New insights into the curing of epoxidized linseed oil with dicarboxylic acids

The effect of systematically increasing chain length of a series of linear α,ω-dicarboxylic acids (DCAs) from C6 to C18 diacids and a cyclic diacid, Pripol 1009F, on thermal and mechanical properties of the resultant epoxy thermosets derived from epoxidized linseed oil (ELO) are reported. Different techniques including differential scanning calorimetry (DSC), solvent extraction, FT-IR, NMR, dynamic mechanical analysis (DMA), tensile tests and thermogravimetric analysis (TGA) are used in this study. The results indicated that the obtained epoxy resins were highly crosslinked polymers with only a small fraction of low molecular weight soluble materials. The glass transition temperature (Tg), tensile strength, Young's modulus, elongation at break and toughness decreased while the thermal stability increased with respect to increasing chain length of DCAs. Interestingly, strain hardening was only observed for adipic acid (C6) sample for which the best mechanical properties observed.

[1]  Loren Isom,et al.  "Green" Chemicals from Renewable Agricultural Biomass - A Mini Review , 2008 .

[2]  Roberto J. J. Williams,et al.  Homopolymerization of epoxy monomers initiated by 4‐(dimethylamino)pyridine , 2006 .

[3]  Yongqian Shi,et al.  Enhanced thermal and flame retardant properties of flame-retardant-wrapped graphene/epoxy resin nanocomposites , 2015 .

[4]  M. Meier,et al.  Plant Oil‐Based Long‐Chain C26 Monomers and Their Polymers , 2012 .

[5]  M. R. Kessler,et al.  Polyurethanes from Solvent-Free Vegetable Oil-Based Polyols , 2014 .

[6]  Joseph J. Bozell,et al.  Chemicals and materials from renewable resources , 2001 .

[7]  Wei Zhang,et al.  Structure and properties of polyurethanes prepared from triglyceride polyols by ozonolysis. , 2005, Biomacromolecules.

[8]  Joseph J. Bozell,et al.  Feedstocks for the future : renewables for the production of chemicals and materials , 2006 .

[9]  S. Erhan,et al.  Ring-Opening Polymerization of Epoxidized Soybean Oil , 2010 .

[10]  Jean-Mathieu Pin,et al.  From epoxidized linseed oil to bioresin: an overall approach of epoxy/anhydride cross-linking. , 2015, ChemSusChem.

[11]  P. Sengupta,et al.  High biobased content epoxy-anhydride thermosets from epoxidized sucrose esters of Fatty acids. , 2011, Biomacromolecules.

[12]  Ludwik Leibler,et al.  Metal-catalyzed transesterification for healing and assembling of thermosets. , 2012, Journal of the American Chemical Society.

[13]  P. Haines,et al.  Principles of Thermal Analysis and Calorimetry , 2002 .

[14]  Nontipa Supanchaiyamat Bio-based thermoset composites from epoxidised linseed oil , 2012 .

[15]  A. Matharu,et al.  Recent Developments on Biobased Curing Agents: A Review of Their Preparation and Use , 2014 .

[16]  Bipin K. Shah,et al.  Biopolymers from vegetable oils via catalyst- and solvent-free "click" chemistry: effects of cross-linking density. , 2012, Biomacromolecules.

[17]  Laurence Lecamp,et al.  A solventless synthesis process of new UV-curable materials based on linseed oil , 2011 .

[18]  Avtar S. Matharu,et al.  Thermosetting resin based on epoxidised linseed oil and bio-derived crosslinker , 2012 .

[19]  Jürgen O. Metzger,et al.  FATS AND OILS AS RENEWABLE FEEDSTOCK FOR CHEMISTRY , 2009 .

[20]  G. G. Stokes "J." , 1890, The New Yale Book of Quotations.

[21]  A. López,et al.  Determination of the activation energies for α and β transitions of a system containing a diglycidyl ether of bisphenol a (DGEBA) and 1,3-bisaminomethylcyclohexane (1,3-BAC) , 1994 .

[22]  B. Mattiasson,et al.  Green approach for the preparation of biodegradable lubricant base stock from epoxidized vegetable oil , 2007 .

[23]  P. Oyanguren,et al.  Epoxies Modified by Palmitic Acid: From Hot‐Melt Adhesives to Plasticized Networks , 2005 .

[24]  Hsieh-Chih Tsai,et al.  Effect of aromatic and aliphatic amines as curing agents in sulfone epoxy monomer curing process , 2013, Polymer Bulletin.

[25]  Ghodsieh Mashouf Roudsari,et al.  Study of the Curing Kinetics of Epoxy Resins with Biobased Hardener and Epoxidized Soybean Oil , 2014 .

[26]  Kevin Barraclough,et al.  I and i , 2001, BMJ : British Medical Journal.

[27]  Ludwik Leibler,et al.  Catalytic Control of the Vitrimer Glass Transition. , 2012, ACS macro letters.

[28]  J. Bozell Feedstocks for the Future: Renewables in Green Chemistry , 2008 .

[29]  Bernard Boutevin,et al.  Biobased thermosetting epoxy: present and future. , 2014, Chemical reviews.

[30]  Joseph J. Bozell Feedstocks for the future : Using technology development as a guide to product identification , 2006 .

[31]  S. Erhan,et al.  Biodegradation Behavior of Some Vegetable Oil-Based Polymers , 2004 .

[32]  W. Marsden I and J , 2012 .

[33]  A. Corma,et al.  Chemical routes for the transformation of biomass into chemicals. , 2007, Chemical reviews.

[34]  Denise Handlarski,et al.  Green , 2007 .

[35]  L. Shechter,et al.  Glycidyl Ether Reactions with Alcohols, Phenols, Carboxylic Acids, and Acid Anhydrides , 1956 .

[36]  Mitsukazu Ochi,et al.  Shrinkage and internal stress during curing of epoxide resins , 1981 .

[37]  C. Fringant,et al.  Polymer networks derived from curing of epoxidised linseed oil: influence of different catalysts and anhydride hardeners , 2000 .

[38]  H. Hiller In: Ullmann''''s Encyclopedia of Industrial Chemistry , 1989 .

[39]  S. Fu,et al.  Preparation and mechanical properties of modified epoxy resins with flexible diamines , 2007 .

[40]  Sevim Z. Erhan,et al.  Epoxidized soybean oil as a potential source of high-temperature lubricants , 2002 .

[41]  Ludwik Leibler,et al.  Silica-Like Malleable Materials from Permanent Organic Networks , 2011, Science.

[42]  P. Madec,et al.  Kinetics and mechanisms of polyesterifications II. Reactions of diacids with diepoxides , 1985 .

[43]  Aaas News,et al.  Book Reviews , 1893, Buffalo Medical and Surgical Journal.

[44]  A. Kandelbauer,et al.  Synthesis and Characterization of a Bio‐Based Resin from Linseed Oil , 2012 .