Bio-based Polyurethane Based on a Dynamic Covalent Network with Damage Tolerance for Controlled Release of Fertilizers

Yu, Zeping; Cheng, Dongdong; Gao, Bin; Yao, Yuanyuan; Liu, Chenghao; Li, Junyin; Wang, Chun; Xie, Jiazhuo; Zhang, Shugang; Zhao, Li; Yang, Yuechao

doi:10.1021/acsami.2c14672

Cited by 17 publications

(7 citation statements)

References 40 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Three-dimensional printing technologies, such as stereolithography (SLA), can incorporate these precursors into their products to increase their bio-content [13]. Several coating applications may benefit from the properties these materials can provide, namely paper coating or incorporation into controlled-released fertilizers (CRFs) [14,15].…”

Section: Introductionmentioning

confidence: 99%

Synthesis of Bio-Based Thermoset Mixture Composed of Methacrylated Rapeseed Oil and Methacrylated Methyl Lactate: One-Pot Synthesis Using Formed Methacrylic Acid as a Continual Reactant

et al. 2023

View full text Add to dashboard Cite

Methacrylated vegetable oils are promising bio-based polymerizable precursors for potential material application in several fields, such as coating technologies or 3D printing. The reactants’ availability for their production is an enormous advantage, but the modified oils also exhibit high apparent viscosity values and poor mechanical properties. This work focuses on a way to produce oil-based polymerizable material precursors in a mixture with a viscosity modifier in a one-batch process. The required methacrylic acid for the modification of epoxidized vegetable oils can be obtained as a secondary product of the methacrylation of methyl lactate forming a polymerizable monomer along with the acid. This reaction results in a yield of over 98% of methacrylic acid. Epoxidized vegetable oil can be added into the same batch using acid for oil modification which results in the one-pot mixture of both methacrylated oil and methyl lactate. The structural verifications of products were provided via FT-IR, 1H NMR, and volumetric methods. This two-step reaction process produces a thermoset mixture with a lower apparent viscosity of 142.6 mPa·s in comparison with methacrylated oil exhibiting a value of 1790.2 mPa·s. Other physical-chemical properties of the resin mixture such as storage modulus (E′ = 1260 MPa), glass transition temperature (Tg = 50.0 °C), or polymerization activation energy (17.3 kJ/mol) are enhanced in comparison with the methacrylated vegetable oil. The synthesized one-pot mixture does not require additional methacrylic acid due to the use of the one formed in the first step of the reaction, while the eventual thermoset mixture exhibits enhanced material properties compared to the methacrylated vegetable oil itself. Precursors synthesized in this work may find their purpose in the field of coating technologies, since these applications require detailed viscosity modifications.

show abstract

Section: Introductionmentioning

confidence: 99%

Synthesis of Bio-Based Thermoset Mixture Composed of Methacrylated Rapeseed Oil and Methacrylated Methyl Lactate: One-Pot Synthesis Using Formed Methacrylic Acid as a Continual Reactant

et al. 2023

View full text Add to dashboard Cite

show abstract

“…(a) Stress–strain curves of VBD-TMP x and (b) mechanical performance of VBD-TMP 60 in this work compared with some biorenewable crosslinked polyurethanes in other research studies and commercial nonrenewable crosslinked polyurethanes. ,,,,,− …”

Section: Resultsmentioning

confidence: 95%

“…Therefore, bio-based thermosetting polyurethanes with different mechanical properties can be facilely prepared by tuning the content of crosslinker TMP. Within the context of biorenewable crosslinked polyurethanes, these VBD-TMP x lie at the high end of mechanical performances (Figure b). ,,,,,− They offer comparable tensile strengths and elongation at break values, but stand out in terms of their high bio-contents and degradability. It is also noteworthy that the stress–strain profiles for VBD-TMP 60 are comparable to or better than some of the commercial nonrenewable crosslinked polyurethanes, such as the Durethane R series and Desmodur MP-101 (Figure b).…”

Section: Resultsmentioning

confidence: 99%

Vanillin-Based Degradable Polyurethane Thermosets Demonstrating High Bio-Content and Mechanical Properties

Zhao

Liu

Wang

et al. 2023

ACS Appl. Polym. Mater.

View full text Add to dashboard Cite

Polyurethanes are widely used polymeric materials, but they are rarely biorenewable and degradable. Although some previously reported bio-based polyurethanes exhibit good thermal and mechanical properties, their bio-content is usually low, resulting from the only replacement of the diol monomer instead of the whole diol/diisocyanate pairs. In addition, traditional polyurethanes are often difficult to degrade, leading to environmental issues. To address these issues, we propose a solution by sourcing both the diols and isocyanates from biorenewable resources and introducing degradability into diols via the Tishchenko reaction, which is the disproportionation of two aldehydes to afford an ester bond with an atom economy of 100%. Commercially available bio-based vanillin was selected as the precursor for a vanillin-based diol (VBD) containing ester bonds. By reacting VBD with L-lysine diisocyanate (LDI) and trimethylolpropane (TMP) as a crosslinker, a series of bio-based thermosetting polyurethanes, VBD-TMP x , with high bio-based carbon content (>70.0%) were synthesized. The chemical structures and properties of monomers as well as polymers were characterized using nuclear magnetic resonance (NMR), Fourier transform infrared (FTIR) spectroscopy, thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), and tensile tests. The obtained VBD-TMP x polyurethanes exhibit comparable mechanical properties (σ = 32.0 MPa; E′ = 2.7 GPa) to commercial thermosetting polyurethanes and demonstrate higher toughness (34 MJ/m 3 ) than previously reported bio-based analogues. Additionally, the inherent ester bond in the VBD monomer enables the complete degradation of VBD-TMP x in a 0.1 M NaOH solution (THF/H 2 O = 1:1, v/v) within 3.5 h. This greatly broadens the available end-of-life choices, including the recovery of the monomers. This study presents a facile approach for creating degradable polyurethane materials with high bio-content and mechanical properties.

show abstract

“…The excellent properties of the coatings were attributed to the cross-linking modification of polyols, the ratio of soft and hard segments, and the reversible reaction of disulfide bonds. In another study, 96 Yu et al successfully prepared CRF coatings using soybean oil polyol, benzil dioxime, and PAPI as raw materials. The hydrogen bond interaction and oxime-urethane bonds facilitated the self-healing of the coatings under heat, resolving the problem of accelerated fertilizer release caused by micropores during the curing of the coating.…”

Section: Application Of Bspumentioning

confidence: 99%

Recent Advances in Tailored Fabrication and Properties of Biobased Self-Healing Polyurethane

Yu,

An,

Zhang

et al. 2023

Biomacromolecules

View full text Add to dashboard Cite

With the emergence of challenges in the environmental degradation and resource scarcity fields, the research of biobased self-healing polyurethane (BSPU) has become a prevailing trend in the technology of the polyurethane industry and a promising direction for developing biomass resources. Here, the production of BSPU from lignocellulose, vegetable oil, chitosan, collagen, and coumarin is classified, and the principles of designing polyurethane based on compelling examples using the latest methods and current research are summarized. Moreover, the impact of biomass materials on self-healing and mechanical properties, as well as the tailored performance method, are presented in detail. Finally, the applications of BSPU in biomedicine, sensors, coatings, etc. are also summarized, and the possible challenges and development prospects are explored to helpfully make progress in the development of BSPU. These findings demonstrate valuable references and practical significance for future BSPU research.

show abstract

Bio-based Polyurethane Based on a Dynamic Covalent Network with Damage Tolerance for Controlled Release of Fertilizers

Cited by 17 publications

References 40 publications

Synthesis of Bio-Based Thermoset Mixture Composed of Methacrylated Rapeseed Oil and Methacrylated Methyl Lactate: One-Pot Synthesis Using Formed Methacrylic Acid as a Continual Reactant

Synthesis of Bio-Based Thermoset Mixture Composed of Methacrylated Rapeseed Oil and Methacrylated Methyl Lactate: One-Pot Synthesis Using Formed Methacrylic Acid as a Continual Reactant

Vanillin-Based Degradable Polyurethane Thermosets Demonstrating High Bio-Content and Mechanical Properties

Recent Advances in Tailored Fabrication and Properties of Biobased Self-Healing Polyurethane

Contact Info

Product

Resources

About