Upgrading vegetable oil thermosets through co-polymer reinforcement with tannin-lipid conjugates Warren Grigsby Chunhua Luo, Neil Edmonds, Jafar Al-Hakkak
Overview: Unsaturated Copolymer Thermosets Polyester Resins Petrochemical-based Maleic anhydride Bisphenol A Styrene Divinyl benzene Unsat. Oil Systems Partial replacement Vegetable oils Styrene Divinyl benzene - req for cross-linking Unsat. Oil Systems Totally bio-based Vegetable oils Polyphenols - assist cross-linking
Introduction Thermoset resins → performance materials polyesters and epoxies renewables substitution? A major challenge with feedstock replacement is performance strength and durability automotive and construction applications Natural oils investigated as raw materials for thermoset resins and co-polymers readily available, potential bio-degradability and multi-functionality differing fatty acid composition and unsaturation → ideal feedstocks Meier, Metzger, Schubert, Chem. Soc. Rev., (11): p
Natural Oil Thermosets Thermosets prepared via unsaturation or introduced functional groups radical, condensation, oxidative polymerization High degree of unsaturation for reactivity thermal or cationic polymerization Natural oils need co-monomers styrene or divinyl benzene for performance Larock et al., Polymer, (4): p ; Biomacromolecules, (2): p
Nature provides a range of condensed tannins Leaf, fruit, stem and bark Polyphenolic, flavanyl sub-unit Tannin usually a cross-linked molecule in adhesives Phenol formaldehyde, Bakelite chemistry Structural applications requiring durability, strength Provide reinforcement in modified PLA plastics Condensed Tannins
Tannins are oligomeric polyphenolics typically n = 4 to 13 Possess rigid aromatic structures Easily functionalised – esters, ethers Potential to substitute petroleum-based co-monomers in natural oil-based co-polymer formulations Thermoset completely composed of renewable resources n
Aims Produce a totally biobased thermoset resin based on vegetable oils and tannins Utilise flavanyl structure → rigidity & cross-linking networks Evaluate differing tannin types, content and fatty acid ester DS natural oils with varying unsaturation & reactivity
Conjugating fatty acids by esterification Tannin Linoleate and Oleate esters formed differing unsaturation → reactivity & cross-linking Two tannin types similar degree of substitution (DS = 2) residual hydroxyls capped by acetate groups ArH HC= X X -CH 2 - -COCH 3 -CH 3 Pine Tannin Quebracho Tannin Luo, Grigsby, Edmonds, Al-Hakkak Acta Biomaterialia 9 (2013) 5226–5233.
Co-polymerization with vegetable oils Used different methods for radical polymerization Co/Zr oxidative catalyst Range of tannin ester contents (PTLA 0→100%) Linseed and tung oils Solvent cast films = hard, rigid → soft, flexible Monitor co-polymerization loss of unsaturation auto-oxidation
Chemical analysis of co-polymer films Cast films evaluated by 13 C NMR and solvent extraction Esterification retained Decrease of C=C Tannin Tannin Linoleate Co-polymer film
Co-polymer material properties DMTA Comparable to typical polyester thermosets PTLA has greater film stiffness (E’) Pure oil least Lower tannin ester content contributes to decreasing E’ and at lower temperatures PineQuebracho
Co-polymer material properties Tan profiles Higher Tg with tannin ester content → greater cross-linking Quebracho tannin Tg 32 to 64˚C Pine tannin Tg 36 to 72 ˚C Higher tannin → peak intensity decrease, over a broader range PineQuebracho
Co-polymer cross-link density Kinetic theory of rubber elasticity → cross-linking density E’ values taken 20˚C above Tg Cross-link density increase with tannin ester content Co-polymer TanninE 25°C ν e 10 3 Tg (%)(GPa) (mol/m3) (C) QTLA PTLA PTLA75-LIN PTLA50-LIN PTLA25-LIN LIN Luo, Grigsby, Edmonds, Al-Hakkak Acta Biomaterialia 9 (2013) 5226–5233
What happens if we change oil/conjugate ? Tannin Oleate esters or lower oil unsaturation Slower reaction undertake at 60˚C, require post-cure at 100˚C Soft-flexible films more oil, greater flexibility
What happens if we change oil/conjugate ? Tannin Oleate esters or lower oil unsaturation Slower reaction Soft-flexible films more oil, greater flexibility More oil → stepwise decrease in softening onset Tg’s typically 9-13˚C Second broader increase >50˚C post-curing, second Tg 2-phase system PineQuebracho Luo, Grigsby, Edmonds, Al-Hakkak Macromolecular Materials and Engineering, 2014, 299(1) pp 65–74.
Summary Tannin fatty acid esters and vegetable oils give varying co-polymerization rates and material properties Tannin esters provide additional cross-linking sites for co-polymerization beyond the triglyceride
Summary Tannin fatty acid esters and vegetable oils give varying co-polymerization rates and material properties Tannin esters provide additional cross-linking sites for co-polymerization beyond the triglyceride Tannin Linoleates Linoleates give greater range in properties and Tg’s Dependent on tannin ester content Single Tg → single co-polymer phase and homogeneity in films Tannin linoleates and oils have similar polymerization rates and cross-linking not case in analogous vegetable oil – styrene/divinyl benzene
Summary Tannin fatty acid esters and vegetable oils give varying co-polymerization rates and material properties Tannin esters provide additional cross-linking sites for co-polymerization beyond the triglyceride Tannin Oleates Introducing lower unsaturation reduces reactivity times slower Tannin oleates give rubber-like materials reduced cross-linking with 1-2 Tg features Offer differing dampening properties → rubbers with relatively rigid domains
Conclusions Tannin fatty acid conjugates can replace styrene and divinyl benzene in vegetable oil co-polymers Tuning reactivity gives co-polymers ranging from soft rubbers to hard thermosets Lineolate esters and >20% tannin content give co-polymer properties reported for styrene-vegetable oil systems Using tannin conjugates realizes a totally bio-based co- polymer thermoset
Acknowledgements The work presented in this study was supported through funding provided through the New Zealand Ministry of Business, Innovation & Employment C.L. thanks the Biopolymer Network Ltd for financial support and PhD scholarship stipend This presentation is dedicated to the late Prof. Allan Easteal who was a supervisor, colleague and contributor to this work
Polymer Properties DSC Thermograms exhibit exothermic peak >100˚C Likely further thermal polymerization & post-cure Higher oil content → broadens, lower temperature Consistent with DMTA
What happens if we change oil/conjugate ? Tannin Oleate esters or lower oil unsaturation Slower reaction Soft-flexible films more oil, greater flexibility Co-polymerTanninE 25°C ν e 10 3 Tg (%)(GPa) (mol/m3) (C) PTLA PTOA PTLA75-LIN PTOA75-LIN PTOA75-TUN