Development of Inherently Flame—Retardant Phosphorylated PLA by Combination of Ring-Opening Polymerization and Reactive Extrusion
Abstract
:1. Introduction
2. Materials and Methods
2.1. Materials
2.2. Syntheses
2.3. Methods
3. Results
3.1. DOPO-Diamine Initiator Preparation and Characterizations
3.2. Synthesis and Properties of DOPO-PLA Oligomers
3.3. Synthesis and Properties of DOPO-PLA-PU by Chain Extension
4. Conclusions
Author Contributions
Funding
Conflicts of Interest
References
- Kuczynski, J.; Boday, D.J. Bio-based materials for high-end electronics applications. Int. J. Sustain. Dev. World 2012, 19, 557–563. [Google Scholar] [CrossRef]
- Wertz, J.T.; Mauldin, T.C.; Boday, D.J. Polylactic acid with improved heat deflection temperatures and self-healing properties for durable goods applications. Appl. Mater. Interfaces 2014, 6, 18511–18516. [Google Scholar] [CrossRef] [PubMed]
- Costes, L.; Laoutid, F.; Dumazert, L.; Lopez-cuesta, J.-M.; Brohez, S.; Delvosalle, C.; Dubois, P. Metallic phytates as efficient bio-based phosphorous flame retardant additives for poly (lactic acid). Polym. Degrad. Stab. 2015, 119, 217–227. [Google Scholar] [CrossRef]
- Wei, L.-L.; Wang, D.-Y.; Chen, H.-B.; Chen, L.; Wang, X.-L.; Wang, Y.-Z. Effect of a phosphorus-containing flame retardant on the thermal properties and ease of ignition of poly (lactic acid). Polym. Degrad. Stab. 2011, 96, 1557–1561. [Google Scholar] [CrossRef]
- Tang, G.; Wang, X.; Zhang, R.; Wang, B.B.; Hong, N.N.; Hu, Y.; Song, L.; Gong, X. Effect of rare earth hypophosphite salts on the fire performance of biobased polylactide composites. Ind. Eng. Chem. Res. 2013, 52, 7362–7372. [Google Scholar] [CrossRef] [Green Version]
- Cayla, A.; Rault, F.; Giraud, S.; Salaün, F.; Fierro, V.; Celzard, A. PLA with Intumescent System Containing Lignin and Ammonium Polyphosphate for Flame Retardant Textile. Polymers 2016, 8, 331. [Google Scholar] [CrossRef] [Green Version]
- Réti, C.; Casetta, M.; Duquesne, S.; Bourbigot, S.; Delobel, R. Flammability properties of intumescent PLA including starch and lignin. Polym. Adv. Technol. 2008, 19, 628–635. [Google Scholar] [CrossRef]
- Murariu, M.; Bonnaud, L.; Paint, Y.; Fontaine, G.; Bourbigot, S.; Dubois, P. New trends in polylactide (PLA)-based materials: “Green” PLA-Calcium sulfate (nano)composites tailored with flame retardant properties. Polym. Degrad. Stab. 2010, 95, 374–381. [Google Scholar] [CrossRef]
- Laoutid, F.; Bonnaud, L.; Alexandre, M.; Lopez-Cuesta, J.-M.; Dubois, P. New prospects in flame retardant polymer materials: From fundamentals to nanocomposites. Mater. Sci. Eng. R Rep. 2009, 63, 100–125. [Google Scholar] [CrossRef]
- Costes, L.; Laoutid, F.; Aguedo, M.; Richel, A.; Brohez, S.; Delvosalle, C.; Dubois, P. Phosphorus and nitrogen derivatization as efficient route for improvement of lignin flame retardant action in PLA. Eur. Polym. J. 2016, 84, 652–667. [Google Scholar] [CrossRef]
- Costes, L.; Laoutid, F.; Brohez, S.; Delvosalle, C.; Dubois, P. Phytic acid–lignin combination: A simple and efficient route for enhancing thermal and flame-retardant properties of polylactide. Eur. Polym. J. 2017, 94, 270–285. [Google Scholar] [CrossRef]
- Prieur, B.; Meub, M.; Wittemann, M.; Klein, R.; Bellayer, S.; Fontaine, G.; Bourbigot, S. Phosphorylation of lignin to flame retard acrylonitrile butadiene styrene (ABS). Polym. Degrad. Stab. 2016, 127, 32–43. [Google Scholar] [CrossRef]
- Chollet, B.; Lopez-Cuesta, J.M.; Laoutid, F.; Ferry, L. Lignin Nanoparticles as a Promising Way for Enhancing Lignin Flame Retardant Effect in Polylactide. Materials 2019, 12, 2132. [Google Scholar] [CrossRef] [PubMed] [Green Version]
- Costes, L.; Laoutid, F.; Khelifa, F.; Rose, G.; Brohez, S.; Delvosalle, C.; Dubois, P. Cellulose/phosphorus combinations for sustainable fire retarded polylactide. Eur. Polym. J. 2016, 74, 218–228. [Google Scholar] [CrossRef]
- Fox, D.M.; Novy, M.; Brown, K.; Zammarano, M.; Harris, R.H., Jr.; Murariu, M.; Carthy, E.D.M.; Seppala, J.E.; Gilman, W.J. Flame retarded poly (lactic acid) using POSS-modified cellulose. 2. Effects of intumescing flame retardant formulations on polymer degradation and composite physical properties. Polym. Degrad. Stab. 2014, 106, 54–62. [Google Scholar] [CrossRef]
- Laoutid, F.; Vahabi, H.; Shabanian, M.; Aryanasab, F.; Zarrintaj, P.; Saeb, M.R. A new direction in design of bio-based flame retardants for poly (lactic acid). Fire Mater. 2018, 42, 914–924. [Google Scholar] [CrossRef]
- Laoutid, F.; Karaseva, V.; Costes, L.; Brohez, S.; Mincheva, R.; Dubois, P. Novel bio-based flame retardant systems derived from tannic acid. J. Renew. Mater. 2018, 6, 559–572. [Google Scholar] [CrossRef] [Green Version]
- De-Yi, W.; Yan-Peng, S.; Ling, L.; Xiu-Li, W.; Yu-Zhong, W. A novel phosphorus-containing poly (lactic acid) toward its flame retardation. Polymer 2011, 52, 233–238. [Google Scholar]
- Schartel, B. Phosphorus-based flame retardancy mechanisms—old hat or a starting point for future development? Materials 2010, 3, 4710–4745. [Google Scholar] [CrossRef] [Green Version]
- Wu, C.S.; Liu, Y.L.; Chiu, Y.-S. Synthesis and characterization of new organosoluble polyaspartimides containing phosphorous. Polymer 2002, 43, 1773–1779. [Google Scholar] [CrossRef]
- Kowalski, A.; Libiszowski, J.; Biela, T.; Cypryk, M.; Duba, A.; Penczek, S. Kinetics and Mechanism of Cyclic Esters Polymerization Initiated with Tin(II) Octoate. Polymerization of ε-Caprolactone and L, L-Lactide Co-initiated with Primary Amines. Macromolecules 2005, 38, 8170–8176. [Google Scholar] [CrossRef]
- Trollsås, M.; Hedrick, J.L.; Mecerreyes, D.; Dubois, P.; Jérôme, R.; Ihre, H.; Hult, A. Highly Functional Branched and Dendri-Graft Aliphatic Polyesters through Ring Opening Polymerization. Macromolecules 1998, 31, 2756–2763. [Google Scholar] [CrossRef]
- Trathnigg, B.; Yan, X. Copolymer Analysis by SEC with Dual Detection. Coupling of Density Detection with UV and RI Detection. Chrornatographia 1992, 33, 467–468. [Google Scholar] [CrossRef]
- Zhao, Y.L.; Cai, Q.; Jiang, J.; Shuai, X.T.; Bei, J.Z.; Chen, C.F.; Xi, F. Synthesis and thermal properties of novel star-shaped poly (L-lactide) s with starburst PAMAM–OH dendrimer macroinitiator. Polymer 2002, 43, 5819–5825. [Google Scholar] [CrossRef]
- Shaver, M.P.; Cameron, D.J.A. Tacticity control in the synthesis of poly (lactic acid) polymer stars with dipentaerythritol cores. Biomacromolecules 2010, 11, 3673–3679. [Google Scholar] [CrossRef] [PubMed] [Green Version]
- Palacio, J.; Orozco, V.H.; López, B.L. Effect of the molecular weight on the physicochemical properties of poly (lactic acid) nanoparticles and on the amount of ovalbumin adsorption. J. Braz. Chem. Soc. 2011, 22, 2304–2311. [Google Scholar] [CrossRef] [Green Version]
- Michell, R.M.; Müller, A.J.; Boschetti-de-Fierro, A.; Fierro, D.; Lison, V.; Raquez, J.-M.; Dubois, P. Novel poly (ester-urethane)s based on polylactide: From reactive extrusion to crystallization and thermal properties. Polymer 2012, 53, 5657–5665. [Google Scholar] [CrossRef]
- Kucharczyk, P.; Pavelkova, A.; Stloukal, P.; Sedlarík, V. Degradation behaviour of PLA-based polyesterurethanes under abiotic and biotic environments. Polym. Degra. Stab. 2016, 129, 222–230. [Google Scholar] [CrossRef] [Green Version]
- Schäfer, A.; Seibold, S.; Lohstroh, W.; Walter, O.; Döring, M.J. Synthesis and properties of flame-retardant epoxy resins based on DOPO and one of its analog DPPO. Appl. Polym. Sci. 2007, 105, 685–696. [Google Scholar] [CrossRef]
- Hao, X.; Kaschta, J.; Hu, X.; Pan, L.Y.; Schubert, D.W. Entanglement network formed in miscible PLA/PMMA blends and its role in rheological and thermo-mechanical properties of the blends. Polymer 2015, 80, 38. [Google Scholar] [CrossRef]
Sample | T5% (°C) | Tmax (°C) | Residue at 700 °C (%) |
---|---|---|---|
PLA | 337 | 374 | 0.4 |
DOPO-PLA | 241 | 267; 338 | 8.5 |
DOPO-PLA-PU | 228 | 265 | 10.4 |
50% DOPO-PLA-PU/50% PLA | 218 | 255 | 5 |
Sample | Tg (°C) | Tm (°C) | ∆Hm (J/g) |
---|---|---|---|
PLA | 60 | 154 | 2 |
DOPO-PLA-PU | 60.5 | – | – |
50% DOPO-PLA-PU/50% PLA | 50.5 | 150 | 3 |
Sample | TTI (s) | pHRR (kW/m2) | pHRR Reduction (%) | THR (MJ/m2) | THR Reduction (%) | UL-94 Classification |
---|---|---|---|---|---|---|
PLA | 40 | 580 | – | 54 | – | No rating |
PLA/10 wt.% DOPO-diamine | 42 | 620 | No reduction | 61.7 | No reduction | No rating |
PLA/20 wt.% DOPO-diamine | 34 | 520 | No reduction | 51 | No reduction | No rating |
DOPO-PLA-PU | 16 | 380 | 35 | 34.5 | –36 | V0 |
© 2019 by the authors. Licensee MDPI, Basel, Switzerland. This article is an open access article distributed under the terms and conditions of the Creative Commons Attribution (CC BY) license (http://creativecommons.org/licenses/by/4.0/).
Share and Cite
Mincheva, R.; Guemiza, H.; Hidan, C.; Moins, S.; Coulembier, O.; Dubois, P.; Laoutid, F. Development of Inherently Flame—Retardant Phosphorylated PLA by Combination of Ring-Opening Polymerization and Reactive Extrusion. Materials 2020, 13, 13. https://doi.org/10.3390/ma13010013
Mincheva R, Guemiza H, Hidan C, Moins S, Coulembier O, Dubois P, Laoutid F. Development of Inherently Flame—Retardant Phosphorylated PLA by Combination of Ring-Opening Polymerization and Reactive Extrusion. Materials. 2020; 13(1):13. https://doi.org/10.3390/ma13010013
Chicago/Turabian StyleMincheva, Rosica, Hazar Guemiza, Chaimaa Hidan, Sébastien Moins, Olivier Coulembier, Philippe Dubois, and Fouad Laoutid. 2020. "Development of Inherently Flame—Retardant Phosphorylated PLA by Combination of Ring-Opening Polymerization and Reactive Extrusion" Materials 13, no. 1: 13. https://doi.org/10.3390/ma13010013