POLYMERS FROM VEGETABLE OILS AS RENEWABLE RESOURCES Laboratory of Sustainable Polymers

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1 CEICS FUM 2011 What s N in CEICS Chemistry & Energy esearch and Innovation PLYMES FM VEGETABLE ILS AS ENEWABLE ESUCES Laboratory of Sustainable Polymers Marina Galià, Gerard Lligadas, Joan Carles onda, Virginia Cádiz

2 Polymers from Vegetable ils as enewable esources Development that meets the needs of the present without compromising the ability of future generations to meet their own needs" The Brundland Commission, 1983 The UN World Summit on Sustainable Development held in Johannesburg in 2002 called for the promotion of a sustainable use of biomass

3 Polymers from Vegetable ils as enewable esources Using renewable resources is not new The soybean car unveiled by enry Ford in 1941 Eco ne The truly environmentally friendly racing car built at Warwick Innovative Manufacturing esearch Centre (WIMC) in 2007

4 Polymers from Vegetable ils as enewable esources During the second half of the last century the petrochemical boom and the spectacular diversification in the structures available from crude oil went to the detriment of any substantial progress in the use of renewable resources. Very modest investments were devoted to renewable resources development and they have not played an appreciable role in bringing about specific functional properties. The necessity of releasing the polymer industry from its dependence on depleting fossil resources is pushing the search for industrially applicable renewable alternatives. The US Department of Energy established in 2004 two lists of building blocks offering alternatives to conventional polymers: Sugars and vegetable oils.

5 Polymers from Vegetable ils as enewable esources 100% 56% 84.6 Mt Mt 62% 60% Animal feed 6% Industrial 14% 20% Nutrition 80% 74% Production of oils and fats that are important as feedstock for the oleochemical industry in 1999/2000 and 2009/2010 il and fat consumption

6 Polymers from Vegetable ils as enewable esources Fatty compounds as starting materials for synthesis oleic acid (1 a) linoleic acid (2 a) linolenic acid (3 a) erucic acid (4 a) ricinoleic acid (5 a) petroselinic acid (6 a) 5-eicosenoic acid (7 a) calendic acid (8 a) α-eleostearic acid (9 a) punicic acid (10 a) santalbic acid (11 a) vernolic acid (12) 10-undecenoic acid (13 a) respective methyl esters (1 b 13 b) and alcohols (1 c 13 c).

7 Polymers from Vegetable ils as enewable esources Arkema

8 Polymers from Vegetable ils as enewable esources Motivation of our research Development of new synthetic methods for efficient, easy and rapid preparation of monomers and polymers. ngoing use of petroleum is not sustainable. What about renewable resources? Plant oils are ideal raw materials for the chemical and polymer industry because of their availability, structural variety, chemical versatility and relative low cost. Triglycerides contain several reactive positions and functionalities useful in many synthetic transformations.

9 Polymers from Vegetable ils as enewable esources Biobased epoxy resins icinus Communis icinoleic acid Undecilenic acid C 3 P UDTGE UDBME DP-III 2 2 as epoxidation reagent No organic solvent is needed Materials with moderate Tg and good thermal stability Good flame retardant behaviour for the P containing materials J Polym Sci Part A: Polym Chem 44, 5630 (2006); 44, 6717 (2006)

10 Polymers from Vegetable ils as enewable esources igh oleic sunflower oil derivatives Alternative to the conventional acrylic systems Good flame retardancy when using phosphorus compounds as reactive modifiers. igh reactivity Alternative to the curing of conventional epoxidized vegetable oils Materials showing high Tg values J Polym Sci Part A: Polym Chem 46, 6843 (2008); 41, 1159 (2009); 47, 4051 (2009); 48, 869 (2010)

11 Polymers from Vegetable ils as enewable esources Silicon containing organic-inorganic hybrid materials + Si catalyst C C Si rganic ybrid Polymers UDTG Inorganic C 3 3 C Si Si C 3 Si Si C 3 TMCTS C 3 Si C 3 Si C 3 UDBM C 3 3 C Si C 3 C 3 C 3 Si Si Si C 3 C 3 3 C Si C 3 TKDS C 3 DMSB

12 Polymers from Vegetable ils as enewable esources ybrid organic-inorganic networks elastomeric materials were obtained in all cases materials with good thermal stabilities good transparency according to a good miscibility J Polym Sci Part A: Polym Chem 43, 6295 (2005); Biomacromolecules 7, 2420 (2006)

13 Polymers from Vegetable ils as enewable esources Biobased nanocomposites from epoxidized linseed oil rganic ybrid Polymers Inorganic Si Si Si Si Si Si Si Si = isobutyl G-PSS good flexibility good transparency 5 wt % G-PSS 2 wt % G-PSS 5 wt % G-PSS 2 wt % G-PSS Biomacromolecules 7, 3521 (2006)

14 Polymers from Vegetable ils as enewable esources ing opening polymerization igh molecular weight polyether-polyols Polyurethanes Controlled molecular weight polyoxazolinepolyols Block copolymers Polyurethanes Metathesis polymerization Thermoplastic and thermostable flame retardant polyesters Shape memory polyurethanes J Polym Sci Part A: Polym Chem 44, 634 (2006); 47, 5760 (2009); 48, 1649 (2010); 48, 4995 (2010); 48, 5009 (2010); 49, 518 (2011); 49, 3069 (2011); Macromol Chem Phys 212, 1392 (2011)

15 Polymers from Vegetable ils as enewable esources Segmented poly(ether urethane) networks from oleic acid: In vitro degradation behaviour -C 2 C 2 C 2 - PD 50 m C 3 C CN-C 2 C 2 C 2 C 2 C-NC LDI 50 m 50 m n-1 X X X = -CC 3,-C 2 - Weight loss (wt%) PU-52 PU-42 PU-31 PU 50 m Degradation time (d) Biomacromolecules 8, 686 (2007); 8, 1858 (2007)

16 Polymers from Vegetable ils as enewable esources Click chemistry: Polymer Synthesis & Functionalization via Thiol-Ene h + DT Step-growth ligomerization < 2h Well-defined Telechelics click 1 UDA click 2 End-groups Modification >50% enewable Content Biomacromolecules 11, 2825 (2010)

17 Polymers from Vegetable ils as enewable esources Biobased Thermoplastic Polyurethanes PU1 PU3 PU2 PU4 No Significant Cytotoxicity esponse of Polyurethane Extracts TMX PU1 PU2 PU3 PU4 J Polym Sci Part A: Polym Chem 49, 2407 (2011)

18 Polymers from Vegetable ils as enewable esources Biobased Functional Telechelic Diols UDA-based SS (M n = 3100) BD-MDI-based S C N C 2 N C C N C 2 N C C N C 2 N C m n MTT Cytotoxicity Test Biobased TPUs with segmented morphology and no cytotoxicity response Biomacromolecules 11, 1646 (2010)

19 Polymers from Vegetable ils as enewable esources Fast-Degrading Polyanhydrides Ac 2 150ºC reflux ( ) PA-UDS ( ) PA-UDS:UDTGS 80:20 vacuum Anhydride (%) Weight (%) M w (%) hodamine B (%) Time (h) Time (h) Time (h) Time (h) (A) (B) (C) Eroded Erodedarea PA-UDS NonNon-erodedarea Erosion Erosion front front (D) 0h 5h 10h 24h Macromol apid Commun 32, 1343 (2011)