WATER-BLOWN POLYURETHANE RIGID FOAMS MODIFIED BY CHEMICAL PLASTICATION

Water-blown polyurethane rigid foams are getting more and more attention, because the traditional blowing agent HCFC141b has already been abolished to prevent the ozone layer from destruction. However, the polyurethane rigid foams blown by water have serious defects, i.e. friability and resulting lower adhesion strength. Thus, the purpose of this study is to resolve the problems by chemical plastication. The maleate was added to polyol-premix containing water or to polyisocyanate,with both of which maleate does not react. To prove the reaction when polyol-premix and polyisocyanate were mixed, the model composite was synthesized and analyzed by IR, NMR and ESI (MS). Furthermore, a series of water-blown polyurethane rigid foams added different amount maleate were successfully prepared. By testing impact strength and adhesion strength of the foams, the actual effect of adding maleate was obtained.     

Environmentally Compatible Hybrid-Type Polyurethane Foams Containing Saccharide and Lignin Components

Semi-rigid polyurethane (PU) foams were prepared using lignin-molasses- poly(ethylene glycol) polyols. Two kinds of lignin, kraft lignin (KL) and sodium lignosulfonate (LS), were used. Both lignin and molasses polyols were mixed with various ratios and were reacted with poly(phenylene methylene) polyisocyanate (MDI) in the presence of silicone surfactant and di-n-butyltin dilaurate. A small amount of water was used as a foaming agent. The apparent density of PU foams increased with increasing lignin content. The compression strength and elastic modulus linearly increase with increasing apparent density, suggesting that mechanical properties are controllable by changing reaction conditions. The PU foams were amorphous and glass transition was detected by differential scanning calorimetry. The glass transition temperature (T_g ) maintained an almost constant value, regardless of the mixing ratio. This indicates that both the phenolic group of lignin and the glucopyranose ring of molasses act as rigid components in PU crosslinking network structures, and both groups contribute to the main chain motion to the same extent. By thermogravimetry (TG), it was confirmed that PU foams are thermally stable up to around 300 °C. By differential scanning calorimetry, T_g was observed at temperatures from 80 to 120 °C.     

Preparation and characterization of rigid polyurethane–polyglycerol nanocomposite foams

This work reports on the preparation of polyurethane–polyisocyanurate (PUR–PIR) foams containing different polyglycerols and layered silicate nanoclays. The rigid polyurethane foams were obtained in a laboratory scale, in a single step method, from a two-component system with a NCO to OH groups ratio equal to two. The reaction mixture consisted of the proper amounts of a commercial oligoetherpolyol, polyglycerol, catalysts, water, nanofiller, and polymeric diphenylmethane diisocyanate. The obtained foams containing 6% of one of three types of montmorillonite (MMT) (Cloisite 30B, Laponite RD, Bentonite) were characterized in terms of their structure, density, brittleness, compressive strength and thermal stability. The nanocomposite foams showed a higher number of cells with a smaller cell size in the presence of MMT, while the foams modified with nanofiller Cloisite 30B presented the best compressive strength and the best fire resistance.     

Structures and physical properties of rigid polyurethane foams with water as the sole blowing agent

Polyurethane rigid foams have been used for many applications such as pipelines insulation materials, automotive parts, solar water heater and construction materials[1,2], due to their desirable physical properties. Traditional rigid foam is made by the reaction of a polyol and 4,4′-diphenylmethane diisocyanate (MDI) with chlorofluorocarbons (CFCs), in particular tri- chlorofluoromethane (CFC-11) and/or HCFC-141b as blowing agents. However, the CFCs blowing agents contain halogens, whic…     

Epoxy modified polyurethane rigid foams

Rigid IPN foams were prepared by sequential polymerization of polyurethane and epoxy systems. Significantly higher compressive modulus and strength were observed with the IPN foams in comparison to the corresponding polyurethane rigid foams. The IPN foams show one glass transition temperature. The single T_g indicates the very small domain size in the PU-epoxy IPN's.     

Chlorine-Functional Silsesquioxanes (POSS-Cl) as Effective Flame Retardants and Reinforcing Additives for Rigid Polyurethane Foams

The subject of the research was the production of silsesquioxane modified rigid polyurethane (PUR) foams (POSS-Cl) with chlorine functional groups (chlorobenzyl, chloropropyl, chlorobenzylethyl) characterized by reduced flammability. The foams were prepared in a one-step additive polymerization reaction of isocyanates with polyols, and the POSS modifier was added to the reaction system in an amount of 2 wt.% polyol. The influence of POSS was analyzed by performing a series of tests, such as determination of the kinetics of foam growth, determination of apparent density, and structure analysis. Compressive strength, three-point bending strength, hardness, and shape stability at reduced and elevated temperatures were tested, and the hydrophobicity of the surface was determined. The most important measurement was the determination of the thermal stability (TGA) and the flammability of the modified systems using a cone calorimeter. The obtained results, after comparing with the results for unmodified foam, showed a large influence of POSS modifiers on the functional properties, especially thermal and fire-retardant, of the obtained PUR-POSS-Cl systems.     

Assessing the progress of degradation in polyurethanes by chemiluminescence and thermal analysis. II. Flexible polyether- and polyester-type polyurethane foams

The thermooxidative and thermal stability of polyether- and polyester-type polyurethane foams were investigated by non-isothermal chemiluminescence (CL), differential scanning calorimetry (DSC) and thermogravimetry (TG). In the presence of air and humidity, the effect of various routes and conditions of polyurethane ageing (induced thermally or by light) on the chemiluminescence, DSC and thermogravimetry patterns was assessed. The rate constants determined from non-isothermal thermogravimetry and chemiluminescence measurements at 250 °C and their not very pronounced dependence on the atmosphere of degradation indicated that depolymerisation of the polyurethane containing the aliphatic polyester and aromatic polyisocyanate moieties preceded or occurred in parallel with thermal oxidation. Under conditions of 50% relative humidity, samples of the polyester-type polyurethane, aged either by light or thermally, as well as specimens of the polyether-type polyurethane, aged by light, gave increased amounts of carbonaceous residue when heated in nitrogen to 550 °C.     

Rigid polyurethane foams reinforced with disilanolisobutyl POSS: Synthesis and properties

This work reports the synthesis of rigid polyurethane (PU) foams modified by disilanolisobutyl polyhedral oligomeric silsesquioxane (DSIPOSS). This open‐cage nanostructure silsesquioxane has 2 hydroxyl groups and therefore can be chemically built directly in the PU backbone to form hybrid polyurethane‐POSS foam. Synthesis procedure using polymeric 4,4′‐diphenylmethane diisocyanate, polyetherol, and DSIPOSS has been elaborated, and the influence of POSS on the cell structure, closed cell content, apparent density, thermal conductivity, and compression strength of the rigid polyurethane composites has been evaluated. The hybrid composite foams containing 1.5 and 2.0 wt% DSIPOSS showed a reduced number of cells and an increased average area of foam cells in comparison with the unmodified PU, while the addition of 0.5wt% of DSIPOSS causes an increase in the number of cells of the foam as compared with the reference and thus a reduction in the average area of cells. X‐ray microtomography provided data on the porous structure of polyurethane hybrid materials, including reduction of the pore surface area. Scanning electron microscopy and energy‐dispersive X‐ray spectroscopy analysis revealed a good homogenization of DSIPOSS in polyurethane matrix. Thermogravimetric analysis results have shown that incorporation of POSS nanoparticles into PU foam does not significantly change the degradation process. The compressive strength of PUF‐POSS hybrids in the direction parallel and perpendicular to the direction of foam rise is greater than the strength of the reference foam already for the lowest DSIPOSS content.     

基于天然聚多糖的环境友好材料（II）-麻纤维和芦苇纤维多元醇的生物降解聚氨酯

以麻纤维和芦苇纤维制备的植物多元醇为原料,合成具有良好性能的生物降解 性硬质聚氨酯泡沫体,其密度40 kg/m~3左右,压缩强度150 kPa,弹性模量4 MPa 。而且多元醇中植物原料含量越大,其性能越好,这使植物原料的充分利用和材料 生产成本的降低成为可能。土壤掩埋实验表明,泡沫体有很好的土壤微生物降解性 。     

Effects of flame‐retardant ramie fiber on enhancing performance of the rigid polyurethane foams

Ramie fiber (RF) with excellent tensile strength was treated by a flame retardant and obtained the modified RF (MRF) that is incombustible. Then, MRF was used to improve the performance of rigid polyurethane foams (RPUF). The mechanical properties of the composite were investigated by compressive strength test and shear stress test. The fire characteristics were studied using a cone calorimeter. And the thermal decomposition and flammable properties were further evaluated using thermogravimetric analysis and limiting oxygen index. The results showed that MRF improve the mechanical properties of RPUF and eliminate the harm of flammability of RF on the RPUF.     

Studying the Suitability of Nineteen Lignins as Partial Polyol Replacement in Rigid Polyurethane/Polyisocyanurate Foam

In this study, nineteen unmodified lignins from various sources (hardwood, softwood, wheat straw, and corn stover) and isolation processes (kraft, soda, organosolv, sulfite, and enzymatic hydrolysis) were used to replace 30 wt.% of petroleum-based polyol in rigid polyurethane/polyisocyanurate (PUR/PIR) foam formulations. Lignin samples were characterized by measuring their ash content, hydroxyl content (Phosphorus Nuclear Magnetic Resonance Spectroscopy), impurities (Inductively Coupled Plasma), and pH. After foam formulation, properties of lignin-based foams were evaluated and compared with a control foam (with no lignin) via cell morphology, closed-cell content, compression strength, apparent density, thermal conductivity, and color analysis. Lignin-based foams passed all measured standard specifications required by ASTM International C1029-15 for type 1 rigid insulation foams, except for three foams. These three foams had poor compressive strengths, significantly larger cell sizes, darker color, lower closed-cell contents, and slower foaming times. The foam made with corn stover enzymatic hydrolysis lignin showed no significant difference from the control foam in terms of compressive strength and outperformed all other lignin-based foams due to its higher aliphatic and p-hydroxyphenyl hydroxyl contents. Lignin-based foams that passed all required performance testing were made with lignins having higher pH, potassium, sodium, calcium, magnesium, and aliphatic/p-hydroxyphenyl hydroxyl group contents than those that failed.     

Improvement in Adhesion between Ethylene–Propylene–Diene Terpolymer (EPDM)-based Elastomer and Polyurethane Coating Using Epoxy–Polysulfide Copolymer As Adhesion Promoter

Epoxy–polysulfide copolymer as an adhesion promoter was added to ethylene–propylene–diene terpolymer and the effect of maleation of terpolymer with maleic anhydride on its adhesion to polyurethane coating was studied. The results show that using epoxy-polysulfide copolymer as the adhesion promoter cause a significant improvement in adhesion of terpolymer to polyurethane coating. The contact angle of the water reduced from 88° for the unmodified terpolymer to 65° for the maleated terpolymer containing 10 phr of epoxy–polysulfide copolymer. Peel strength was also increased from 0.2 N/mm for the unmodified terpolymer to 1.12 N/mm for the above-mentioned modified elastomer. Effect of the composition of the polymer blends on the loss tangent and storage modulus was studied to evaluate phase separation and crosslink density. The improvement of adhesion to polyurethane occurred without phase separation, which was further confirmed by the results of the mechanical and morphological investigations.     

Synthesis of CO2 Copolymer Based Polyurethane Foams

CO2-copolymer based polyurethane foams were synthesized and characterized in this paper. The foams were found to have higher strength and lower heat of combustion than the conventional polyether polyurethane foams. They may find wide applications in many fields.     

Glass transition and thermal degradation of rigid polyurethane foams derived from castor oil–molasses polyols

Rigid polyurethane (PU) foams having saccharide and castor oil structures in the molecular chain were prepared by reaction between reactive alcoholic hydroxyl group and isocyanate. The apparent density of PU foams was in a range from 0.05 to 0.15 g cm^?3. Thermal properties of the above polyurethane foams were studied by differential scanning calorimetry, thermogravimetry and thermal conductivity measurement. Glass transitions were observed in two steps. The low-temperature side glass transition was observed at around 220 K, regardless of castor oil content. This transition is attributed to the molecular motion of alkyl chain groups of castor oil. The high-temperature side glass transition observed in the temperature range from 350 to 390 K depends on the amount of molasses polyol content. The high-temperature side glass transition is attributed to the molecular motion of saccharides, such as sucrose, glucose, fructose as well as isocyanate phenyl rings, which act as rigid components. Thermal decomposition was observed in two steps at 570 and 620–670 K. Thermal conductivity was observed at around 0.032 J sec^?1 m^?1 K^?1. Compression strength and modulus of PU foams were obtained by mechanical test. It was confirmed that the thermal and mechanical properties of PU foams could be controlled by changing the mixing ratio of castor oil and molasses for suitable practical applications.     

Chemical Recycling and Liquefaction of Rigid Polyurethane Foam Wastes through Microwave Assisted Glycolysis Process

Glycolysis of polyurethane rigid foams (PUFs) was performed utilizing microwave irradiation at atmospheric pressure. The effects of various metal hydroxide and acetate catalysts as well as different microwave powers were investigated. All reactions were monitored by FTIR spectroscopy. The recovered liquid product containing OH functional groups was applied as a portion of the polyol in formulation of a new polyurethane rigid foam product. The reactivity factors and densities were compared with the foam produced from totally virgin polyol.     

Preparation and characterization of biopolyol via liquefaction of rice straw

Biopolyols were prepared by the liquefaction of rice straw under the mild condition. The optimum liquefaction effect was obtained at 5 : 1 volume ratio of PEG400 to DEG, 4 : 1 liquid–solid ratio, H₂SO₄ 3%, time 2.5 h, and reaction temperature120°C. Products were characterized by FTIR and gel permeation chromatograms (GPC) measurements. The hydroxyl value and weight-average molecular weight of the biopolyol produced based on the above optimal conditions were 260 mg KOH/g polyol and 420 g mol^–1, respectively. Biopolyol obtained is suitable for the preparation of rigid polyurethane foam. This study has certain significance for the high added value use of rice straw and reducing the production cost and improvement biodegradability of polyurethane foams.     

Polyurethane‐graphene nanocomposite foams with enhanced thermal insulating properties

The improvement of thermal insulating performance of polyurethane rigid foams is a crucial task for their use. In this work, the effect of graphene on these properties has been studied by preparing and testing unfilled, 0.3 and 0.5 wt% graphene‐filled polyurethane foams. It was found that graphene is able, at very low content (0.3 wt%), to reduce the radiative contribution of the initial thermal conductivity by both decreasing the cell size and increasing the extinction coefficient. Due to the low graphene contents considered, no concerns about the solid‐phase contribution of thermal conductivity arise. Polyurethane–graphene nanocomposite foams showed also slower aging rate with respect to unfilled foams. Copyright © 2015 John Wiley & Sons, Ltd.     

Evaluation of Hydrophobic Polyurethane Foam as Sorbent Material for Oil Spill Recovery

In this work, hydrophobic polyurethane foam was prepared using hy-drosilicone oil-grafted polybutadiene as soft segment via foaming technology. It was found that the hydrophobic polyurethane foams exhibited good hydrophobic capability and were regenerated easily. Of great interest, the hydrophobic polyurethane foams expand in contact with the oils. This indicates that the process of sorption by the hydrophobic polyurethane foams involves both the filling of the pores with oils and the absorption of oils by the polymer regions (polyurethane elastomer skeleton), and the adsorption capacity of the hydrophobic polyurethane foams can be enhanced by the swelling of the polyurethane elastomer skeleton. We can use this finding to improve the adsorption capacity of the hydrophobic polyurethane foams without merely changing the porosity. The effect of the swelling property of the hydrophobic polyurethane foams on the sorption capacity was further investigated. The results suggest that the hydrophobic polyurethane foams are promising in the application of oil spill recovery.     

Preparation of magnetic polyurethane rigid foam nanocomposites

Super paramagnetic Fe₃O₄@SiO₂ nanoparticle was incorporated into polyurethane rigid foams in order to prepare new corresponded magnetic nanocomposite foams via one-shot method. The core–shell-structured nanoparticles were prepared by sol–gel method and characterized by transmission electron microscopy, X-ray diffraction, as well as Fourier transform infrared spectroscopy techniques. Magnetic nanoparticles were used up to 3 % in the foam formulations and the samples prepared successfully. Thermal, mechanical, and magnetic properties of nanocomposites were studied and the results showed superior properties in comparison with pristine foams.     

Urea hard segment morphology in flexible polyurethane foam

A series of flexible polyurethane slabstock foam samples were prepared with varying water content and studied using transmission electron microscopy (TEM), video-enhanced optical microscopy (VEM), and small-angle X-ray scattering (SAXS). A new TEM sample preparation technique was developed in which the foam is impregnated with water, frozen, and microtomed, and the polyether soft segment is selectively degraded in the electron beam. Structures of two size scales were detected. A texture with grains (“urea aggregates”) 50–200 nm in size was imaged using both VEM and low-magnification TEM for foams with formulations containing more than 2 pphp water. For the first time, images of urea hard segment microdomains in polyurethane foam (approximately 5 nm in size) were obtained using high-magnification TEM. A microdomain spacing of approximately 6–8 nm was estimated from the SAXS scattering profiles. Glycerol was added to one of the formulations in order to modify the urea microphase separation and to give insight into morphology development in molded polyurethane foam systems. No structure was observed in low-magnification TEM images of the glycerol-modified foam, although smaller structures (hard segments) were detected at high magnification and by SAXS. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 573–581, 1998