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At least 19 records

Properties and performance of lignin-based polyurethane foams from lignin and castor oil as synergistic bio-polyols

Lignin and castor oil with intrinsic hydroxyl groups are attractive green resources for polyurethane (PU) applications. However, lignin's heterogeneous and highly crosslinked structure, poor processability, as well as the feedstock variability, lead to inconsistent and poor performance of the final foam products. Castor oil-based polyurethane foam (PUF) has a relatively high price and density, which are big hurdles to its practical applications. Here, in this study, we hypothesized that synergistic bio-polyol mixtures composed of lignin and castor oil could balance the drawbacks from individual component. Castor oil could improve the dispersity of lignin, while lignin simultaneously addressed the issues caused by PUF prepared with castor oil, such as its high density and low thermal stability. For a comprehensive understanding of the effects of structural properties of lignin on its PUF processing and applications, various lignin fractions were isolated by co-solvent enhanced lignocellulosic fractionation (CELF) from different species, including hardwood, softwood, and herbaceous plants, and the processed lignins with different molecular weights were applied with castor oil. The lignin fractions with lower molecular weight showed good dispersity in castor oil with a high lignin content (up to 50 wt%) and completely replaced petroleum-based polyols. The produced foam with 50 wt% low-molecular-weight lignin fractions from woody biomass showed comparable/higher compressive strength (up to 20 psi) and thermal insulation performance (up to 5.69 R-value in −1 for 50 % L-Pine foam). In addition, this study revealed the relationship between lignin's structural properties and foam performance, providing insights for practical applications of lignin-based PUF.

Jeong, Soyeon [State Univ. of New York (SUNY), Syr↗

Polyurethane Foams Based on Biopolyols from Castor Oil and Glycerol

In this work, the synthesis of biopolyols derived from castor oil and different glycerols was performed by chemical glycerolysis with sodium hydroxide as catalyst at 225 °C. The biopolyol obtained from high purity glycerol led to predominantly MAG formation, whereas the biopolyol produced using crude glycerol, byproduct from biodiesel industry, resulted in higher DAG, TAG and FFA content due to the higher amount of water. Both biopolyols were employed for the synthesis of polyurethane (PU) foams by bulk polymerization using methylene diphenyl diisocyanate (MDI) at different NCO:OH ratios. The foams were evaluated by apparent density, insoluble fraction, Fourier transform infrared spectroscopy, scanning electron microscope and thermogravimetric analysis. The results showed that crude glycerol provided PU foams as much as commercial glycerol, however the characteristics may be different, mainly due to the presence of water in the reaction medium.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

Synthesis and acoustic properties study of castor‐oil‐based polyurethane foams with the addition of graphene‐oxide‐modified straw fibers

Abstract Polyurethane foam (PUF) can absorb sound by air friction and structural vibrations of cell walls. It is widely used as acoustic material in the automotive industry. According to existing studies, graphene oxide (GO) can improve the acoustic properties of PUF. However, GO tends to coalesce inside PUF. In this paper, straw fibers were modified with different concentrations of GO solution to embed GO on the surface of plant fibers. The GO was dispersed in the PUF using straw fibers. In addition, some studies show that the wrinkled morphology of the GO surface is believed to play a mechanical interlocking role in improving interfacial bonding, thus enhancing the stress transfer between the plant fibers and the polyurethane (PU) matrix and improving the mechanical properties of the PU composites. The acoustic and mechanical properties of the modified PU materials were observed by treating plant fibers with appropriate amounts of GO solution. The experimental study shows that the sample modified with 1 g L −1 GO solution reaches a maximum average sound absorption coefficient of 0.5838 when the straw fiber content reaches 0.5 g, and the sample modified with 2 g L −1 GO solution reaches a maximum transmission loss of 10.5333 when the straw fiber content reaches 1 g. © 2022 Society of Industrial Chemistry.

Yang, Keyao↗

Investigation of damping liquids for aircraft instruments

This report covers the results of an investigation carried on at the Bureau of Standards under a research authorization from, and with the financial assistance of, the National Advisory Committee for Aeronautics. The choice of a damping liquid for aircraft instruments is difficult owing to the range of temperature at which aircraft operate. Temperature changes affect the viscosity tremendously. The investigation was undertaken with the object of finding liquids of various viscosities otherwise suitable which had a minimum change in viscosity with temperature. The new data relate largely to solutions. The effect of temperature on the kinematic viscosity of the following liquids and solutions was determined in the temperature interval -18 degrees to +30 degrees C. (1) solutions of animal and vegetable oils in xylene. These were poppy-seed oil, two samples of neat's-foot oils, castor oil, and linseed oil. (2) solutions of mineral oil in xylene. These were Squibb's petrolatum of naphthene base and transformer oil. (3) glycerine solutions in ethyl alcohol and in mixture of 50-50 ethyl alcohol and water. (4) mixtures of normal butyl alcohol with methyl alcohol. (5) individual liquids, kerosene, mineral spirits, xylene, recoil oil. The apparatus consisted of four capillary-tube viscometers, which were immersed in a liquid bath in order to secure temperature control. The method of calibration and the related experimental data are presented.

Keulegan, G H↗

Water-Blown Castor Oil-Based Polyurethane Foams with Soy Protein as a Reactive Reinforcing Filler

To decrease the usage of petroleum based materials, a kind of bio-resource based composite foams were developed with soy protein isolate (SPI) as reactive reinforcing filler in castor oil based polyurethane foams (PUF) prepared by self-rising method using water as a blowing agent. The resulting composite foams were evaluated for their morphology, density, mechanical and biodegradation properties, etc. Fourier transform infrared spectroscopy study exhibited characteristic peaks for SPI and PUF and indicated that the amino groups and hydroxyl groups on SPI reacted with polyphenyl polymethylene polyisocyanates (PAPI) to increase the crosslinking degrees of the composite foams. Densities of the resultant composites were found to increase with increasing SPI content. Mechanical properties of the samples were improved with the increase of SPI content. The compost tests further proved that the composite PUF had better biodegradability than neat PUF. Therefore, this research has provided a simple method of preparing the bio-resource based polyurethane foams, while exploring the potential of using SPI in polyurethane foam applications.

36 MATERIALS SCIENCE↗

Fast-responding bio-based shape memory thermoplastic polyurethanes

Fast response shape-memory polyurethanes were prepared from bio-based polyols, diphenyl methane diisocyanate and butane diol. The bio-based polyester polyols were synthesized from 9-hydroxynonanoic acid, a product obtained by ozonolysis of fatty acids extracted from soy oil and castor oil. The morphology of polyurethanes was investigated by synchrotron ultra-small angle X-ray scattering, which revealed the inter-domain spacing between the hard and soft phases, the degree of phase separation, and the level of intermixing between the hard and soft phases. We also conducted thorough investigations of the thermal, mechanical, and dielectric properties of the polyurethanes, and found that high crystallization rate of the soft segment gives these polyurethanes unique properties suitable for shapememory applications, such as adjustable transition temperatures, high degree of elastic elongations, and good mechanical strength. In conclusion, these materials are also potentially biodegradable and biocompatible, therefore suitable for biomedical and environmental applications.

36 MATERIALS SCIENCE↗

Experiments on the stability of a liquid bridge in an axial electric field

The behavior of a neutrally buoyant liquid bridge was studied in the presence of axial electric fields. Silicone oil and a castor-oil-eugenol mixture were used to form cylinders with slenderness ratios larger than pi with strong, axial, dc electric fields. Below a certain field strength, a smooth transition to an axisymmetric, vaselike shape occurred. Circulation patterns were observed in these bridges. At lower field strengths, the bridge shape was more deformed and, at a well-defined field, pinch-off occurred. With ac fields, the field strength required to stabilize the bridge was higher and the collapse of the cylinder was much sharper. Upon interchanging the fluids, a steady axial field was found to destabilize cylinders with slenderness ratios less than 3. This behavior is consistent with that anticipated if the fluids behave as leaky dielectrics but not if they act as perfect dielectrics.

Sankaran, Subramanian↗

Vegetable Oil Based Polyurethane Containing 1,2,3-Triazolium Functional Groups as Antimicrobial Wound Dressing

Preparation of antimicrobial polyurethane wound dressing membranes from a mixture of castor oil and a novel soybean oil-based polyol containing 1,2,3-triazolium rings (QTSBO) was described in this research. QTSBO was prepared through N-alkylation of 1,2,3-triazole functional soybean oil (TSBO) with methyl iodide, and TSBO was synthesized from an azidated soybean oil and propargyl alcohol through click reaction. The excellent tensile strength of these dressings under dry state and minimum deterioration of this property at fully hydrated state guaranteed the mechanical protection of wounds during the entire period of the healing process. The measured quantities of equilibrium water absorption and water vapor transmission rate for the optimized dressings confirmed the applicability of the selected formulations for the preservation of proper moist environment over low exuding wounds. The cyto-compatibility of dressings was verified by the excellent ability of the dressings to support the growth and proliferation of dermal fibroblasts. Due to the presence of 1,2,3-triazolium rings the dressing showed efficient antimicrobial activity against different bacterial and fungal stains. Therefore, these dressing could promote wound healing by preserving moist and hygienic environment over the wound bed.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Better together: Protein partnerships for lineage-specific oil accumulation

Plant-derived oils are a major agricultural product that exist in both ubiquitous forms such as common vegetable oils and in specialized forms such as castor oil and coconut oil. These specialized oils are the result of lineage-specific metabolic pathways that create oils rich in unusual fatty acids. Considerable progress has been made toward understanding the enzymes that mediate fatty acid biosynthesis, triacylglycerol assembly, and oil storage. However, efforts to translate this knowledge into renewable bioproducts via engineered oil-producing plants and algae have had limited success. Here, we review recent evidence that protein–protein interactions in each of the three major phases of oil formation appear to have profound effects on specialized oil accumulation. We suggest that furthering our knowledge of the noncatalytic attributes of enzymes and other proteins involved in oil formation will be a critical step toward creating renewable bioproducts derived from high performing, engineered oilseeds.

59 BASIC BIOLOGICAL SCIENCES↗

Polymeric materials from renewable resources

The goals of our studies have been the use of renewable raw materials in the preparation of polymeric materials with diversified properties. In this context, lignosulfonate, which is produced in large scale around the world, but not widely used in the production of polymeric materials, was used to replace phenol and polyols in the preparation of phenolic- (Ligno-PH) and polyurethane-type (Ligno-PU) polymers, respectively. These polymers were used to prepare composites reinforced with sisal lignocellulosic fibers. The use of lignosulfonate in the formulation of both types of polymers was beneficial, because in general composites with improved properties, specially impact strength, were obtained. Composites were also prepared from the so called “biopolyethylene” (HDPE), curaua lignocellulosic fiber, and castor oil (CO). All composites HDBPE/CO/Fiber exhibited higher impact strength, when compared to those of the corresponding HDBPE/Fiber. These results, combined with others (eg SEM images of the fractured surfaces) indicated that, in addition to acting as a plasticizer, this oil may have acted as a compatibilizer of the hydrophilic fiber with the hydrophobic polymer. The set of results indicated that (i) mats with nano (diameter ≤ 100nm) and/or ultrafine (submicron scale) fibers were produced, (ii) hybrid fibers were produced (bio-based mats composites), (iii) cellulosic pulp (CP) and/or lignin (Lig) can be combined with PET matrices to control properties such as stiffness and hydrophilicity of the respective mats. Materials with diversified properties were prepared from high content of renewable raw materials, thus fulfilling the proposed targets.

36 MATERIALS SCIENCE↗

Two-step Conversion of Crude Glycerol Generated by Biodiesel Production into Biopolyols: Synthesis, Structural and Physical Chemical Characterization

In this work biopolyols were synthesized via two-step process from crude glycerol and castor oil. For better evaluation of analyzed process, the impact of its time and temperature on the structure and properties of biopolyols was determined. Obtained results fully justified conducting of synthesis in two steps. Prepared materials were characterized by hydroxyl value and water content comparable to polyols industrially applied in manufacturing of polyurethane materials. Synthesized biopolyols were characterized in terms of their chemical structure using spectroscopic techniques: Fourier transform infrared (FTIR) spectroscopy and nuclear magnetic resonance spectroscopy. Obtained data confirmed the influence of synthesis’ parameters on the chemical structure of prepared biopolyols and correlated with their other parameters. On both stages of reaction, collected by-products were also analyzed with FTIR spectroscopy.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Degradation Study of Biobased Polyester–Polyurethane and its Nanocomposite Under Natural Soil Burial, UV Radiation and Hydrolytic-Salt Water Circumstances

The current study focuses on the development of a formulation of polyester polyurethane (PEPU) samples using castor oil (CO) modified polyester polyol and partially biobased aliphatic isocyanate. The CO modified polyester polyol was synthesized employing transesterification reaction between CO and diethylene glycol in the presence litharge (PbO) catalyst. Subsequently, the modification of CO was confirmed using proton nuclear magnetic resonance ({sup 1}HNMR) spectra analysis. In the next stage, the biobased polyester polyurethane nanocomposites (PEPUNC) were prepared by incorporating 3 wt% OMMT nanoclay within PEPU through in situ polymerization technique. The produced PEPU was confirmed by Fourier transform infrared spectroscopy (FTIR) and {sup 1}HNMR spectra analysis. Further, the degradation properties of developed PEPU subjected to soil-burial, UV exposure and hydrolytic-salt water medium were noted by FTIR spectroscopy. Corresponding weight loss, mechanical measurements and morphological studies through scanning electron microscopy (SEM) analysis were studied. The results showed that the addition of OMMT nanoclay within the PEPU matrix produces significant improvement in the degradation rate which indicated the susceptibility of OMMT nanoclay to humidity upon exposure to soil burial. The produced microorganisms from the soil resulted in significant chemical and morphological changes in the entire structure of the PEPU. Additionally, the highest degradation and percentage of weight loss was observed under soil burial as compared to UV exposure and hydrolytic-salt water medium.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Friction and Wear Modifiers Using Solvent Partitioning of Hydrophilic Surface-interactive Chemicals Contained in Boundary Layer-targeted Emulsions

A wear and/or friction reducing additive for a lubricating fluid in which the additive is a combination of a moderately hydrophilic single-phase compound and an anti-wear and/or anti-friction aqueous salt solution. The aqueous salt solution produces a coating on boundary layer surfaces. The lubricating fluid can be an emulsion-free hydrophobic oil, hydraulic fluid, antifreeze, or water. Preferably, the moderately hydrophilic single-phase compound is sulfonated castor oil and the aqueous salt solution additionally contains boric acid and zinc oxide. The emulsions produced by the aqueous salt solutions, the moderately hydrophilic single-phase compounds, or the combination thereof provide targeted boundary layer organizers that significantly enhance the anti-wear and/or anti-friction properties of the base lubricant by decreasing wear and/or friction of sliding and/or rolling surfaces at boundary layers.

Richmond, Robert Chafee↗

Friction and Wear Modifiers Using Solvent Partitioning of Hydrophilic Surface-Interactive Chemicals Contained in Boundary Layer-Targeted Emulsions

A wear and/or friction reducing additive for a lubricating fluid in which the additive is a combination of a moderately hydrophilic single-phase compound and an anti-wear and/or anti-friction aqueous salt solution. The aqueous salt solution produces a coating on boundary layer surfaces. The lubricating fluid can be an emulsion-free hydrophobic oil, hydraulic fluid, antifreeze, or water. Preferably, the moderately hydrophilic single-phase compound is sulfonated castor oil and the aqueous salt solution additionally contains boric acid and zinc oxide. The emulsions produced by the aqueous salt solutions, the moderately hydrophilic single-phase compounds, or the combination thereof provide targeted boundary layer organizers that significantly enhance the anti-wear and/or anti-friction properties of the base lubricant by decreasing wear and/or friction of sliding and/or rolling surfaces at boundary layers.

Richmond, Robert Chaffee↗

Friction and Wear Modifiers Using Solvent Partitioning of Hydrophilic Surface-Interactive Chemicals Contained in Boundary Layer-Targeted Emulsions

A wear and/or friction reducing additive for a lubricating fluid in which the additive is a combination of a moderately hydrophilic single-phase compound and an anti-wear and/or anti-friction aqueous salt solution. The aqueous salt solution produces a coating on boundary layer surfaces. The lubricating fluid can be an emulsion-free hydrophobic oil, hydraulic fluid, antifreeze, water, or a water-based lubricant. Preferably, the moderately hydrophilic single-phase compound is sulfonated castor oil and the aqueous salt solution additionally contains boric acid and zinc oxide. The emulsions produced by the aqueous salt solutions, the moderately hydrophilic single-phase compounds, or the combination thereof provide targeted boundary layer organizers that significantly enhance the anti-wear and/or anti-friction properties of the base lubricant by decreasing wear and/or friction of sliding and/or rolling surfaces at boundary layers.

Richmond, Robert Chaffee↗

Structure/property relationships in copolymers comprising renewable isosorbide, glucarodilactone, and 2,5-bis(hydroxymethyl)furan subunits

Carbohydrates and their derivatives have great potential as building blocks for the development of renewable materials that are cost and performance competitive with conventional petroleum-based materials. To this end, the rigid carbohydrate-derived diols, glucarodilactone and isosorbide were functionalized with a castor oil derivative, 10-undecenoic acid, forming α,ω-dienes suitable for acyclic diene metathesis (ADMET) polymerization. Equimolar copolymerizations of these two monomers, glucarodilactone undecenoate (GDLU) and isosorbide undecenoate (GDLU), transform brittle homopolymers into elastic materials with shape memory capabilities. To understand the source of these properties, a series of copolymers consisting of a range of GDLU and IU compositions (100:0, 77:23, 76:24, 52:48, 48:52, 18:82, 0:100 mol percent GDLU to IU) was synthesized. The material and chemical properties were characterized by uniaxial tensile testing, small-amplitude oscillatory shear rheology, X-ray scattering and hydrolytic degradation testing. Small compositional changes in this family were shown to have a drastic impact on the observed mechanical performance and degradability of these materials. Rheological measurements of GDLU-containing copolymers found evidence for the presence of transient networking within these materials. We posit that the transient network within this material is responsible for the elasticity and shape memory abilities of the GDL-containing materials. In confirmation of these properties, a novel α,ω-diene 2,5-bis(hydroxymethylfuran) undecenoate (BHMFU) was developed and served as a direct replacement for either GDLU or IU in copolymerizations. The replacement of GDLU resulted in a total loss of the elasticity and shape memory of the copolymers, supporting the role of GDLU in the mechanical performance.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Biobased chemical recycling: aminolysis of PET using renewable reagents and monomers to synthesize new semi-aromatic polyamides

Chemical recycling of PET is a method of depolymerizing polymer chains to monomeric components enabling the synthesis of second-generation materials with virgin-like quality. Commercial chemical recycling techniques rely upon high pressure methanolysis to create precursors capable of synthesizing a second-generation PET resin. However, despite the circular approach of methanolysis, a product with a very short lifespan and similar value is created. The approach of the current study is to utilize aminolysis as an ambient pressure technique to create precursors for higher value materials with longer lifespans to address the current crisis in plastic waste. Semi-aromatic polyamides (SAP) are desired in this circumstance because of their high melting point and heat resistance combined with good melt-processability similar to aliphatic polyamides. In this study SAPs were synthesized using precursors recovered from the aminolysis of PET employing biobased diamines and dicarboxylic acids. While aminolysis has been explored in previous studies, this work investigated the use of biobased components from castor oil: decamethylene diamine during recycling and sebacic acid during polymerization. Polymer synthesis resulted in the formation of SAPs similar to polyphthalamides (PPA) with novel structures given the aromatic portion from terephthalic acid (TPA) and aliphatic portion from the diamines and diacids. The synthesized materials exhibited excellent thermal stability with high glass transition temperatures. Novel polymers were created with varying aliphatic chain length to understand fundamental parameters needed to produce a valuable polymer from post-consumer waste.

High performance Applications↗