Soybean Oil-based Polyurethane Research Articles

Outstanding performance of flower-like NiO nanostructures in epoxied soybean oil-based polyurethane nanocomposite coatings: Investigation of anticorrosion and antibacterial properties

Nowadays, nanocomposite coatings have gained much attention from both academic and industrial aspects mainly because of the outstanding properties which they can offer simultaneously. Specifically, anti-corrosion properties can make them one of the best choices to solve destructive corrosion problems. Nickel oxide (NiO) nanoparticles have been synthesized to create these outstanding properties in vegetable oil-based polyurethane coatings. To this end, epoxidized soyabean oil was utilized to synthesize polyol and produce polyurethane coatings, and NiO nanoparticles were incorporated into the obtained coatings. The obtained coatings were evaluated through the FTIR, H NMR, and FESEM techniques and their performance in terms of water uptake, anticorrosion and antibacterial properties were investigated. The obtained results clearly showed that the presence of NiO nanoparticles has had an undeniable effect on the performance of the coating in protecting mild steel substrate against corrosion. Moreover, using these nanoparticles has created remarkable antibacterial properties in the coating besides improved mechanical performance compared to pure polyurethane coating.

Design of novel polyurethane-based ionene nanocarriers for cancer therapy: Synthesis, in-vitro, and in-vivo studies

New strategies for constructing versatile nanocarriers are needed for cancer therapy to overcome the multiple challenges of targeted delivery. This work explores the advantages of polyurethane with main-chain quaternary ammonium salt moieties (ionene) as a novel carrier for targeted drug delivery. We have developed a novel cationic soybean oil-based polyurethane ionene nanocarrier (CPUI) that can act as an effective anticancer agent and efficiently deliver the anticancer drug 5-fluorouracil (5FU). We also report a potential anticancer drug delivery system targeting the folate receptor. In vitro experiments with blank CPUI carriers on the 4T1 (mouse breast cancer cell line) and the NIH-3T3 (mouse fibroblast cell line) revealed high cytotoxicity for the cancer cells but only low cytotoxicity for the normal fibroblast cells. The CPUI nanoparticles were readily loaded with 5FU (5FU-CPUI) in water using electrostatic interactions between the cationic quaternary ammonium groups of ionene and the anionic 5FU. The in vivo study in mice with tumors showed that the blank CPUI carriers significantly inhibited tumor growth, even more than the free drug (5FU). The inhibitory effect on tumor growth was slightly enhanced when the carriers were loaded with 5FU. The prepared nanoparticles had a high loading capacity of 41.8 %. Further enhancement of the inhibitory effect was observed when folic acid (FA) was added as a targeting moiety to the system via ion exchange with the bromine counterion of the quaternary ammonium moieties. The results suggest that the efficacy of FA-CPUI-5FU nanoparticles as vehicles for drug delivery can be enhanced via folate receptor (FR) mediated endocytosis in 4T1 cells and these novel nanocarriers may provide a potential platform for effective targeted drug delivery to tumor tissue and breast cancer therapy in the clinic.

Redox-responsive waterborne polyurethane nanocarriers for targeted doxorubicin delivery

Nanocarriers of different origins that respond to stimuli have been synthesized and used in various biomedical applications, such as intracellular drug delivery. To develop highly efficient nanocarriers, novel clickable and cleavable soybean oil-based polyurethane nanomicelles (CPUM), and polyurethane-hyaluronic acid nanomicelles (CPUM-HA) were prepared. The prepared nanocarriers exhibited controlling self-assembly properties, stimuli-responsiveness, good cytocompatibility, and high loading capacity for doxorubicin (DOX). The addition of the reducing agent glutathione (GSH) to the drug release medium resulted in GSH-triggered species size change (aggregation of nanomicelles) and enhanced release of DOX, leading to higher cytotoxicity in tumors. MTT, confocal laser scanning microscopy (CLSM), and flow cytometry results showed that the CPUM-HA-DOX nanocarriers exhibited increased cytotoxicity and cellular uptake compared to the CPUM-DOX nanocarriers. The in vivo and ex vivo results suggested that the CPUM-HA nanomicelles could provide a potential platform for effective targeted delivery of cytotoxic drug molecules to the tumor tissue and breast cancer therapy in the clinic.

Synthesis, Characterization and Properties of Soybean Oil-Based Polyurethane.

At present, the consumption of polyurethane is huge in various industries. As a result, it has become a research hotspot to use environmentally friendly and renewable bio-based raw materials (instead of petroleum-based raw materials) to prepare polyurethane. In this paper, epoxy soybean oil (ESO) was used as raw material, and polyethylene glycol (PEG-600) was used for ring opening. Fourier transform infrared (FT-IR) and proton nuclear magnetic resonance (1H NMR) analysis proved that soybean oil-based polyester polyols was prepared. Soybean oil-based polyurethane (SPU) was synthesized by the reaction of the soybean oil-based polyol with isophorone diisocyanate (IPDI), so as to save energy and protect the environment. The properties of SPU films were adjusted by changing the R value (the molar ration of -NCO/-OH) and the film forming temperature. The chemical structure and properties of the SPU were characterized by FTIR, 1H NMR, gel permeation chromatography (GPC), scanning electron microscopy (SEM), thermogravimetric analysis (TGA), and differential scanning calorimetry (DSC). The results show that the mechanical strength, water contact angle, microphase separation degree, barrier property, and thermal stability of SPU films gradually increase, while the transparency, oxygen permeability coefficient and moisture permeability coefficient of SPU films gradually decrease with the increase of R value and film forming temperature.

Natural and acid-treated attapulgite reinforced soybean oil-based polyurethane/epoxy resin interpenetrating polymer networks

Soybean oil-based polyurethane (PU)/epoxy (EP) interpenetrating polymer network (IPN) nanocomposites were prepared with natural attapulgite (N-ATT) and acid-treated attapulgite (A-ATT). The structure, glass transition, damping properties, thermal stability, mechanical properties and morphology of PU/EP IPN/ATT nanocomposites were characterized by X-ray diffraction (XRD), dynamic mechanical analysis (DMA), thermogravimetric analyzer, universal test machine and scanning electronic microscope (SEM). XRD showed that interaction with PU did not change the crystal structures of ATT. DMA results revealed the addition of ATT improved the glass transition temperature of the soybean oil-based PU/EP IPN, especially for A-ATT. However, the incorporation of ATT slightly decreased the damping properties of the soybean oil-based PU/EP IPN. Tensile tests confirmed that A-ATT had a significant reinforcement effect on the soybean oil-based PU/EP IPN. The tensile strength of the soybean oil-based PU/EP IPN increased by 56% with the addition of 4 mass% A-ATT. SEM demonstrated the relatively uniform dispersion of both N-ATT and A-ATT in the soybean oil-based PU/EP IPN matrix.

Synthesis and properties of epoxy soybean oil-based polyurethanes modified by 3,13-dimethyhydroxysilyl double-decker phenylsilsesquioxane

Nowadays, environmental problems such as petroleum resources exhaustion, pollution and global warming are in ceaseless aggravation. Consequently, vegetable oil becomes one of the most important resources due to its cheapness, easily availability and environmental regeneration. In this study, a series of sustainable polyurethanes based on epoxy soybean oil modified by different contents of 3,13-dimethyhydroxysilyl double-decker phenylsilsesquioxane [DDSQ(Me)OH] have been prepared. Polyol prepared with epoxy soybean oil has effectively replaced the petroleum-based polyol and the DDSQ(Me)OH performed as chain extender together with 1,4-butanediol (BDO). The structure of DDSQ(Me)OH was verified by 1H NMR and MALDI–TOF–MS. The structure and properties of sustainable polyurethanes were characterized by FTIR, DSC, TGA, SEM, tensile test and static contact angle. TGA demonstrated that hybrid polyurethanes were thermally stable due to the covalent incorporation of DDSQ(Me)OH in polymer main chain, the 5% weight loss temperatures (Td5) of hybrid polyurethane can be 21 °C higher than pure PU. DSC revealed the improved glass transition temperature (Tg) of polyurethanes, and the Tg can be 12.4 °C improved compared with pure polyurethane. SEM showed that the aggregation of DDSQ(Me)OH has dispersed homogeneously in the hybrid polyurethanes matrix. The results of the static contact angle revealed that with the increase of DDSQ(Me)OH content, the surface hydrophobicity has been enhanced significantly, and the static contact angle of water for hybrid polyurethanes can be up to about 110.2°.

Evaluation of Foaming and Nucleation and Growth Mechanism of Soy-Based Polyurethane Foams

The foaming and nucleation and growth mechanism of soybean oil-based polyurethane (SPU) were determined by the degree of hydrogen bonding, and isocyanate groups. New types of SPU were prepared by the different NCO/OH molar ratio (isocyanate index) from 1.0 to 2.0 in a soy polyol/polyether polyol (MDI) system. Foaming and nucleation and growth mechanisms of SPU were studied by fluorescence microscope (FM), scanning electron microscope (SEM), energy disperse spectroscopy (EDS) and Fourier transform infrared spectroscopy (FT-IR). It indicated that the isocyanate index affected remarkably the velocity of foaming and the critical nucleation radius of SPU and the ester functional group increased with the increase of isocyanate index. The nucleation and growth phase transition were dominated by the diffusion controlled nucleation and isocyanate content was the key factor of foam formation.

Preparation and Characterization of Soybean Oil-Based Polyurethanes for Digital Doming Applications.

Polyurethane-resin doming is currently one of the fastest growing markets in the field of industrial graphics and product identification. Semi-rigid bio-based polyurethanes were prepared deriving from soybean oil as a valuable alternative to fossil materials for digital doming and applied to digital mosaic technology. Bio-resins produced can favorably compete with the analogous fossil polymers, giving high-quality surface coatings (ascertained by SEM analyses). In addition, polyurethane synthesis was accomplished by using a mercury- and tin-free catalyst (the commercially available zinc derivative K22) bringing significant benefits in terms of cost efficiency and eco-sustainability.

A novel polyurethanes from epoxidized soybean oil synthesized by ring opening with bifunctional compounds

The present work reports the first synthesis of biobased polyurethanes utilizing soy-based polyols that are synthesized by epoxy ring opening of epoxidized soybean oil with chemicals bearing two different functionalities. Apart from polyols, the syntheses of which are described in our previous report where thioglycolic acid (TGA) and methyl ester of TGA (MTGA) were utilized for ring opening, a new polyol that was prepared by epoxy ring opening with glycolic acid (GA) was used for the synthesis of the polyurethanes. GA, which has both hydroxyl and carboxyl functionality, was used to open epoxy ring for the first time. The soybean oil-based polyurethanes (PUs) were formed by the reaction of 4,4′-methylenebis(phenyl isocyanate) (MDI) with the polyols that were synthesized using TGA (polyol-1), GA (polyol-2) and MTGA (polyol-3) to open epoxy rings, in bulk. The PUs were characterized using DSC, FTIR, XRD, SEM and thermogravimetric analysis. New polyurethanes demonstrated a wide range of tensile properties ranging from very flexible to rigid (from 3.44 to 39.7 MPa) as the molar ratio of OH to NCO was changed from 1.85/1 to 2.12/1. With the same polyol/MDI ratio, the best tensile properties were obtained with polyol 1 which has the highest OH functionality.

Organomontmorillonite-modified soybean oil-based polyurethane/epoxy resin interpenetrating polymer networks (IPNs)

In this work, in order to investigate the reinforcement effects of organomontmorillonite (OMMT) in soybean oil-based polyurethane (PU)/epoxy (EP) interpenetrating polymer networks (IPNs), a series of OMMT-modified PU/EP IPNs were prepared. The impacts of OMMT on the structure, morphology, glass transition, damping properties, thermal stability, and mechanical properties of the PU/EP IPNs were characterized by X-ray diffraction, scanning electronic microscope, dynamic mechanical analysis, thermogravimetry analysis, and tensile test. Results reveal that the addition of OMMT increases the glass transition temperature of the PU/EP IPNs. However, the damping properties of the PU/EP IPNs are lowered with the incorporation of OMMT. The addition of OMMT heightens the thermal stability of the PU/EP IPNs. Tensile tests show that the addition of OMMT significantly increases the tensile strength and tensile modulus of the PU/EP IPNs. With 4 and 6 % loading of OMMT, the tensile strength and tensile modulus increase 64 and 391 %, respectively.

Synthesis and characterization of hybrid latexes from soybean oil-based polyurethane and poly(2,2,2-trifluoroethyl methacrylate)

A class of novel fluorine containing core-shell hybrid latexes were obtained from soybean oil-based polyurethanes and poly(2,2,2-trifluoroethyl methacrylate) (PTFEMA) by two-step synthesis under mild reaction conditions. Structural and morphology properties of the resulting hybrid latexs have been characterized by FT-IR and TEM. In addition, thermal properties (DSC, TGA) and coating performance (contact angle, stress-strain curve, and surface free energy) were investigated and discussed. The hybrid latexes exhibit outstanding thermal stability and coating performance. More importantly, through this method, low-valued foods are successfully transformed into high-valued functional materials which bring new solutions for preparing materials from renewable sources.

Soybean Oil‐Based Polyurethane Networks: Shape‐Memory Effects and Surface Morphologies

AbstractVegetable oil‐based shape‐memory polyurethane networks are an emerging class of bio‐based functional materials with great potential applications. In this study, a series of different structural soybean oil polyols were synthesized, and utilized to fabricate polyurethane networks by reacting with 1,6‐diisocyanatohexane. The soybean oil‐based polyurethanes (SOPUs) were characterized with differential scanning calorimetry (DSC), dynamic mechanical tests (DMA), tensile testing, shape‐memory testing, and atomic force microscopy (AFM). It was found that SOPUs with a preserved triglyceride structure were fixed in a temporary shape at −20 °C, while others were fixed in temporary shapes at 4 °C. Although the recovery speeds were different, all the samples could completely regain their permanent shapes at 37 °C (human body temperature). Furthermore, different SOPUs exhibited different surface structures, which might provide the materials with additional values.

Soybean oil‐based polyurethane networks as candidate biomaterials: Synthesis and biocompatibility

AbstractBiobased polymeric materials are gaining increasing attention in biomedical areas. Here, we report a new class of biocompatible polyurethanes prepared from soybean oil‐based polyol that was synthesized by ring‐opening reaction of epoxidized monoglyceride (EMG) with lactic acid. By adjusting the molar ratio of hydroxyl to isocyanate group and the content of chain extender, soybean oil‐based polyurethanes with tensile strength of 9.30–27.1 MPa and elongation at break of 74.1–110.7% were prepared, while usual lipid‐based polyurethanes with the same 1,6‐diisocyanatohexane as reactant hardly have tensile strength higher than 5 MPa. Mouse fibroblast cells (L‐929) showed good adhesion and growth behavior on the polyurethane samples with more hydrophilic surfaces, and the cell viabilities of more than 50% were achieved with commercial tissue culture polystyrene (TCPS) disk as control. The good mechanical property and biocompatibility of the soybean oil‐based polyurethanes will make them suitable for wide range of potential biomedical applications.Practical applications: The synthesized soybean oil‐based polyurethanes have adjustable tensile strengths from 9.30–27.1 MPa and elongation at break of 74.1–110.7%. Along with their good biocompatibility, the polyurethanes can potentially replace wide range of part of petroleum‐based polymeric materials, particularly as biomedical materials.

Linseed and soybean oil-based polyurethanes prepared via the non-isocyanate route and catalytic carbon dioxide conversion

Soy- and linseed oil-based polyurethanes were prepared without using isocyanate monomers by curing carbonated soybean (CSBO) and linseed (CLSO) oils with different diamines. The conversion of the epoxidized seed oils with carbon dioxide to form cyclic carbonates was catalyzed with tetra-butylammonium bromide (TBAB) and silica-supported 4-pyrrolidinopyridinium iodide (SiO2–(I)), which was readily recovered without requiring the conventional purification by solvent extraction of TBAB. Carbonate formation was monitored as a function of catalyst type and pressure, indicating slower conversion rates for the supported catalyst. Quantitative epoxy conversion was achieved and the amount of immobilized carbon dioxide increased from 15.2 wt% for CSBO to 19.6% for CLSO. The seed oil carbonates with variable carbonate content (20.2 to 26.8 wt%) were cured with 1,2-ethane diamine (EDA), 1,4-butane diamine (BDA) and isophorone diamine (IPDA) in order to examine the thermal and mechanical properties of the resulting non-isocyanate polyurethanes (NIPU). In contrast to the flexible conventional CSBO/EDA-NIPU, it was possible to increase NIPU glass transition temperatures from 17 °C to 60 °C and to improve stiffness, as expressed by Young's modulus, by three orders of magnitude. Higher crosslink densities accounted for reduced water swelling and toluene uptake.

Thermal and X-Ray Diffraction Studies on Interpenetrating Polymer Networks of Soybean Oil-Based Polyurethane and Cardanol-Based Dye

The mixed ester polyol (MEP) is obtained from refined soybean oil on treatment with glycerol at 210°C in presence of lithrage. The probable structure of MEP was established by IR spectra. The polyurethane synthesized from MEP and diphenyl methane diisocyanate (DPMDI) with varying NCO:OH ratios were reacted with cardanol-o-aminophenol dye using ethyleneglycol dimethacrylate (EGDM) as a cross-linking agent and benzoyl peroxide as initiator. The PU was thoroughly characterized by IR spectroscopy. The thermal behavior of the Interpenetrating polymer networks was characterized by TG and the Morphology was studied by XRD studies.

Thermal and mechanical properties of glass reinforced soy-based polyurethane composites

Two series of polyurethane resins were prepared using Soypolyol 204 derived from soybean oil and petrochemical polyol Jeffol G30-650. Polyurethanes from soybean oil have good thermal, oxidative and weather stability, and can be used as a matrix in composite materials. The objective of this study was to compare the mechanical properties of untreated E-glass fiber reinforced composites prepared with soybean oil-based polyurethanes to that of the petrochemical polyol based ones. The effect of the polyurethane resin on physical and mechanical properties was studied. The results showed that mechanical properties such as tensile and flexural strength, tensile and flexural modulus of the Soypolyol based composites were comparable with those from composites based on petrochemical polyol. Since soy-based polyurethanes offer better thermal, oxidative and hydrolytic stability than petrochemical based ones, they could be a viable alternative to the petrochemical urethane matrix resins for composites.