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Development of Non-isocyanate Polyurethanes from Biobased Furanic Chemicals

Zhang, Lu
http://orcid.org/0000-0002-6417-964X
http://rave.ohiolink.edu/etdc/view?acc_num=osu1574777307668391

Abstract Details

2019, Doctor of Philosophy, Ohio State University, Food, Agricultural and Biological Engineering.
As issues associated with climate change become more and more prominent, reducing CO2 emissions and petroleum consumption has become more important now than ever before. In this regard, the concept of biorefining has emerged to accelerate the transition to the production of products from biomass as an alternative to petroleum. To support the integrated biorefinery, researchers have identified a number of biobased platform chemicals that are key to bridging the gap between biomass and biobased products. One of these platform chemicals is 5-hydroxymethylfurfural (HMF), which has been widely studied as a precursor for the production of biobased polyesters. However, its chemical structure indicates that it might also be a suitable precursor for the synthesis of biobased non-isocyanate polyurethanes (NIPUs). In this work, an integrated plan was provided for the synthesis of innovative NIPUs from biomass relying on HMF as an intermediate. In the first step, a highly efficient, stable, and magnetically-recoverable catalyst was developed for the synthesis of HMF from fructose and chicory root-derived inulin. To synthesize the catalyst, a heteropolyacid, H3PW12O40 (HPW), was immobilized on the surfaces of SiO2 and TiO2-coated Fe3O4 nanoparticles, and the resulting nanocatalyst (Fe3O4@SiO2@TiO2−HPW) was shown to have a high specific surface area and catalytic activity to HMF production. After reactions, the catalyst could be easily separated using an external magnet, and the catalytic activity of the catalyst was well-conserved after reuses. HMF was subsequently upgraded to 2,5-furandicarboxylic acid (FDCA) using a new transition metal-free aerobic oxidation approach, in which high product yields were obtained in the presence of NaOH in dimethylformamide (DMF) at room temperature. To explore the potential of FDCA for new applications, a new synthetic strategy was developed for the synthesis of NIPUs from FDCA. FDCA was used to prepare a bis(cyclic carbonate) for the first time, and the bis(cyclic carbonate) was further reacted with diamines to yield a series of novel FDCA-derived NIPUs. Results showed that these FDCA-derived NIPUs had similar properties (e.g., molecular weights and thermal properties) compared to those synthesized from non-renewable terephthalic acid. In addition to FDCA, 2,5-bis(hydroxymethyl)furan (BHMF) is another important HMF derivative that has great potential for making NIPUs. A series of highly efficient AgCu catalysts were developed for the electrochemical hydrogenation of HMF to BHMF. The AgCu catalysts were prepared by galvanic displacement of Ag on nanotextured Cu particles which were obtained from dealloyed AlCu, and the results showed that the AgCu catalysts had high catalytic activity and excellent reusability. Finally, BHMF, in combination of 1,4-butanediol (BD), was used as a diol to synthesize linear NIPUs through transurethanization. The linear furan-bearing NIPUs were then crosslinked by means of reversible Diels–Alder reactions, generating NIPU materials that are recyclable, mendable, and self-healing. In summary, this study highlights new strategies for the production of various biobased NIPUs from biomass using HMF as an intermediate, and these HMF-derived NIPUs have great potential as replacements to fossil-based NIPUs.
Frederick Michel (Advisor)
Anne Co (Committee Member)
Katrina Cornish (Committee Member)
Ajay Shah (Committee Member)
227 p.
Agricultural Engineering

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Citations

  • Zhang, L. (2019). Development of Non-isocyanate Polyurethanes from Biobased Furanic Chemicals [Doctoral dissertation, Ohio State University]. OhioLINK Electronic Theses and Dissertations Center. http://rave.ohiolink.edu/etdc/view?acc_num=osu1574777307668391

    APA Style (7th edition)

  • Zhang, Lu. Development of Non-isocyanate Polyurethanes from Biobased Furanic Chemicals. 2019. Ohio State University, Doctoral dissertation. OhioLINK Electronic Theses and Dissertations Center, http://rave.ohiolink.edu/etdc/view?acc_num=osu1574777307668391.

    MLA Style (8th edition)

  • Zhang, Lu. "Development of Non-isocyanate Polyurethanes from Biobased Furanic Chemicals." Doctoral dissertation, Ohio State University, 2019. http://rave.ohiolink.edu/etdc/view?acc_num=osu1574777307668391

    Chicago Manual of Style (17th edition)

osu1574777307668391
498
© 2019, all rights reserved.
This open access ETD is published by The Ohio State University and OhioLINK.