K, Louis C, Matthew A, Abdulla W, Howard A, Yehuda S. The putative adverse effects of bisphenol A on autoimmune diseases. Endocrine, Metabolic & Immune Disorders Drug Targets, 2021, 21: 2212–3873
Sun H, Liu Z, Liu K, Gibril M E, Kong F, Wang S. Lignin-based superhydrophobic melamine resin sponges and their application in oil/water separation. Industrial Crops and Products, 2021, 170: 113798
Xu C, Qu C, Lu M, Meng U, Chen B, Jiao E, Zhang E, Wu K, Shi J. Effect of modified bamboo lignin replacing part of C5 petroleum resin on properties of polyurethane/polysiloxane pressure-sensitive adhesive and its application on the wood substrate. Journal of Colloid and Interface Science, 2021, 602: 394–405
Zhang Y, Huang R, Yu J, Jiang X. Facile fabrication of sodium carboxymethyl cellulose/reduced graphene oxide composite hydrogel and its application for Pb(II) removal. Micro & Nano Letters, 2020, 16(1): 30–38
Pinheiro J A, Marpues N D N, Villetti M A, Balaban R C. Polymer-decorated cellulose nanocrystals as environmentally friendly additives for olefin-based drilling fluids. International Journal of Molecular Sciences, 2020, 22(1): 352
Shipra J, Tamanna T, Bharti G. Rosin-modified o-cresol novolac based vinyl ester thermosets containing methacrylated lignin model compounds: synthesis, curing and thermo-mechanical analysis. Journal of Polymer Research, 2021, 28(4): 111
Zhu E Q, Xu G F, Sun S, Yang J, Yang H Y, Wang D W, Guo Z H, Shi Z J, Deng J. Rosin acid modification of bamboo powder and thermoplasticity of its products based on hydrothermal pretreatment. Advanced Composites and Hybrid Materials, 2021, 4(3): 584–590
Ossei-Bremang R N, Kemausuor F. A decision support system for the selection of sustainable biomass resources for bioenergy production. Environment Systems & Decisions, 2021, 41(3): 437–454
Yang L, Wang X, Dai M, Chen B, Qiao Y, Deng H, Zhang D, Zhang Y, Almeida C M V. Shifting from fossil-based economy to bio-based economy: status quo, challenges, and prospects. Energy, 2021, 228: 7411
Hao C, Liu T, Zhang S, Liu W, Shan Y, Zhang J. Triethanolamine-mediated covalent adaptable epoxy network: excellent mechanical properties, fast repairing, and easy recycling. Macromolecules, 2020, 53(8): 3110–3118
He C, Shi S, Wang D, Helms B A, Russell T P. Poly(oxime-ester) vitrimers with catalyst-free bond exchange. Journal of the American Chemical Society, 2019, 141(35): 13753–13757
Xu Y, Fu P, Dai S, Zhang H, Bi L, Jiang J, Chen Y. Catalyst-free self-healing fully bio-based vitrimers derived from tung oil: strong mechanical properties, shape memory, and recyclability. Industrial Crops and Products, 2021, 171: 113978
Xu Y, Dai S, Bi L, Jiang J, Zhang H, Chen Y. Catalyst-free self-healing bio-based vitrimer for a recyclable, reprocessable, and self-adhered carbon fiber reinforced composite. Chemical Engineering Journal, 2022, 429: 132518
Song J, Kim H, Jae W, Kim T, Futalan C M, Kim J. Porous ZnO/C microspheres prepared with maleopimaric acid as an anode material for lithium-ion batteries. Carbon, 2020, 165: 55–66
Yan X, Zhai Z, Xu J, Song Z, Shang S, Rao X. Hybrids of CO2-responsive water-redispersible single-walled carbon nanotubes by a surfactant based on natural rosin. ACS Omega, 2019, 4(21): 19478–19482
Xu X, Song Z, Shang S, Cui S, Rao X. Synthesis and properties of novel rosin-based water-borne polyurethane. Polymer International, 2011, 60(10): 1521–1526
Yang X, Guo L, Xu X, Shang S, Liu H. A fully bio-based epoxy vitrimer: self-healing, triple-shape memory and reprocessing triggered by dynamic covalent bond exchange. Materials & Design, 2020, 186: 108248
Altuna F I, Espósito L H, Ruseckaite R A, Stefani P M. Thermal and mechanical properties of anhydride-cured epoxy resins with different contents of biobased epoxidized soybean oil. Journal of Applied Polymer Science, 2011, 120(2): 789–798
Magdalena M, Monika S. The influence of curing systems on the cure characteristics and physical properties of styrene-butadiene elastomer. Materials, 2020, 13(23): 5329
Cheng S, Wojnarowska Z, Musial M, Kolodziej S, Drockenmuller E, Paluch M. Studies on ion dynamics of polymerized ionic liquids through the free volume theory. Polymer, 2021, 212: 123286
Tao Y, Fang L, Dai M, Wang C, Sun J, Fang Q. Sustainable alternative to bisphenol A epoxy resin: high-performance recyclable epoxy vitrimers derived from protocatechuic acid. Polymer Chemistry, 2020, 11(27): 4500–4506
Puspita I, Kurniati M, Winarti C, Maddu A. Cassava waste pulp—poly(acrylamide-acrylic acid) based hydrogels using gamma irradiation. Journal of Physics: Conference Series, 2021, 1912(1): 012017
Shi X, Ge Q, Lu H, Yu K. The nonequilibrium behaviors of covalent adaptable network polymers during the topology transition. Soft Matter, 2021, 17(8): 2104–2119
Reisinger D, Kaiser S, Rossegger E, Alabiso W, Rieger B, Schlogl S. Introduction of photolatent bases for locally controlling dynamic exchange reactions in thermo-activated vitrimers. Angewandte Chemie International Edition, 2021, 60(26): 14302–14306
Capelot M, Unterlass M M, Tournilhac F, Leibler L. Catalytic control of the vitrimer glass transition. ACS Macro Letters, 2012, 1(7): 789–792
Han R, Campbell K P. Dysferlin and muscle membrane repair. Current Opinion in Cell Biology, 2007, 19(4): 409–416
Tan P S, Somashekar A A, Casari P, Bhattacharyya D. Healing efficiency characterization of self-repairing polymer composites based on damage continuum mechanics. Composite Structures, 2019, 208: 367–376
Wang S, Urban M W. Self-healing polymers. Nature Reviews Materials, 2020, 5(8): 562–583
Wei K, Zhu G, Tang Y, Liu T, Xie J. The effects of crosslink density on thermo-mechanical properties of shape-memory hydroepoxy resin. Journal of Materials Research, 2013, 28(20): 2903–2910
Tian G, Zhu G, Xu S, Ren T. An investigation on sunlight-induced shape memory behaviors of PCL/TiN composites film. Smart Materials and Structures, 2019, 28(10): 105006
Teng J, Wang Z, Liu J, Sun X. Thermodynamic and shape memory properties of TPI/HDPE hybrid shape memory polymer. Polymer Testing, 2020, 81(C): 106257
Wang Z, Chang M, Kong F, Yun K. Optimization of thermo-mechanical properties of shape memory polymer composites based on a network model. Chemical Engineering Science, 2019, 207(C): 1017–1029
Wang Y, Zhou L, Wang Z, Huang H, Ye L. Analysis of internal stresses induced by strain recovery in a single SMA fiber-matrix composite. Composites Part B: Engineering, 2011, 42(5): 1135–1143
Shi Q, Yu K, Kuang X, Mu X, Dunn C K, Dunn M L, Wang T, Jerry Qi H. Recyclable 3D printing of vitrimer epoxy. Materials Horizons, 2017, 4(4): 598–607
Acknowledgements
This research was supported by the National Natural Science Foundation of China (Grant No. 32171734) and the Scientific Research Funds of Huaqiao University (Grant No. 20BS201).
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Shen, Y., Tang, W., Li, J. et al. Rosin side chain type catalyst-free vitrimers with high cross-link density, mechanical strength, and thermal stability. Front. Chem. Sci. Eng. 17, 1267–1279 (2023). https://doi.org/10.1007/s11705-022-2291-7
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DOI: https://doi.org/10.1007/s11705-022-2291-7