Article Open Access

Transparent, Hydrolysable and Flame Retarded Bio-based Epoxy Resins via Catalyst-free Polymerization of Triglycidyl Isocyanurate and Aliphatic Diacids

Sustainable Polymer & Energy. 2023, 1(2), 10008; https://doi.org/10.35534/spe.2023.10008
Tianlong Ma 1,    Donglin Tang 1, 2, *   
1
Department of Polymer Materials Science Engineering, South China University of Technology, Guangzhou 510640, China
2
Guangdong Provincial Key Laboratory of Luminescence from Molecular Aggregates, South China University of Technology, Guangzhou 510640, China
*
Authors to whom correspondence should be addressed.

Received: 24 Mar 2023    Accepted: 26 May 2023    Published: 01 Jun 2023   

Abstract

In this study, transparent and hydrolysable intrinsic flame retarded epoxy resins were synthesized successfully by melting polymerization without any catalyst, simply from bio-based triglycidyl isocyanurate and aliphatic diacids. Due to the possibility of transesterification along with the ring-opening reaction, the most suitable feed ratio of [COOH]/[epoxy] is found to be 60%. By changing the carbon number of diacid from 8 to 12, ER08-60, ER10-60 and ER12-60 were synthesized. The flame retardancy of ER08-60 is found to be excellent, with a UL-94 rating at V-0 and a LOI value at 27.6%. It is revealed from this study that upon heating isocyanurate ring decomposes first and CO2 released prevents the contact of materials with oxygen, thus preventing further combustion. The tensile strength and bending strength of ER08-60 can reach 86.6 MPa and 75.4 MPa, respectively. Additionally, all epoxy resins are able to hydrolyze quickly in both acid and alkaline solutions. It is worth to mention that these epoxy resins are transparent, with a transmittance of around 85%.

References

1.
Auvergne R, Caillol S, David G, Boutevin B, Pascault JP. Biobased thermosetting epoxy: present and future.  Chem. Rev. 2014, 114, 1082–1115. [Google Scholar]
2.
Domun N, Hadavinia H, Zhang T, Sainsbury T, Liaghat GH, Vahid S. Improving the fracture toughness and the strength of epoxy using nanomaterials-a review of the current status.  Nanoscale 2015, 7, 10294–10329. [Google Scholar]
3.
Chen L, Chai S, Liu K, Ning N, Gao J, Liu Q, et al. Enhanced epoxy/silica composites mechanical properties by introducing graphene oxide to the interface.  ACS Appl. Mater. Interfaces 2012, 4, 4398–4404. [Google Scholar]
4.
Zhang W, Huang J, Guo X, Zhang W, Qian L, Qin Z. Double organic groups-containing polyhedral oligomeric silsesquioxane filled epoxy with enhanced fire safety.  J. Appl. Polym. Sci. 2022, 139, e52461. [Google Scholar]
5.
Yang Q, Jia Y, Zhou X, Zhang H. Mechanically reinforced flame-retardant epoxy resins by layered double hydroxide in situ decorated carbon nanotubes.  ACS Appl. Polym. Mater. 2022, 4, 6731–6741. [Google Scholar]
6.
Wan J, Zhao J, Zhang X, Fan H, Zhang J, Hu D, et al. Epoxy thermosets and materials derived from bio-based monomeric phenols: Transformations and performances.  Prog. Polym. Sci. 2020, 108, 101287. [Google Scholar]
7.
Wang X, Guo W, Song L, Hu Y. Intrinsically flame retardant bio-based epoxy thermosets: A review.  Compos. Part B Eng. 2019, 179, 107487. [Google Scholar]
8.
Rad ER, Vahabi H, de Anda AR, Saeb MR, Thomas S. Bio-epoxy resins with inherent flame retardancy.  Prog. Org. Coat. 2019, 135, 608–612. [Google Scholar]
9.
Kamjornsupamitr T, Hunt AJ, Supanchaiyamat N. Development of hyperbranched crosslinkers from bio-derived platform molecules for the synthesis of epoxidised soybean oil based thermosets. RSC Adv. 2018, 8, 37267–37276. [Google Scholar]
10.
Tellers J, Willems P, Tjeerdsma B, Guigo N, Sbirrazzuoli N. Eutectic hardener from food-based chemicals to obtain fully bio-based and durable thermosets.  Green Chem. 2020, 22, 3104–3110. [Google Scholar]
11.
Lu Y, Zhang Y, Zhang K. Renewable biomass resources to access halogen- and phosphorus-free flame retardant thermosets with ultra-low heat release capacity.  Chem. Eng. J. 2022, 448, 137670. [Google Scholar]
12.
Bhakare MA, Lokhande KD, Bondarde MP, Dhumal PS, Some S. Dual functions of bioinspired, water-based, reusable composite as a highly efficient flame retardant and strong adhesive.  Chem. Eng. J. 2023, 454, 140421. [Google Scholar]
13.
Ménard R, Negrell C, Fache M, Ferry L, Sonnier R, David G. From a bio-based phosphorus-containing epoxy monomer to fully bio-based flame-retardant thermosets.  RSC Adv. 2015, 5, 70856–70867. [Google Scholar]
14.
Wu Q, Xiao L, Chen J, Peng Z. Facile fabrication of high-performance epoxy systems with superior mechanical properties, flame retardancy, and smoke suppression.  J. Appl. Polym. Sci. 2022, 140, e53480. [Google Scholar]
15.
Wang S, Ma S, Xu C, Liu Y, Dai J, Wang Z, et al. Vanillin-derived high-performance flame retardant epoxy resins: facile synthesis and properties.  Macromolecules 2017, 50, 1892–1901. [Google Scholar]
16.
Qi Y, Weng Z, Kou Y, Song L, Li J, Wang J, et al. Synthesize and introduce bio-based aromatic s-triazine in epoxy resin: enabling extremely high thermal stability, mechanical properties, and flame retardancy to achieve high-performance sustainable polymers.  Chem. Eng. J. 2021, 406, 126881. [Google Scholar]
17.
Shao Z, Wang H, Li M, Chen T, Xu Y, Yuan C, et al. Effect of functionalized graphene oxide with phosphaphenanthrene and isocyanurate on flammability, mechanical properties, and thermal stability of epoxy composites.  J. Appl. Polym. Sci. 2019, 137, 48761. [Google Scholar]
18.
Hou R, Zhang Z, Zhang G, Tang D. Synthesis and properties of thermoplastic polyisocyanurates: polyisocyanuratoamide, polyisocyanurato(ester-amide) and polyisocyanurato(urea-ester).  J. Renew. Mater. 2020, 8, 397–403. [Google Scholar]
19.
Chen Z, Hou R, Cheng J, Fang F, Tang D, Zhang G. Polyisocyanuratoesters: renewable linear polyesters with high flame retardancy.  J. Renew. Mater. 2018, 6, 584–590. [Google Scholar]
20.
Hou B, Zhang W, Lu H, Song K, Geng Z, Ye X, et al. Multielement Flame-Retardant System Constructed with Metal POSS-Organic Frameworks for Epoxy Resin.  ACS Appl. Mater. Interfaces 2022, 14, 49326–49337. [Google Scholar]
21.
Yuan ZG, Shu ZH, Qi L, Cai WA, Liu WB, Wang J, et al. Curing behavior, mechanical, and flame‐retardant properties of epoxy‐based composites filled by expandable graphite and ammonium polyphosphate.  J. Appl. Polymer Sci. 2022, 140, e53267. [Google Scholar]
22.
Qi Y, Weng Z, Zhang K, Wang J, Zhang S, Liu C, et al. Magnolol-based bio-epoxy resin with acceptable glass transition temperature, processability and flame retardancy.  Chem. Eng. J. 2020, 387, 124115. [Google Scholar]
23.
Liu G, Gao S. Synergistic effect between aluminum hypophosphite and a new intumescent flame retardant system in poly(lactic acid).  J. Appl. Polymer Sci. 2018, 135, 46359. [Google Scholar]
24.
Wang X, Hu Y, Song L, Xing W, Lu H. Preparation, flame retardancy, and thermal degradation of epoxy thermosets modified with phosphorous/nitrogen-containing glycidyl derivative.  Polymers Adv. Technol. 2012, 23, 190–197. [Google Scholar]
25.
Wu K, Kandola BK, Kandare E, Hu Y. Flame retardant effect of polyhedral oligomeric silsesquioxane and triglycidyl isocyanurate on glass fibre-reinforced epoxy composites.  Polymer Composites 2011, 32, 378–389. [Google Scholar]
26.
Abdullayev Y, Javadova V, Valiyev I, Talybov A, Salmanov C, Autschbach J. Ionic Liquid-Mediated Urea Pyrolysis to Cyanuric Acid: Experimental Protocol and Mechanistic Insights.  Ind. Eng. Chem. Res. 2022, 61, 15076–15084. [Google Scholar]
27.
Ding C, Shuttleworth PS, Makin S, Clark JH, Matharu AS.  New insights into the curing of epoxidized linseed oil with dicarboxylic acids.  Green Chem. 2015, 17, 4000–4008. [Google Scholar]
28.
Liu H, Wu X, Liu Y, Guo Z, Ge Q, Sun Z. The curing characteristics and properties of bisphenol A epoxy resin/maleopimaric acid curing system.  J. Mater. Res. Technol. 2022, 21, 1655–1665. [Google Scholar]
29.
Schwaiger M, Resch-Fauster K. Mechanical flexible epoxy resins with 100% bio‐based carbon content based on epoxidized vegetable oils.  J. Appl. Polymer Sci. 2022, 139, e53233. [Google Scholar]
30.
Li A, Li K. Pressure-Sensitive Adhesives Based on Epoxidized Soybean Oil and Dicarboxylic Acids.  ACS Sustain. Chem. Eng. 2014, 2, 2090–2096. [Google Scholar]
31.
Li S, Ren J, Yuan H, Yu T, Yuan W. Influence of ammonium polyphosphate on the flame retardancy and mechanical properties of ramie fiber-reinforced poly(lactic acid) biocomposites.  Polymer Int. 2010, 59, 242–248. [Google Scholar]
32.
Eroğlu M. Characterization of the network structure of hydroxyl terminated poly(butadiene) elastomers prepared by different reactive systems.  J. Appl. Polymer Sci. 1998, 70, 1129–1135.. [Google Scholar]
33.
Aprem A, Joseph K, Thomas S. Studies on double networks in natural rubber vulcanizates.  J. Appl. Polymer Sci. 2004, 91, 1068–1076. [Google Scholar]
Creative Commons

© 2024 by the authors; licensee SCIEPublish, SCISCAN co. Ltd. This article is an open access article distributed under the CC BY license (https://creativecommons.org/licenses/by/4.0/).