Bio-based Polyols Research Articles

Imine-containing Self-healing Waterborne Polyurethane Elastomeric Coating Derived from Bio-based Polyester Polyol

Imine-containing Self-healing Waterborne Polyurethane Elastomeric Coating Derived from Bio-based Polyester Polyol

Optimization of reed-based polyol production driven by response surface methodology and machine learning: Process modeling and hydroxyl value prediction

In pursuit of sustainable development goals, the transformation of biomass resources into high-value chemicals has become a focal point within the academic community. Despite being a biomass resource, reed (Phragmites australis) has not yet fully realized its potential in the production of bio-based polyols. This study utilized Response Surface Methodology (RSM) and an Artificial Neural Network (ANN) enhanced by a Genetic Algorithm (GA) to model and optimize the liquefaction process of reeds. Furthermore, this study employed a pre-existing predictive model to estimate the hydroxyl value of reed-derived liquefaction products, thereby aiming to curtail expenses during the biomass chemical development phase. The results demonstrated that both the RSM and GA-ANN models accurately predict bio-polyol yield, with the RSM model outperforming the ANN model. Based on optimal conditions predicted by the RSM model, the best experimental process parameters were established: raw material particle size 2–12 mesh, solid-liquid ratio 5:1, glycerol content 32.5 %, catalyst content 3.6 %, temperature 169 °C, and reaction time 58 minutes. Under these conditions, the polyol yield reached 89.145 %, with a relative deviation of 2.366 %, and the bio-polyol exhibited a viscosity of 0.51 Pa·s. The predicted hydroxyl value for the bio-based polyol was found to be 399.19 mg KOH/g. The liquefied product is rich in hydroxyl groups, indicating its potential application value in preparing bio-based polymer materials. This study introduces innovative approaches to the economical production of bio-based polyols at the laboratory scale, which may pave the way for their broader industrial implementation.

Environmental benefits of valorising food waste into bio-based polyols for the production of polyurethane rigid foams

Under the global pursuit of sustainable development, waste streams are being recognised as renewable feedstocks to produce value-added products. Given this, food waste (FW) was explored to synthesise bio-based polyols to further develop polyurethane rigid foams (PURF). However, relevant environmental aspects are yet to be examined to support this biorefinery scheme as a green and sustainable solution. In this work, we examined the environmental performance associated with the production of PURF using polyols derived from a FW biorefinery scheme by life cycle assessment (LCA). Analysis was first conducted at the polyol level. Different allocation and offset options were examined to configure the LCA model. Based on mass allocation, compared with fossil-based production, the production of FW-derived polyols achieved reductions of 24.30 % and 34.19 % in global warming potential (GWP) and cumulative energy demand (CED), respectively. At the midpoint level, FW-derived polyols had reduced impacts on human carcinogenic toxicity, freshwater eutrophication, and fossil resource scarcity but caused additional burdens on freshwater and marine ecotoxicity. Key environmental hotspots at this level included diethylene glycol, ion exchange resin (epoxidation catalyst), and hydrogen peroxide. The lipid content in FW also played a significant role. It was demonstrated that reducing the use of enzymes for FW hydrolysis to a cost-effective level remarkably mitigated the overall impacts of FW-derived polyol production. At the next level, we examined the production of FW-derived PURF using the obtained polyols. When 70 % of the polyols were replaced with bio-based products, the resultant PURF production achieved a GWP and CED of 5.67 kg CO2eq and 110.66 MJ/kg, respectively. In general, FW-derived PURF leads to environmental benefits compared to fossil-based ones. However, isocyanate used for foam formulation was the dominant contributor, causing almost two-thirds of the total impacts. The flame retardant also caused considerable impacts. Through the systematic examination of FW-derived polyols and PURF, this study demonstrated that FW-derived PURF could benefit the sustainable development of FW biorefineries and bio-based plastic industries, while the identified environmental hotspots need to be further studied and replaced with greener substitutes. AcronymsUnlabelled TableCEDCumulative energy demandDEGDiethylene glycolDALYDisability-adjusted life yearsFWFood wasteGWPGlobal warming potentialLCALife cycle assessmentLCILife cycle inventoryMDIMethylene diphenyl diisocyanateNIPUNon-isocyanate polyurethanespMDIPolymeric 4,4′-methylene diphenyl isocyanatePURFPolyurethane rigid foamsPUsPolyurethanesTPhPTriphenyl phosphateTCPPTris(1-chloro-2-propyl) phosphate

Biopolyurethane coatings with silica-titania microspheres (MICROSCAFS®) as functional filler for corrosion protection

In this work, we studied a biopolyurethane (BioPU) coating derived from a bio-based polyol and isocyanate for the protection of carbon steel against corrosion. The direct utilization of polyols obtained from raw biomass represents a novelty in polyurethane coatings production. The protective properties of these coatings were enhanced by incorporating unique silica-titania (ST) MICROSCAFS®, which are microspheres exhibiting interconnected macro- and mesoporosity. They were loaded with tannic acid (TA), an eco-friendly corrosion inhibitor. Confirmation of TA loading into the ST carriers (therefore called ST\\TA) was achieved through Attenuated total reflectance - Fourier-transform infrared spectroscopy (ATR-FTIR) and Thermogravimetric (TG) analyses. TG analysis revealed that ST\\TA particles contain approximately 34 wt% TA, and their average particle diameter is approximately 25 ± 5 μm, observed by SEM. The TGA shows slightly improved thermal resistance of the coatings modified with the filler MICROSCAFS®. Furthermore, it was observed that the fillers strengthened the coating hardness without negatively affecting the adhesion strength. Electrochemical Impedance Spectroscopy (EIS) results demonstrated that all modified coatings exhibited very good to excellent resistance in mild corrosive environments. The coatings maintained a high impedance modulus (|Z|) at low frequencies and phase angle values close to −90° across a wide frequency range, over an immersion period of 80 days in a 0.05 M NaCl solution. After 80 days of immersion, the best coating, BPU-ST\\TA, displayed |Z| of 3 × 1010 Ω cm2. Scanning Vibrating Electrode Technique (SVET) analysis revealed the inhibitory behaviour of TA. For the BPU-ST\\TA sample, inhibition of both anodic and cathodic activities was clearly visible, with a significant reduction of the current densities starting at 1 h and up to at least 24 h of immersion. In summary, the BioPU coatings modified with tannic acid-loaded MICROSCAFS® exhibit improved barrier properties and notable corrosion inhibition capacity in mild corrosive environments.

Bio-Based Polyurethane Composites from Macauba Kernel Oil: Part 1, Matrix Synthesis from Glycerol-Based Polyol

Polyurethanes are the result of a reaction between an isocyanate and a polyol. The large variety of possible reagents creates many possible polyurethanes to be made, such as soft foams, rigid foams, coatings, and adhesives. This polymer is one of the most produced and consumed polymers in the world with an ever-increasing demand. Despite its usual petrochemical nature, research on bio-based polyurethanes flourishes due to the ease in creating bio-based polyols. This work covers the synthesis of a novel macauba kernel oil polyol by the epoxidation of the oil, followed by a ring-opening reaction of the epoxide with glycerol, used for the preparation of polyurethane foams using different NCO/OH ratios. The FTIR and H1 results confirm the formation of the epoxide and polyol, and the polymers in all NCO/OH ratios were confirmed by FTIR, showing great similarities between the samples, especially PU 1.0 and PU 1.2. Despite the TGs showing close behaviors for the three samples, their DTGs showed great difference between the samples, with PU 1.0 presenting a regular PU DTG profile with three degradation peaks while the other two sample presented five degradation peaks, indicating a higher crosslinking density in them.

Synthesis of bio-polyol-functionalized nanocrystalline celluloses as reactive/reinforcing components in bio-based polyurethane foams by homogeneous environment modification

Nanocrystalline Cellulose (NCC or CNC) is widely used as a filler in polymer composites due to its high specific strength, tensile modulus, aspect ratio, and sustainability.However, CNC hydrophilicity complicates its dispersion in hydrophobic polymeric matrices giving rise to aggregate structures and thus compromising its reinforcing action. CNC functionalization in a homogeneous environment, through silanization with trichloro(butyl)silane as a coupling agent and subsequent grafting with bio-based polyols, is herein investigated aiming to enhance CNC dispersibility improving the filler-matrix interaction between the hydrophobic PU and hydrophilic CNC. The modified CNCs (m_Ci) have been studied by XRD, SEM, and TGA analyses. The TGA results show that the amount of grafted polyol is strongly influenced by both its molar mass and OH number and the maximum amount of grafted polyol reaches up to 0.32 mmol per grams of functionalized CNC, within the explored conditions. The effect of different concentrations (1–3 wt%) of m_Ci on the physical, morphological, and mechanical properties of the resulting bio-based composite polyurethane foams is evaluated. Composite PU foams present compressive modulus up to 4.81 MPa and strength up to 255 kPa more than five times higher than those reinforced with unmodified CNC or with modified CNC in heterogeneous chemical environment. The improvement of mechanical properties of the examined PU foams, as a consequence of the incorporation of bio-polyols modified CNCs where polyol's OH groups interact with polyurethane precursors, could further broaden the use of these materials in building applications.

Flame Retardant Rigid Polyurethane Foam Derived from Biobased Polyols and Water as Co-Blowing Agent: Synergistic Effect of Expanded Graphite and Boron Nitride

Using a bio-based polyol system one-shot free-rising method, bio-based flame-retardant rigid polyurethane foam (FR-RPUF) was prepared. Environmentally friendly blowing agent (Cyclopentane) and co-blowing agent water along with expanded graphite (EG) and boron nitride (BN) were used as admixtures to develop a synergistic flame-retardant composite at a variable ratio of EG and BN respectively. The flame retardancy of the composite was evaluated using various techniques like burning tests, UL 94, and cone calorimetry. At the same time, the morphological aspects and functional groups were analyzed by scanning electron microscopy (SEM) and Fourier Transform Infrared spectroscopy (FTIR) respectively. The FR-RPUF synthesized using EG and BN at a ratio of 1:1 has impressive flame-retardancy and smoke-suppressing properties, with a "V-1" rating in the UL-94 vertical burning testing. Additionally, EG/BN- FR-RPUF has a compressive modulus of 4.92MPa, making it suitable for discontinuous panel applications.

Cryogenic Insulation-Towards Environmentally Friendly Polyurethane Foams.

Cryogenics is the science and technology of very low temperatures, typically below 120 K. The most common applications are liquified natural gas carriers, ground-based tanks, and propellant tanks for space launchers. A crucial aspect of cryogenic technology is effective insulation to minimise boil-off from storage tanks and prevent frost build-up. Rigid closed-cell foams are prominent in various applications, including cryogenic insulation, due to their balance between thermal and mechanical properties. Polyurethane (PU) foam is widely used for internal insulation in cryogenic tanks, providing durability under thermal shocks and operational loads. External insulation, used in liquified natural gas carriers and ground-based tanks, generally demands less compressive strength and can utilise lower-density foams. The evolution of cryogenic insulation materials has seen the incorporation of environmentally friendly blowing agents and bio-based polyols to enhance sustainability. Fourth-generation physical blowing agents, such as HFO-1233zd(E) and HFO-1336mzz(Z), offer low global warming potential and improved thermal conductivity. Additionally, bio-based polyols from renewable resources like different natural oils and recycled polyethylene terephthalate (PET) are being integrated into rigid PU foams, showing promising properties for cryogenic applications. Research continues to optimise these materials for better mechanical performance and environmental impact.

Sustainable castor oil-based microcellular polyurethane foam with desirable flame retardancy, vibration damping performance and recyclability

Microcellular polyurethane foam (MPUF) is extensively utilized as a vibration dampening material. However, its long chain and porous composition render it highly susceptible to combustion. Herein, we grafted the flame retardant 9,10-dihydro-9-oxa-10-phospha-phenanthrene-10-oxide (DOPO) onto the castor oil by a simple method to obtain a bio-based flame-retardant polyester polyol (COBH). Then, a bio-based flame-retardant MPUF was synthesized by one-pot synthesis of COBH, polyether polyol, and isocyanate. The target MPUF exhibits excellent flame retardancy, with the limiting oxygen index (LOI) sharply increasing from 19.3 % to 27.6 % and the peak of heat release rate (PHRR) decreasing significantly by 60.1 % as compared to MPUF prepared using unmodified castor oil. In addition, the MPUF shows good vibration dampening performance with a maximum loss factor of 5.2 and a maximum Sc-factor of 250. Moreover, the MPUF can be processed into MPU film by compression molding. The MPU film has adjustable mechanical properties and reusability. This study provides a feasible method for the preparation of flame-retardant, recyclable, bio-based MPUF with good vibration damping properties, thus expanding the practical applications of MPUF in the automotive, aerospace, and packaging and transportation industries.

Fabrication of nickel phytate modified bio-based polyol rigid polyurethane foam with enhanced compression-resistant and improved flame-retardant

A bio-based flame retardant nickel phytate (PA-Ni) was synthesized and combined with soybean oil-based polyol (SO) to create a green rigid polyurethane foam (RPUF) with enhanced compressive strength, good thermal stability and flame retardant. The results showed that the RPUF-SO2/Ni3 with 3 wt% PA-Ni had the highest initial and termination temperature, maximum thermal decomposition rate temperature and carbon residue, and better thermal stability. Its limiting oxygen index was increased by 2.6% compared with RPUF-SO2 without PA-Ni added, and the peak heat release rate (PHRR) and total heat release rate (THR) were reduced by 14.92% and 19.92%, respectively. In addition, RPUF-SO2/Ni3 had the lowest Ds under the conditions of flame (18.90) and flameless (22.41), and had the best smoke suppression effect. And the compressive strength of RPUF-SO/Ni3 was significantly enhanced by the addition of PA-Ni. The results show that the improvement of flame retardancy of RPUF is mainly the result of the combined effect of gas-phase and condensed-phase flame retardancy, among which the flame retardancy of RPUF-SO/Ni3 was the best. The current findings offer a practical way to produce green and low-carbon RPUF as well as promising prospects for the material's safe application.

A novel naturally superoleophilic coconut oil-based foam with inherent hydrophobic properties for oil and grease sorption

Absorption methods using polyurethane foams (PUFs) have recently gained popularity in treating oil spills. However, conventional petroleum-based PUFs lack selectivity and are commonly surface-modified using complicated processes that require toxic and harmful solvents to enhance their hydrophobicity and oil sorption capacities. In this paper, a novel naturally superoleophilic foam with inherent hydrophobic properties has been developed through the conventional one-shot foaming method with the integration of coconut oil-based polyol. This bio-based polyol was explicitly handpicked as it is chiefly saturated, highly abundant, and inexpensive. The foam is characterized by an oil sorption capacity range of 14.89–24.65 g g−1 for different types of oil, equivalent to 578–871 times its weight. Its hydrophobic behavior is expressed through a water contact angle of ~ 139°. The foam also showcased excellent chemical stability and high recyclability without a significant loss in absorption capacity after 20 cycles. The incorporation of the coconut oil-based polyol is also shown to improve the morphological, mechanical, and thermal behavior of the foam. It can be inferred from these findings that this novel material holds great potential for revolutionizing sorbents, pioneering a more sustainable and eco-friendly functional material produced via a facile method.

Investigation of bio-based rigid polyurethane foams synthesized with lignin and castor oil

In this study, polyurethane (PU) foams were manufactured using kraft lignin and castor oil as bio-based polyols by replacing 5–20 wt% and 10–100 wt% of conventional polyol, respectively. To investigate the effects of unmodified bio-based polyols on PU foam production, reactivity and morphology within PU composites was analyzed as well as mechanical and thermal properties of the resulting foams. Bio-based PU foam production was carried out after characterizing the reagents used in the foaming process (including hydroxyl group content, molecular weight distribution, and viscosity). To compare the resulting bio-based PU foams, control foam were produced without any bio-based polyol under the same experimental conditions. For lignin-incorporated PU foams, two types, LPU and lpu, were manufactured with index ratio of 1.01 and 1.3, respectively. The compressive strength of LPU foams increased with lignin content from 5 wt% (LPU5: 147 kPa) to 20 wt% (LPU20: 207 kPa), although it remained lower than that of the control foam (PU0: 326 kPa). Similarly, the compressive strength of lpu foams was lower than that of the control foam (pu0: 441 kPa), with values of 164 kPa (lpu5), 163 kPa (lpu10), 167 kPa (lpu15), and 147 kPa (lpu20). At 10 wt% lignin content, both foams (LPU10 and lpu10) exhibited the smallest and most homogenous pore sizes and structures. For castor oil-incorporated PU foams with an index of 1.01, denoted as CPU, increasing castor oil content resulted in larger cell sizes and void fractions, transitioning to an open-cell structure and decreasing the compressive strength of the foams from 284 kPa (CPU10) to 23 kPa (CPU100). Fourier transform infrared (FT-IR) results indicated the formation of characteristic urethane linkages in PU foams and confirmed that bio-based polyols were less reactive with isocyanate compared to traditional polyol. Thermogravimetric analysis (TGA) showed that incorporating lignin and castor oil affected the thermal decomposition behavior. The thermal stability of lignin-incorporated PU foams improved as the lignin content increased with char yields increasing from 11.5 wt% (LPU5) to 15.8 wt% (LPU20) and from 12.4 wt% (lpu5) to 17.5 wt% (lpu20). Conversely, the addition of castor oil resulted in decreased thermal stability, with char yields decreasing from 10.6 wt% (CPU10) to 4.2 wt% (CPU100). This research provides a comprehensive understanding of PU foams incorporating unmodified biomass-derived polyols (lignin and castor oil), suggesting their potential for value-added utilization as bio-based products.

Valorisation of food waste into bio-based polyurethane rigid foams: From experimental investigation to techno-economic analysis

Food waste (FW) constitutes a significant portion of municipal solid waste and thus requires proper treatment. A ‘waste-to-wealth’ concept, in this case, urges the valorisation of FW to produce value-added products, given that such waste contains significant quantities of diverse nutrients. While most of these efforts have been focused on the recovery of carbohydrates, this paper introduces an FW biorefinery scheme to valorise FW lipids (FWLs) into bio-based polyols for polyurethane rigid foams (PURF). Considering economic viability, cost-effective dosages of enzymes for FW hydrolysis were first investigated. Subsequently, the obtained FWLs were converted into bio-based polyols through stepwise epoxidation and oxirane ring-opening. Characterisation results showed that FW hydrolysis aided the development of FWL-derived polyols into PURF. Moreover, the obtained PURF exhibited excellent properties that are suitable for thermal insulation applications in the fields of civil engineering and appliances. A further techno-economic analysis demonstrated a promising profitability of valorising FW into PURF. Proven as material-intensive, critical cost drivers of the proposed valorisation scheme mainly included the price of the PURF and the chemicals required for the synthesis. The FW processing rate also significantly influenced the economic viability. By providing a successful valorisation pathway from FW to PURF and highlighting vital economic variables, this work aims to provide insights to promote the sustainable development of FW biorefineries and relevant bio-based polymer industries.

Synthesis and characterization of bio‐based poly(urethane‐urea) nanocomposite coatings employing cellulose nanocrystals incorporated by two different routes

AbstractDuring the last decades, the interest in the development of materials fully or partially biobased has increased. Polyurethanes are extensively used in a wide range of industries because of their versatility. The present work explores the synthesis of partially biobased poly(urethane‐urea) (PUU) composites employing soy‐based polyol (SPO) and cellulose nanocrystals (CNC). The latter were incorporated during the synthesis (in‐situ) or after the synthesis (ex‐situ). The possibility of a technological application as coatings was investigated for the designed materials. Polycaprolactone diol was used as a soft segment due to high functionality of the soy‐based polyol. The physicochemical, thermal and mechanical properties of the prepared matrices were analyzed. Poly(urethane‐urea)s containing up to 20% by weight of biobased polyol showed coating application potentiality. Compared to a polycaprolactone‐based polyurethane, the utilization of the bioprecursor enhanced light absorption in the UV–Vis region. In addition, partially biobased systems showed better mechanical resistance (Young's modulus increased up to 6 times) and hydrophobicity (sweeling decreased from 60 to 8 per cent by weight). Incorporation of cellulose nanocrystals affected primarily the physicochemical and rheological properties of dispersions. Regarding coating properties, nanocrystals utilization complemented the soy‐based polyol improving the performance of the films. Furthermore, the incorporation route affected the dispersions and films properties.Highlights SPO was incorporated up to 20 per cent by weight in PUU composites. Higher SPO contents improved UV–Vis absorption and tensile strength of films. Films were less hydrophilic as more SPO was incorporated. The CNC‐reinforcement was complementary to the utilization of the SPO. CNC incorporation route affects properties and performance of the coatings.

Elucidating the Impact of Polyol Functional Moieties on Exothermic Poly(urethane-urea) Polymerization: A Thermo-Kinetic Simulation Approach

The pursuit of sustainable polyurethane (PU) product development necessitates a profound understanding of precursor materials. Particularly, polyol plays a crucial role, since PU properties are heavily influenced by the type of polyol employed during production. While traditional PUs are solely derived from hydroxyl functionalized polyols, the emergence of amine-hydroxyl hybrid polyols has garnered significant attention due to their potential for enhancing PU product properties. These hybrid polyols are characterized by the presence of both amine and hydroxyl functional groups. However, characterizing these polyols remains a daunting challenge due to the lack of established experimental testing standards for properties, such as fractional hydroxyl and amine moieties and thermo-kinetic parameters for amine reactions with isocyanates. Additionally, characterization methods demand extensive time and resources and pose risks to health and the environment. To bridge these gaps, this study employed computational simulation via MATLAB to determine the moieties’ fractions and thermo-kinetic parameters for hybrid polyols. The computational method integrated energy balance and reaction kinetics analysis for various polyols to elucidate the influence of functional moieties on the thermo-kinetic behavior of PU formations. Validation of the simulated results was conducted by comparing their experimental and simulated prepolymer and foam temperature profiles, highlighting the direct influence of fractional moieties on PU formations. The comparisons revealed an average relative error of less than 5%, indicating the accuracy and credibility of the simulation. Thus, this study represents a pivotal opportunity for advancing knowledge and driving sustainable developments in bio-based polyol characterization for PU production streamlining and formulation optimization.

Biodegradable Polyurethane Pressure-Sensitive Adhesives Using Biobased Polyols with Distinct Intrinsic Properties

Biodegradable Polyurethane Pressure-Sensitive Adhesives Using Biobased Polyols with Distinct Intrinsic Properties

Ceresin wax enhances hydrophobicity and density of bio-based polyurethane of controlled-release fertilizers: Streamlined production, improved nutrient release performance, and reduced cost

Bio-based coated controlled-release fertilizers (BCRFs) can significantly improve nutrient utilization and reduce pollution. However, challenges such as spray gun clogging, adhesion and tearing between fertilizers during the actual production of BCRFs pose a severe challenge to production chain development. In addition, the poor hydrophobicity and cross-linking properties of bio-based coatings severely affect the controlled release properties of BCRFs. Although some measures have been taken to ameliorate the above problems, the cumbersome and costly modification process is challenging to be applied on a large scale. Therefore, the primary goal of this work is to search for a more straightforward and efficient method of production and modification to address the aforementioned unresolved challenges in the field of CRFs. In this study, bio-based polyester polyol (BPP) was used as the base for polyurethane reaction, and low-viscosity castor oil (CO) was used as the modifier to reduce the viscosity of BPP. This led to the preparation of Inter-Modified Coated Controlled-Release Fertilizers (ICRFs) to prevent spray gun clogging. Building upon this, hydrophobic and dense wax-based coated fertilizer (WBCF) was prepared by modifying ICRF with Ceresin wax to alleviate the challenges associated with adhesion and tearing between fertilizer particles during the coating process. The WBCF exhibited remarkable controlled-release characteristics, with a nitrogen (N) release longevity of nearly 180 days, requiring only 3 % of the coating materials. This work provides a simple and efficient strategy for overcoming the key constraints in the development and production of CRFs and provides insights into developing green, low-cost fertilizers with excellent controlled-release properties.

Development of lactic acid based chain extender and soybean oil-derived polyurethanes for ecofriendly sustained drug delivery systems

In the present study, a range of sustainable, biocompatible and biodegradable polyurethanes (PU-1 to PU-4) were synthesized using different combinations of biobased polyol (obtained through the epoxidation of soybean oil, followed by ring opening with ethanol) and polyethylene glycol (PEG) and isophorone diisocyanate. The sustainable chain extender used in this study was synthesized by the esterification of lactic acid with ethylene glycol (EG). The synthesized PU samples were characterized through scanning electron microscopy (SEM), Fourier transformed infrared (FTIR) and nuclear magnetic resonance (1H NMR and 13C NMR) spectroscopy. Wetting ability and thermal degradation analysis (TGA) of the samples were also studied. Subsequently, these PUs were examined as potential drug delivery systems using Gabapentin as a model drug, which was loaded in the polymer matrix using the solvent evaporation method. The drug release studies were carried out in 0.06 N HCl as a release medium according to the method outlined in the United States Pharmacopeia. The maximum drug release was observed for sample PU-P1, which was found to be 53.0 % after 6 h. Moreover, a comparison of different PU samples revealed a trend wherein the values of drug release were decreased with an increase in the PEG content.

Structure versus hydrolytic and thermal stability of bio-based thermoplastic polyurethane elastomers composed of hard and soft building blocks with high content of green carbon

Nowadays, sustainability plays a key role in the design and synthesis of new materials. One of the methods for the preparation of green materials is incorporation into their structure the monomers with a high content of green carbon. Therefore, the aim of this work was to investigate the influence of the type and molecular mass of two bio-based polyester polyols and bio-glycol on the properties of aliphatic partially bio-based thermoplastic polyurethane elastomers (bio-TPU). Two series of bio-TPUs materials composed of hard and soft building blocks with high green carbon content were prepared via the two-step method (prepolymer method). Two amorphous bio-based polyester polyols with the molecular mass ~ 2000 (P1) and ~ 3000 (P2) were used. Bio-TPUs were prepared at three different molar ratio of [NCO]/[OH]: 0.9, 0.95, and 1.0. In order to determine the influence of bio-based polyols and the content of hard segments on the properties of bio-TPU, relevant test methods were used. The Fourier transform infrared spectroscopy (FTIR), differential scanning calorimetry (DSC), and thermogravimetry (TG) revealed hydrolytic and thermal stability of bio-TPUs. Viscoelastic behavior, mechanical and physical properties were examined in terms of dynamic mechanical thermal analysis (DMTA), tensile test, hardness, and density. Analysis of the measurement results confirmed the significant influence of the molecular mass of the bio-based polyols and the molar ratio of [NCO]/[OH] on the bio-TPUs properties. Due to good mechanical properties, low density, and thermal stability up to 300 °C, the obtained materials can find many useful applications. This issue is essential in terms of sustainable development and reduction in the CO2 emissions to the atmosphere.

Adsorption of cationic dyes from aqueous solution onto modified nanocellulose reinforced porous bio based polyurethane hybrid composites

In this study polyurethane (PU) based porous composites were synthesized by using the biobased polyol derived from chaulmoogra and grape seed oils. These polyols were used for the preparation of porous PU composites using methylene diphenyl diisocyanate as hard segment and polyethylene glycol (PEG6000) as soft segment with 1,4-diazabicyclo[2, 2, 2]octane (DABCO) as catalyst. Swelling ratio of the PU were analyzed by using water, salt, acid and base buffers. Nanocellulose prepared from moringa olifera seed pods were modified (aminated, carboxylated and phosphorylated) and were added as fillers (1, 3, and 5 weight %) to obtain porous polyurethane composites. The prepared samples were also characterized by using XRD, SEM, FT-IR, along with other physical and chemical methods. The SEM results show the nanofibrillation of cellulose and closed cell porosity in polyurethane. The strength of nanocellulose filled polyurethane composites (mNC-PU) increased with the increase in the mNC-content. Using the obtained mNC as filler, porous polyurethane composite with good adsorption capacity were prepared, and were used for the adsorption of Indigo carmine (IC), Rhodamine-B(Rh-D) and mixed (binary) dye system. The experimental process parameters optimization was carried out using Box Behnken Design. The predicted and the experimental percentage of dye removal were found to be in good agreement with a maximum of experimental percentage dye removal being in the range of 85 to 94 % for both IC dye and Rh-D dye individually and from mixed dye system. The coefficient of determination value and adjusted coefficient of determination value indicated that the model had significant fit. An increase in pH was found to increase the sorption capacities of the porous polyurethane towards the dyes. Maximum adsorption was found in the higher pH range of 9–12.