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Catalyzed non-isocyanate polyurethane (NIPU) coatings from bio-based poly(cyclic carbonates)

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Abstract

Formulations of bio-based poly(cyclic carbonates) and amines using cooperative catalysis were studied to produce non-isocyanate polyurethanes (NIPUs). Concerns on the use of isocyanates as starting materials for polyurethanes (PUs) have risen due to their effects on human health after exposure and also because their synthesis involves the use of phosgene. Polyurethanes are highly versatile materials used in widespread industries such as automotive, building, construction, and packaging. They have also been used as flexible and rigid foams, adhesives, coatings, thermoplastic, or thermoset materials. Traditionally, PUs are synthesized from polyols and polyisocyanates. In order to circumvent the concerns, much research has been devoted to exploring alternative approaches to the synthesis of PUs. NIPU synthesis using cyclic carbonates and amines has gained popularity as one of the new approaches. In this study, novel bio-based resins were synthesized by converting epoxidized sucrose soyate into carbonated sucrose soyate (CSS) under supercritical conditions. Initial studies have shown promise in systems where CSS is crosslinked with multifunctional amines generating coatings with good solvent resistance. This work focused on studying the effect of catalysts and developing formulations of bio-based non-isocyanate polyurethane coatings.

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References

  1. Demharter, A, “Polyurethane Rigid Foam, A Proven Thermal Insulating Material for Applications Between + 130 C and − 196 C.” Cryogenics, 38 (1) 113–117 (1998)

    Article  Google Scholar 

  2. Krol, P, “Synthesis Methods, Chemical Structures and Phase Structures of Linear Polyurethanes. Properties and Applications of Linear Polyurethanes in Polyurethane Elastomers, Copolymers and Ionomers.” Prog. Mater. Sci., 52 (6) 915–1015 (2007)

    Article  Google Scholar 

  3. Santerre, JP, Woodhouse, K, Laroche, G, Labow, RS, “Understanding the Biodegradation of Polyurethanes: From Classical Implants to Tissue Engineering Materials.” Biomaterials, 26 (35) 7457–7470 (2005)

    Article  Google Scholar 

  4. Zdrahala, RJ, Zdrahala, IJ, “Biomedical Applications of Polyurethanes: A Review of Past Promises, Present Realities, and a Vibrant Future.” J. Biomater. Appl., 14 (1) 67–90 (1999)

    Article  Google Scholar 

  5. Verschoor, L, Verschoor, AH, “Nonoccupational and Occupational Exposure to Isocyanates.” Curr. Opin. Pulm. Med., 20 (2) 199–204 (2014)

    Article  Google Scholar 

  6. Lockey, JE, Redlich, CA, Streicher, R, Pfahles-Hutchens, A, Hakkinen, PJ, Ellison, GL, Harber, P, Utell, M, Holland, J, Comai, A, “Isocyanates and Human Health: Multi-stakeholder Information Needs and Research Priorities.” J. Occup. Environ. Med. Am. Coll. Occup. Environ. Med., 57 (1) 44 (2015)

    Article  Google Scholar 

  7. Rokicki, G, Parzuchowski, PG, Mazurek, M, “Non-isocyanate Polyurethanes: Synthesis, Properties, and Applications.” Polym. Adv. Technol., 26 (7) 707–761 (2015)

    Article  Google Scholar 

  8. Figovsky, OL, Leykin, AD, Shapovalov, LL, “Non-isocyanate Polyurethanes-Yesterday, Today and Tomorrow.” Int. Sci. J. Altern. Energy Ecol., 3–4 95–108 (2016)

    Article  Google Scholar 

  9. Maisonneuve, L, Lamarzelle, OA, Rix, E, Grau, E, Cramail, H, “Isocyanate-Free Routes to Polyurethanes and Poly (Hydroxy Urethane)s.” Chem. Rev., 115 (22) 12407–12439 (2015)

    Article  Google Scholar 

  10. Kathalewar, MS, Joshi, PB, Sabnis, AS, Malshe, VC, “Non-isocyanate Polyurethanes: From Chemistry to Applications.” RSC Adv., 3 (13) 4110–4129 (2013)

    Article  Google Scholar 

  11. Delebecq, E, Pascault, J-P, Boutevin, B, Ganachaud, FO, “On the Versatility of Urethane/Urea Bonds: Reversibility, Blocked Isocyanate, and Non-isocyanate Polyurethane.” Chem. Rev., 113 (1) 80–118 (2012)

    Article  Google Scholar 

  12. Guan, J, Song, Y, Lin, Y, Yin, X, Zuo, M, Zhao, Y, Tao, X, Zheng, Q, “Progress in Study of Non-isocyanate Polyurethane.” Ind. Eng. Chem. Res., 50 (11) 6517–6527 (2011)

    Article  Google Scholar 

  13. Farhadian, A, Afshani, G, Babapour, M, Babaei Miyardan, A, Nabid, MR, Safari, N, “A Facile and Green Route for Conversion of Bifunctional Epoxide and Vegetable Oils to Cyclic Carbonate: A Green Route to CO2 Fixation.” ChemistrySelect, 2 (4) 1431–1435 (2017)

    Article  Google Scholar 

  14. Büttner, H, Steinbauer, J, Wulf, C, Dindaroglu, M, Schmalz, HG, Werner, T, “Organocatalyzed Synthesis of Oleochemical Carbonates from CO2 and Renewables.” ChemSusChem, 10 (6) 1076–1079 (2017)

    Article  Google Scholar 

  15. Guzmán, AF, Echeverri, DA, Rios, LA, “Carbonation of Epoxidized Castor Oil: A New Bio-based Building Block for the Chemical Industry.” J. Chem. Technol. Biotechnol., 92 (5) 1104–1110 (2017)

    Article  Google Scholar 

  16. Poussard, L, Mariage, J, Grignard, B, Detrembleur, C, Jérôme, C, Calberg, C, Heinrichs, B, De Winter, J, Gerbaux, P, Raquez, JM, “Non-isocyanate Polyurethanes from Carbonated Soybean Oil Using Monomeric or Oligomeric Diamines to Achieve Thermosets or Thermoplastics.” Macromolecules, 49 (6) 2162–2171 (2016)

    Article  Google Scholar 

  17. Javni, I, Hong, DP, Petrović, ZS, “Soy-Based Polyurethanes by Nonisocyanate Route.” J. Appl. Polym. Sci., 108 (6) 3867–3875 (2008)

    Article  Google Scholar 

  18. Tamami, B, Sohn, S, Wilkes, GL, “Incorporation of Carbon Dioxide into Soybean Oil and Subsequent Preparation and Studies of Nonisocyanate Polyurethane Networks.” J. Appl. Polym. Sci., 92 (2) 883–891 (2004)

    Article  Google Scholar 

  19. Howie JK, Schaefer JJ, Trout JE, “Synthesis of Polyol Medium Fatty Acid Polyesters.” US Patent 6,995,232, 2006

  20. Corrigan PJ, “Synthesis of Polyol Fatty Acid Polyesters.” US Patent 6,620,952, 2003

  21. Schaefer JJ, Trout JE, “Synthesis of Purified, Partially Esterified Polyol Polyester Fatty Acid Compositions.” US Patent 6,887,947, 2005

  22. Webster, DC, Sengupta, PP, Chen, Z, Pan, X, Paramarta, A., "Highly Functional Epoxidized Resins and Coatings." US Patent 9,096,773, 2015

  23. Pan, X, Webster, DC, “New Biobased High Functionality Polyols and Their Use in Polyurethane Coatings.” ChemSusChem, 5 (2) 419–429 (2012)

    Article  Google Scholar 

  24. Paramarta, A, Pan, X, Webster, DC, “Highly Functional Acrylated Biobased Resin System.” Radtech Rep., 1 26–32 (2013)

    Google Scholar 

  25. Nelson, TJ, Bultema, L, Eidenschink, N, Webster, DC, “Bio-based High Functionality Polyols and Their Use in 1 K Polyurethane Coatings.” J. Renew. Mater., 1 (2) 141–153 (2013)

    Article  Google Scholar 

  26. Kovash, CS, Pavlacky, E, Selvakumar, S, Sibi, MP, Webster, DC, “Thermoset Coatings from Epoxidized Sucrose Soyate and Blocked, Bio-Based Dicarboxylic Acids.” ChemSusChem, 7 (8) 2289–2294 (2014)

    Article  Google Scholar 

  27. Ma, S, Webster, DC, Jabeen, F, “Hard and Flexible, Degradable Thermosets from Renewable Bioresources with the Assistance of Water and Ethanol.” Macromolecules, 49 (10) 3780–3788 (2016)

    Article  Google Scholar 

  28. Ma, S, Webster, DC, “Naturally Occurring Acids as Cross-Linkers to Yield VOC-Free, High-Performance, Fully Bio-based, Degradable Thermosets.” Macromolecules, 48 (19) 7127–7137 (2015)

    Article  Google Scholar 

  29. Paramarta, A, Webster, DC, “The Exploration of Michael-Addition Reaction Chemistry to Create High Performance, Ambient Cure Thermoset Coatings Based on Soybean Oil.” Prog. Org. Coat., 108 59–67 (2017)

    Article  Google Scholar 

  30. Paramarta, A, Webster, DC, “Bio-based High Performance Epoxy-Anhydride Thermosets for Structural Composites: The Effect of Composition Variables.” React. Funct. Polym., 105 140–149 (2016)

    Article  Google Scholar 

  31. Webster DC, Yu AZ, “Biobased Highly Functional Oligomers and Thermosets Therefrom.” US Patent 9,765,233, 2017

  32. Yu, AZ, Rahimi, A, Webster, DC, “High Performance Bio-based Thermosets from Dimethacrylated Epoxidized Sucrose Soyate (DMESS).” Eur. Polym. J., 99 202–211 (2018)

    Article  Google Scholar 

  33. Yu, AZ, Sahouani, JM, Setien, RA, Webster, DC, “Effect of Nature and Extent of Functional Group Modification on Properties of Thermosets from Methacrylated Epoxidized Sucrose Soyate.” React. Funct. Polym., 128 29–39 (2018)

    Article  Google Scholar 

  34. Pan, X, Sengupta, P, Webster, DC, “Novel Biobased Epoxy Compounds: Epoxidized Sucrose Esters of Fatty Acids.” Green Chem., 13 (4) 965–975 (2011)

    Article  Google Scholar 

  35. Monono, EM, Webster, DC, Wiesenborn, DP, “Pilot Scale (10 kg) Production and Characterization of Epoxidized Sucrose Soyate.” Ind. Crops Prod., 74 987–997 (2015)

    Article  Google Scholar 

  36. Monono, EM, Bahr, JA, Pryor, SW, Webster, DC, Wiesenborn, DP, “Optimizing Process Parameters of Epoxidized Sucrose Soyate Synthesis for Industrial Scale Production.” Org. Process Res. Dev., 19 (11) 1683–1692 (2015)

    Article  Google Scholar 

  37. Samanta, S, Selvakumar, S, Bahr, J, Wickramaratne, DS, Sibi, M, Chisholm, BJ, “Synthesis and Characterization of Polyurethane Networks Derived from Soybean-Oil-Based Cyclic Carbonates and Bioderivable Diamines.” ACS Sustain. Chem. Eng., 4 (12) 6551–6561 (2016)

    Article  Google Scholar 

  38. Lambeth, RH, Henderson, TJ, “Organocatalytic Synthesis of (Poly) Hydroxyurethanes from Cyclic Carbonates and Amines.” Polymer, 54 (21) 5568–5573 (2013)

    Article  Google Scholar 

  39. Lombardo, VM, Dhulst, EA, Leitsch, EK, Wilmot, N, Heath, WH, Gies, AP, Miller, MD, Torkelson, JM, Scheidt, KA, “Cooperative Catalysis of Cyclic Carbonate Ring Opening: application Towards Non-Isocyanate Polyurethane Materials.” Eur. J. Org. Chem., 2015 (13) 2791–2795 (2015)

    Article  Google Scholar 

  40. Cornille, A, Blain, M, Auvergne, R, Andrioletti, B, Boutevin, B, Caillol, S, “A Study of Cyclic Carbonate Aminolysis at Room Temperature: Effect of Cyclic Carbonate Structures and Solvents on Polyhydroxyurethane Synthesis.” Polym. Chem., 8 (3) 592–604 (2017)

    Article  Google Scholar 

  41. Webster, DC, Crain, AL, “Synthesis and Applications of Cyclic Carbonate Functional Polymers in Thermosetting Coatings.” Prog. Org. Coat., 40 (1) 275–282 (2000)

    Article  Google Scholar 

  42. Garipov, RM, Sysoev, VA, Mikheev, VV, Zagidullin, AI, Deberdeev, RY, Irzhak, VI, Berlin, AA, Reactivity of Cyclocarbonate Groups in Modified Epoxy–Amine Compositions, pp. 289–292. Springer, Berlin (2003)

    Google Scholar 

  43. Stockmayer, WH, “Molecular Distribution in Condensation Polymers.” J. Polym. Sci. Part A Polym. Chem., 9 (1) 69–71 (1952)

    Google Scholar 

  44. Stockmayer, WH, “Molecular Distribution in Condensation Polymers.” J. Polym. Sci. Part A Polym. Chem., 11 (5) 424 (1953)

    Google Scholar 

  45. Durand, D, Bruneau, CM, “Statistics of Random Macromolecular Networks, 2. Stepwise Polymerization of Polyfunctional Monomers Bearing A and B Coreactive Groups.” Macromol. Chem. Phys., 183 (4) 1021–1035 (1982)

    Article  Google Scholar 

  46. Durand, D, Bruneau, C-M, “Average Functionalities of Macromolecules in Stepwise Polyfunctional Polymerization.” Polymer, 23 (1) 69–72 (1982)

    Article  Google Scholar 

  47. Miller, DR, Macosko, CW, “Average Property Relations for Nonlinear Polymerization with Unequal Reactivity.” Macromolecules, 11 (4) 656–662 (1978)

    Article  Google Scholar 

  48. Miller, DR, Valles, EM, Macosko, CW, “Calculation of Molecular Parameters for Stepwise Polyfunctional Polymerization.” Polym. Eng. Sci., 19 (4) 272–283 (1979)

    Article  Google Scholar 

  49. Stafford, JW, “Multifunctional Polycondensation and Gelation: A Kinetic Approach.” J. Polym. Sci. Part A Polym. Chem., 19 (12) 3219–3236 (1981)

    Article  Google Scholar 

  50. Nelson, TJ, Masaki, B, Morseth, Z, Webster, DC, “Highly Functional Biobased Polyols and Their Use in Melamine–Formaldehyde Coatings.” J. Coat. Technol. Res., 10 (6) 757–767 (2013)

    Article  Google Scholar 

Download references

Acknowledgments

This work was supported by the National Science Foundation EPSCoR Award under Grant No. IIA-1355466.

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Correspondence to Dean C. Webster.

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Yu, A.Z., Setien, R.A., Sahouani, J.M. et al. Catalyzed non-isocyanate polyurethane (NIPU) coatings from bio-based poly(cyclic carbonates). J Coat Technol Res 16, 41–57 (2019). https://doi.org/10.1007/s11998-018-0135-7

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