A. Rescifina

L. Rubino

M. Galimberti

V. Patamia

Vincenzina Barbera

English

Archivio istituzionale della ricerca - Politecnico di Milano

1V. Barbera et al  - From natural sources to materials… MoDeSt – 2021    Lampedusa (I), September 2nd 2021From natural sources to materials: isocyanate-free polyurethanes from (R)-(+)-limonene oxideVincenzina BarberaaL. Rubino, a A. Rescifina, b V. Patamia, b M. Galimberti avincenzina.barbera@polimi.ita Politecnico di Milano, Department of Chemistry, Materials and Chemical Engineering “G. Natta”b Università di Catania, Dipartimento di Scienze del Farmaco e della Salute2V. Barbera et al  - From natural sources to materials… MoDeSt – 2021    Lampedusa (I), September 2nd 2021Politecnico di Milano, Department of Chemistry, Materials and Chemical Engineering “G. Natta”ISCaMaPInnovative Sustainable Chemistry and Materials and Proteomics Group3V. Barbera et al  - From natural sources to materials… MoDeSt – 2021    Lampedusa (I), September 2nd 2021Natural sourcesISCaMaPWastes and residuesBuilding blocksfor chemical platformsProteins4V. Barbera et al  - From natural sources to materials… MoDeSt – 2021    Lampedusa (I), September 2nd 2021ISCaMaP Chemicals,  Additives, Modifiers, Polymers Natural sourcesInnovative chemicalsInnovative materialsWastes and residuesBuilding blocksfor chemical platformsProteins5V. Barbera et al  - From natural sources to materials… MoDeSt – 2021    Lampedusa (I), September 2nd 2021ISMaterials group6V. Barbera et al  - From natural sources to materials… MoDeSt – 2021    Lampedusa (I), September 2nd 2021From natural sources to materialsWastes from citrus fruits processing industries generate large amounts of products. Terpenes, in particular Limonene, are the major components of essential oils of citrus fruitPolyurethanes7V. Barbera et al  - From natural sources to materials… MoDeSt – 2021    Lampedusa (I), September 2nd 2021A rational designLimonene: a biosourced buiding blockC10H18IUPAC: 1-methyl-4-(prop-1-en-2-yl)cyclohexene Starting building block for many reaction pathways Reactivity8V. Barbera et al  - From natural sources to materials… MoDeSt – 2021    Lampedusa (I), September 2nd 2021Why polyurethanes?➢ no co-products (polyaddition!)➢ versatile polymers➢ commercial valueThe urethane bond9V. Barbera et al  - From natural sources to materials… MoDeSt – 2021    Lampedusa (I), September 2nd 2021The world of polyurethanes TPUFlexibleRigidBiomedicalWaterborne10V. Barbera et al  - From natural sources to materials… MoDeSt – 2021    Lampedusa (I), September 2nd 2021Concerns about polyurethanes➢ Isocyanate production: phosgenation➢ Isocyanate reactivity: storage➢ Isocyanate toxicity➢ Isocyanate reactivity: by-products11V. Barbera et al  - From natural sources to materials… MoDeSt – 2021    Lampedusa (I), September 2nd 2021Isocyanate toxicity The most used isocyanates, TDI and MDI, are classified as CMR (Carcinogen, Mutagen, Reprotoxic) substancesOCN NCONCONCOOCN NCO2,4-TDI 2,6-TDI 4,4’-MDI12V. Barbera et al  - From natural sources to materials… MoDeSt – 2021    Lampedusa (I), September 2nd 2021This work. The rational designobjective13V. Barbera et al  - From natural sources to materials… MoDeSt – 2021    Lampedusa (I), September 2nd 2021This work. The rational designobjective14V. Barbera et al  - From natural sources to materials… MoDeSt – 2021    Lampedusa (I), September 2nd 2021This work. Polyurethanes from (R)-(+)-limoneneThe strategyCyclic carbamateIsocyanate free PU15V. Barbera et al  - From natural sources to materials… MoDeSt – 2021    Lampedusa (I), September 2nd 2021This work. Polyurethanes from (R)-(+)-limoneneHNOHR NOOR(R)-(+)-limonenebio-sourcedbuilding blockThe strategy𝛽-amino alcohols Cyclic carbamates16V. Barbera et al  - From natural sources to materials… MoDeSt – 2021    Lampedusa (I), September 2nd 2021Polyurethanes from (R)-(+)-limoneneCH3, (CH2)5CH3, Bn, PhL. Rubino, A.Rescifina, V. Patamia, M. Galimberti, V. Barbera (2021). Submitted for pubblication17V. Barbera et al  - From natural sources to materials… MoDeSt – 2021    Lampedusa (I), September 2nd 20211trans-limonene oxide cis-limonene oxide2 2’O OO(R)-(+)-limonene epoxidePolyurethanes from (R)-(+)-limonene18V. Barbera et al  - From natural sources to materials… MoDeSt – 2021    Lampedusa (I), September 2nd 2021The aminolysis is regio- and diastereoselective. The approach of the nucleophile is known tobe trans-diaxial (Fürst-Plattner rule). In the case of cis-limonene oxide, the reaction occursvia a SN1-type mechanism with inversion of configuration at the C-1. For trans-limoneneoxide, a SN2-type reaction can be envisioned at C-2.cistrans[1] Leffingwell, J. C., & Royals, E. E. (1965). Tetrahedron Letters, 6(43), 3829-3837.[2] Royals, E. E., & Leffingwell, J. C. (1966). The Journal of Organic Chemistry, 31(6), 1937-1944.[3] Newhall, W. F. (1964).. The Journal of Organic Chemistry, 29(1), 185-187.Aminolysis of (R)-(+)-limonene oxide19V. Barbera et al  - From natural sources to materials… MoDeSt – 2021    Lampedusa (I), September 2nd 2021trans-limonene oxide cis-limonene oxide2 2’Route B Route AO OHNOHR333’NHOHR+RNH2RNH2+HNCH3NHOH3COH HNOHNH23a 3a’ 3cAminolysis of (R)-(+)-limonene oxideNH2-CH 3 aq. (40%)20V. Barbera et al  - From natural sources to materials… MoDeSt – 2021    Lampedusa (I), September 2nd 2021IIIIIIIVVVIδ +δ -δ +δ-OOHHNH2NOHOHOHOHNH2OHHNRRR ROAminolysis of (R)-(+)-limonene oxide: mechanismcis-limonene oxidetrans-limonene oxide21V. Barbera et al  - From natural sources to materials… MoDeSt – 2021    Lampedusa (I), September 2nd 2021IIIIIIIVVVIδ +δ -δ +δ-OOHHNH2NOHOHOHOHNH2OHHNRRR ROAminolysis of (R)-(+)-limonene oxide: mechanismtrans-limonene oxide22V. Barbera et al  - From natural sources to materials… MoDeSt – 2021    Lampedusa (I), September 2nd 2021   	 3a   	3a’Aminolysis of (R)-(+)-limonene oxide: computational studies23V. Barbera et al  - From natural sources to materials… MoDeSt – 2021    Lampedusa (I), September 2nd 2021Aminolysis of (R)-(+)-limonene oxide: computational studies	3c24V. Barbera et al  - From natural sources to materials… MoDeSt – 2021    Lampedusa (I), September 2nd 2021sp3A Library of molecules… and so on!25V. Barbera et al  - From natural sources to materials… MoDeSt – 2021    Lampedusa (I), September 2nd 2021Polyurethanes from (R)-(+)-limoneneSynthesis of a library of cyclic carbamates via DAC chemistryGreen synthesesNo toxic reagentsHigh YieldsCH3, (CH2)5CH3, Bn, PhL. Rubino, A.Rescifina, V. Patamia, M. Galimberti, V. Barbera (2021). Manuscript in preparation26V. Barbera et al  - From natural sources to materials… MoDeSt – 2021    Lampedusa (I), September 2nd 2021Isocyanate-free Polyurethane via cationic ring opening polymerization of five-membered cyclic carbamatesC11H17O2(5R)-7a-methyl-5-(prop-1-en-2-yl)hexahydrobenzo[d]oxazol-2(3H)-onePolyurethanes from biosourced materials27V. Barbera et al  - From natural sources to materials… MoDeSt – 2021    Lampedusa (I), September 2nd 2021Polyurethanes from terpenes: awardIsocyanate-free polyurethanes from terpenes: ROP of five-membered cyclic carbamates and cyclic carbonates Lucia Rubino, Vincenzina Barbera, Fatima Margani, Roberto Guadagnin, Maurizio GalimbertiPolitecnico di Milano, Department of Chemistry, Materials and Chemical Engineering “G. Natta”, Via Mancinelli 7, 20131 Milano, Italyluciarita.rubino@polimi.itReferences:[1] C.R. McElroy, F. Aricò, F. Benetollo, P. Tundo, J. Appl. Chem., 2011, 84(3), 707.[2] L. Rubino, V. Barbera, M. Galimberti. Manuscript in preparation[3] M. Bähr, A. Bitto, R. Mülhaupt, J. Green Chem., 2012, 14(5), 1447.[4] Qin, X., Wang, J., Han, B., Wang, B., Mao, L., & Zhang, L. Front. Chem. 2018, 6, 240.Acknowledgement: Pirelli Tyre for the financial supportSynthetic route to five-memberedcyclic carbamates (Route A) from D-limonene. A library was synthetized.Products characterized by: 1H-NMR, 13C-NMR, GC/MS, IR, Mass spectrometryThe strategyObjectives☺ Use of natural sources as building blocks for innovative platforms of chemicals;☺ Synthesis of isocyanate-free polyurethanes via Ring-Opening Polymerization (ROP) of 5-membered cyclic carbamates andcarbonates;☺ Use of PU as super elastomer materials to replace traditional tyre compounds.1Route BRoute AOOOD-limonenebio-sourced building blockCyclic carbamates fromD-limoneneCyclic carbonates fromD-limonene5NOOR42 3H2O, 100°C24hO OOTBD, 120°C24h4ORH2NHNOHR NOORSynthetic route to five-memberedcyclic carbonates (Route B) from D-limonene.Products characterized by: 1H-NMR, 13C-NMR, GC/MS, IR, Mass spectrometryIntroductionPolyurethanes (PU) represent one of the most versatile class of polymers, being suitable for a large variety of applications. Theyare industrially prepared by chemical reaction between polyols and isocyanates.Isocyanates are known to be highly toxic for health and environment ☹Cat:  BF3O(Et)2Monomer / Cat  =  1 / 0.015r.t., 12h, solvent free                   Synthesis of a library of cyclic carbamates via DAC chemistryR = CH2CH3, Bn, NH-PhGreen synthesesNo toxic reagentsHigh YieldsConclusionsStarting from the natural terpene D-limonene, green and sustainablereaction pathways were studied and performed to obtain key intermediatesfor the synthesis of isocyanate-free polyurethanes. PU oligomers wereefficiently obtained from the ROP of D-limonene cyclic carbamates, thusreplacing the use of hazardous chemicals as isocyanates.Synthesis of cyclic carbonates with CO2Polycarbonates were obtained.Synthesis of PU in progress!Cationic ROP OHR1NH2R2sp3 sp22 5OCO2OOOOOO* *nROPLucia Rubino(Post Doc)PhD Project28V. Barbera et al  - From natural sources to materials… MoDeSt – 2021    Lampedusa (I), September 2nd 2021Politecnico di Milano, Department of Chemistry, Materials and Chemical Engineering “G. Natta”ISMaterials groupInnovative Materials Group

From natural sources to materials: isocyanate-free polyurethanes from (R)-(+)-limonene oxide

https://re.public.polimi.it/bitstream/11311/1234908/1/V.%20Barbera%20et%20al%20-%20From%20natural%20sources%20to%20materials...%20-%20MoDeSt%202021%20-%202.1.2021_.pdf

From natural sources to materials: isocyanate-free polyurethanes from (R)-(+)-limonene oxide

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