Liquid‐type nucleating agent for improving thermal insulating properties of rigid polyurethane foams by HFC‐365mfc as a blowing agent

The effects of liquid‐type additives on the morphology, thermal conductivity, and mechanical strength of polyurethane (PUR) foams were investigated. The PUR foams synthesized with perfluoroalkane showed a smaller average cell diameter and a lower thermal conductivity than PUR foams prepared with propylenecarbonate or acetone. The average cell diameter of the PUR foams decreased from 228 to 155 μm and the thermal conductivity decreased from 0.0227 to 0.0196 kcal/mh °C when the perfluoroalkane content was 0.0 to 2.0 php (parts per hundred polyol by weight). The perfluoroalkane likely acted as a nucleating agent during the formation of the PUR foams. The addition of perfluoroalkane induced the smaller cells size of the PUR foams probably due to lower surface tension of the polyol and perfluoroalkane mixture, resulting in high nucleation rate. The smaller cell size appears to be the main reason for the improvement in the thermal insulating and the mechanical properties of these PUR foams. The compressive strength of the PUR foams prepared with perfluoroalkane was higher than the PUR foams prepared with the propylenecarbonate and acetone. Based on the morphology, thermal conductivity, and compressive strength, it is suggested that the perfluoroalkane is an efficient liquid‐type additive for the improving the thermal insulation of PUR foams. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43557.     

A facile strategy to fabricate microencapsulated expandable graphite as a flame‐retardant for rigid polyurethane foams

A facile strategy is reported for one‐step preparation of reactive microencapsulated expandable graphite (EG) for flame‐retardant rigid polyurethane foams (RPUF), which is based on in situ emulsion polymerization and the use of poly(glycidyl methacrylate) (PGMA) as reactive polymer shell. FTIR and SEM observations well demonstrate the formation of PGMA microencapsulated EG (EG@PGMA) particles. The encapsulation of PGMA shell significantly improves the expandability of EG particles from 42 to 70 mL g^?1. RPUF/EG@PGMA composite with only 10 wt % EG@PGMA loading reaches the UL‐94 V‐0 rating. The limiting oxygen indexes increase remarkably from 21.0 to 27.5 vol %. Additionally, the improved chemical and physical interaction enhance the interfacial bonding between EG and matrix, thus resulting in improved mechanical properties of RPUF/EG@PGMA. These attractive features suggest that the strategy proposed here can serve as a promising means to prepare highly efficient, reactive microencapsulated EG and corresponding good flame‐retarding RPUF with high mechanical properties. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42364.     

Extrusion of microcellular polysulfone using chemical blowing agents

Microporous polysulfone hollow fibers were developed with the help of chemical blowing agents by means of extrusion. Two chemical blowing agents, azodicarbonamide and 5-phenyltetrazol, were selected, and the foam morphology dependent on the concentration of blowing agent was examined by scanning electron micrograph. By means of changing the processing parameters, e.g., temperature and screw speed, the structures of the foam, usable as membrane, can be controlled. © 1998 John Wiley & Sons, Inc. J. Appl. Polym. Sci. 69: 1753–1760, 1998     

Properties of rigid polyurethane foams prepared from recycled aircraft deicing agent with hexamethylene diisocyanate

Polyurethane (PUR) rigid foams were prepared from recycled aircraft deicing agent (aircraft deicing fluid) with reaction of hexamethylene diisocyanate at temperature of 55°C. The effect of [NCO]/[OH] ratio on properties of microscopic structure, cell size distribution, compressive strength, apparent density, as well as thermal conductivity (k) was studied. Higher [NCO]/[OH] ratio helped achieve better micromorphology, higher apparent density, and compressive strength of the PUR foams. With the [NCO]/[OH] ratio of 0.75 and 0.8, some shrinking happened during foam rising, causing a decrease in total volume of the PUR foam, and leading to higher apparent density as well as sharply increased compressive strength. All PUR foams displayed good thermal insulation properties in this study. With [NCO]/[OH] ratio increased from 0.7 to 0.8, the k value increased significantly from 34.3 to 42.2 mW m^?1 K^?1. The k value here was chiefly governed by the apparent density of the foams, which was in turn a function of the ratio of [NCO]/[OH]. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci., 2013     

Sequential liquefaction of Nicotiana tabacum stems biomass by crude polyhydric alcohols for the production of polyols and rigid polyurethane foams

In this work, Nicotiana tabacum stalks and castor oil‐based polyol was synthesized via two step process. Preliminarily, stalks were liquefied using acid catalyst to procure glycol‐glycoside and the optimized conditions for liquefaction of N. tabacum stem's biomass was 150 °C temperature for 180 min time using PTSA as catalyst. Progressively, the glycol‐glycoside obtained from the former step was further reacted with castor oil in the presence of lithium hydroxide to get dark brown‐colored polyol with hydroxyl value was running in between 200 and 400 I_OH. Glycol‐glycoside and polyols were characterized by chemical and instrumental methods. Further by employing open‐cup method involving the mixing of polyol and isocyanate adducts, the desired poly urethane rigid foam was obtained. The product was tested for their physical, mechanical, thermal, and morphological characteristics, while the thermal conductivity was in the range of 0.013 to 0.017 Kcal/mh °C. The performed study may yield high quality rigid or semi‐rigid polyurethane foams that are commonly used as insulation materials. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43974.     

Synthesis of biopolyols by mild oxypropylation of liquefied starch and its application to polyurethane rigid foams

The liquefaction of starch in the presence of commercial polyol resulted in liquefaction products (LPs) with much lower hydroxyl values compared to those resulting from glycerol liquefaction. With the use of the obtained LPs (as initiators) and a catalytic amount of potassium hydroxide, oxypropylation was conducted under mild conditions (at 120°C, inner pressure generation of <0.2 MPa). Urethane resin foams were prepared from the obtained biopolyols. The reactivities of the biopolyols toward isocyanates were almost the same as those of commercial polyols. The physical properties of the obtained foams were as good or better than the ones obtained with the commercial polyols, including the sucrose/glycerol polyol GR‐84T. The biomass content values of the foams prepared with the biopolyols ranked among the highest in the world. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Improvement of nanoclays dispersion through microwave processing in polyurethane rigid nanocomposite foams

Polyurethane rigid nanocomposite foams were synthesized by in situ‐polymerization using both pristine and organically modified layered silicates. The effect of synthesis conditions, in particular the effect of different dispersing techniques, on morphology and mechanical properties of polyurethane nanocomposite foams was studied. To promote dispersion, clays were dispersed either in polyols or isocyanate and were subjected to a well known dispersion method, like ultrasonication, but also to a new dispersion method, based on microwaving. The morphological characterization of the foams, carried on using X‐ray diffraction, scanning electron microscopy, and transmission electron microscopy, proved that the technology based on microwave processing is able to provide very good silicates dispersion and requires very short application time to be effective. Further confirmations of the importance of the clay organo‐modifier are still present. Mechanical characterization of foams show that clay interferes with H‐bond formation and then the overall compressive performance of PU nanocomposite foams depends on the competition between the positive reinforcing effect of clay and the negative effect on H‐bond formation. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

不同发泡剂及工艺条件对BR／SBR／NR发泡材料相结构及尺寸稳定性的影响

分别采用一段和两段模压法制备了以顺丁橡胶（BR）／丁苯橡胶（SBR）／天然橡胶（NR）为基体的橡胶发泡材料,研究了三种化学发泡剂N,N＇-二甲基戊次甲基四胺（H）、4,4＇-氧代双（苯磺酰肼）（OBSH）以及H／OBSH（质量比1：1）复配对发泡及硫化特性的影-向,以及3种发泡剂和2种成型工艺对收缩率及相结构的影响。结果表明,发泡剂H对硫化性能影响最大,含发泡剂H的混炼胶在分解过程中释放的热量最多;加入3种发泡剂都具有一种较大的泡孔镶嵌在较小的泡孔丛中的泡孔形态;密度和线收缩率均随着时间的增加而增加,经H／OBSH复配的发泡剂更适合该体系成型,材料线收缩率均比单独使用H和OBSH小,两段模压法可以有效地提高发泡材料的尺寸稳定性,收缩率降低至3．88％,同时发泡剂使用率最多可提高31．67％。     

Chemical and physical blowing agents in structural polyurethane foams: Simulation and characterization

Physical blowing agents such as n‐pentane and methyl formate and, for comparison, chemical blowing agents such as water were used to prepare structural polyurethane rigid foams of different densities by reaction injection molding. Experimental runs were carried out with formulations based on oligomeric isocyanate and a mixture of polyether polyols. The constitutive equations for the vaporization rate of the two blowing agents and the polymerization kinetics data are reported. Experimental results were compared with the prediction of a simplified theoretical model, and they showed a satisfactory agreement in terms of temperatures and density profile. All the specimens were characterized by physical‐mechanical properties such as hardness, impact strength, flexural strength and elastic modulus and the results were reported in function of the densities. The best mechanical performance were obtained with the physical blowing agents, due to a better density distribution profile and a thicker skin layer.     

Reactivity of the raw materials and their effects on the structure and properties of rigid polyurethane foams

Formulations for rigid polyurethane foams (RPUFs) based on crude 4,4′‐diphenylmethane diisocyanate, polyether polyol, triethylenediamine, 1,4‐butane diol, poly(siloxane ether), methylene chloride, and water were studied. The stoichiometric ratios of various foam ingredients and their effects on physical properties such as the cream time, gel time, tack‐free time, and density of the RPUF samples were studied. The results indicated that the rate of RPUF formation increased with the catalyst (triethylenediamine and tin) and water content. The density of the RPUF samples blown with water, methylene chloride, and a mixture of water and methylene chloride decreased from 240.1 to 33.4 kg/m³ with an increase in the blowing agent contents. However, the RPUF density increased with increasing contents of 1,4‐butane diol. The cell morphology and thermal properties of the RPUF samples were investigated with scanning electron microscopy, thermogravimetric analysis, derivative thermogravimetry, and differential thermal analysis. Scanning electron microscopy results revealed an average increase in the cell size of the RPUF samples from 162 to 278 μm with increased water content. A thermal behavior study indicated that the RPUF samples decomposed in nitrogen and degraded in air through two and three weight‐loss stages, respectively. Foam pyrolysis in nitrogen and combustion in air led to 15 and 0% char residue, respectively. The results indicated that the thermal stability of the RPUFs was better in nitrogen than in an air atmosphere. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Characterization of rigid polyurethane foams containing microencapsulted phase change materials: Microcapsules type effect

Rigid polyurethane (RPU) foams were synthesized incorporating up to 18 wt % of two different kinds of thermo‐regulating microcapsules having a different shell material consisting of polystyrene or poly(methyl methacrylate), named as mSP‐(PS‐RT27) and Micronal®DS 5001X, respectively. The type of microcapsules and their content affected the final foam height, which decreased with the content and particle size. However, the foam rising curve shape was not dependent on the microcapsules type or content and was successfully predicted by means of a model of reaction curve of four tanks in series. Thermal energy storage (TES) capacity of PU foams was improved by incorporating both, mSP‐(PS‐RT27) or Micronal®DS 5001X, with the values close to those reported in the literature (16 J/g) for the highest content. Nevertheless, the highest particle size of the microcapsules from PS and the agglomeration of the microcapsules from poly(methyl methacrylate), promoted by their additive SiO₂, led to the strut rupture, damaging the final mechanical properties. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Effects of TiO2, ZnO,and Fe3O4 nanofillers on rheological behavior,microstructure, and reaction kinetics of rigid polyurethane foams

Effects of different types and shapes of titanium dioxide, zinc oxide, and magnetite nanofillers on the rheological behavior of polyol/nanofiller suspensions, on the rigid polyurethane foam formation reaction, and hence on the final microstructure were investigated. The rheological percolation threshold of polyol/nanofiller suspensions decreased as the aspect ratio of nonspherical nanoparticles (platelet or rod) increased, regardless of the nanofiller type. The results of reaction kinetics showed that above a critical surface area (≈30 m²), independently of nanofiller type, the reaction rate increased as the surface area increased. The introduction of oxide surfaces reduced the final cell size until a critical surface area (≈30 m²). However, above this critical value cell size distribution gets wider and the cell size can no longer be correlated with the surface area. In the latter case, an increase of the reaction rate and the polymerization reaction being exothermic may facilitate uncontrolled cell nucleation, growth, and hence coalescence which results in an uncontrolled foam structure. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43658.     

Intumescent foams—A novel flame retardant system for flexible polyurethane foams

A combination of intumescent components was evaluated as a novel flame retardant system in a flexible polyurethane foam, and the incorporation of these components gave rise to a significant enhancement of the flame retardant properties of the foam. The heat release rate was lowered at an early stage as well as throughout the fire, the total heat production was decreased and the time to ignition was prolonged. Mechanical measurements of the foam revealed enhanced properties in terms of stiffness accompanied by a large decrease in elongation at break as compared with a reference foam. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Layer double hydroxide and sodium montmorillonite multilayer coatings for the flammability reduction of flexible polyurethane foams

Flexible polyurethane foam (PUF) is coated by layer‐by‐layer (LbL) assembly using branched polyethyleneimine (BPEI), poly(acrylic acid) (PAA), and two different charged nanoparticles, such as sodium montmorillonite (Na‐MMT) and layered double hydroxide (LDH). Three different deposition strategies, that is, bilayer, trilayer, and quadlayer, exhibit different coating growth, morphology, and flammability properties. Changing the nanosheet from LDH to MMT dramatically alter the coating mass for the same number of layers. A five bilayer PAA/BPEI+LDH coating reduced the peak heat release rate by 40% and the average heat release rate by 70%, which is two times more effective than commercial fire retardants (FRs) and other LbL‐FR coatings for PUF. MMT and LDH mixed multilayers resulted in effective flame‐retardant coatings with less coating mass by manipulating the deposition strategy. This study manifests the flexibility of LbL to fine‐tune flammability reduction by switching the coating weight gains, which is significant to accelerate the development of other LbL coating regardless of the intended applications. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41767.     

Aspects of foaming a glass‐reinforced polypropylene with chemical blowing agents

This work explores the influence of a chemical blowing agent on different aspects of producing a short glass‐fiber‐reinforced polypropylene foam, examining the rheology of the system, the developed morphology of the part, and the resulting mechanical properties. Two different forms of an endothermic blowing agent, namely powder versus masterbatch, were compared to determine their effects on the process history and properties of an injection molded part. Samples were produced on an injection molding machine between 230 and 270°C using the low‐pressure foaming technique. Rheology of the resulting plasticized melt by the two different blowing agents was measured on an in‐line rheometer, showing a greater reduction in shear viscosity for the masterbatch additive, which correspondingly reduced the extent of fiber breakage observed. The final molded samples were analyzed for their foam structure (i.e., cell size, cell density, and skin thickness) as well as the properties of the glass fibers incorporated (namely, fiber length distribution). Tensile properties were found to diminish with increasing blowing agent content, though differences were observed based on the type of CBA used despite the similarities in foam structure produced. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 4696–4706, 2006     

Metal acetylacetonate–amine and metal nitrate–amine complexes as low‐emission catalysts for rigid polyurethane foam preparation

Six metal–amine complexes, Cu(acac)₂(trien), Zn(acac)₂(en), Zn(acac)₂(trien), Cu(NO₃)₂(en)₂, Cu(NO₃)₂(trien), and Cu(NO₃)₂(tetraen), are synthesized from metal acetylacetonates [M(acac)₂, where M = Cu and Zn] or metal nitrate [M(NO₃)₂, where M = Cu] and aliphatic amines (en = ethylenediamine, trien = triethylenetetramine, and tetraen = tetraethylenepentamine). These metal–amine complexes can be used as catalysts in the preparation of rigid polyurethane (RPUR) foams. All metal–amine complexes emit very weak odor when compared with N,N‐dimethylcyclohexylamine (DMCHA), which is a commercial catalyst commonly used in the preparation of RPUR foams. DMCHA emits very strong amine odor that affects working environment in RPUR foam processing. Among all metal complexes, Cu(acac)₂(trien) has the highest catalytic activity. In comparison with DMCHA, Cu(acac)₂(trien) shows slightly higher catalytic activity in gelling reaction but lower catalytic activity in blowing reaction. RPUR foam prepared from Cu(acac)₂(trien) has lower density and compressive strength than that prepared from DMCHA. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42332.     

Sustainable rigid polyurethane foams based on recycled polyols from chemical recycling of waste polyurethane foams

The preparation and characteristics of rigid polyurethane foams (RPUFs) based on recycled polyol obtained by glycolysis of waste RPUF scraps from end-of-life refrigerators were investigated. To deactivate the amine adducts derived from isocyanates, the recycled product obtained after depolymerization was chemically modified via addition polymerization of propylene oxide. Two kinds of recycled polyols with different hydroxyl values and viscosity were blended with conventional virgin polyether polyol to prepare the RPUFs. The effects of the recycled polyols on the physical properties of RPUFs such as cell structures, compressive strength, thermal conductivity, and limiting oxygen index were discussed. It was found that the RPUFs from recycled polyols showed superior compressive strength, thermal insulation property, and self-extinguishing property compared with conventional control foam. The results of this study reveal that the recycled polyols could be used as feedstock for RPUFs with superior performance. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47916.     

New polyol for production of rigid polyurethane‐polyisocyanurate foams,Part 2: Preparation of rigid polyurethane‐polyisocyanurate foams with the new polyol

The method of preparation, determination of foaming parameters, and methods for the determination of physicochemical properties of polyurethane‐polyisocyanurate (PUR‐PIR) foams prepared with the use of N,N′‐di(methyleneoxy‐2‐hydroxyethyl)urea and boric acid derivatives are presented in this paper. It was found that application of the borate as a polyol component and simultaneously as a flame retardant in the recipe for production of PUR‐PIR foams was very favorable. The foams prepared were characterized by reduced brittleness, higher compressive strength and content of closed cells, as well as considerably lower flammability in comparison with standard foam. The results show that the new polyol prepared on the basis of N,N′‐di(methyleneoxy‐2‐hydroxyethyl)urea and boric acid can be applied for production of rigid PUR‐PIR foams, and it improves their physicochemical properties. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Foam stability and polymer phase morphology of flexible polyurethane foams synthesized from castor oil

Foam stability and segmented polymeric phase morphology of polyurethane foams synthesized partially and completely from castor oil are investigated. Preliminary analysis of the impact of alterations in the polymeric phase on macroscopic stress dissipation in foams is also carried out. The stability and morphology show unique trends depending on the concentration of castor oil used in foam synthesis. While low and intermediate concentrations of castor oil does not significantly affect the foaming process; at high concentrations, the volumetrically expanding liquid matrix remains in a nonequilibrium state during the entire foaming period, resulting in significant foam decay from top. This increases the final foam cell density and decreases the plateau border thickness at bottom. In the polymeric phase of castor oil based foams, the fraction of monodentate urea increases at the cost of non‐hydrogen bonded urea. These monodentate urea domains undergo flocculation in foams synthesized completely from castor oil, thus prominently modifying the segmented morphology. The glass transition temperature of soft segments of partially substituted foams shows moderate increase, with indications of phase mixing between the polyether and castor oil generated urethane domains. Foams synthesized entirely from castor oil have significant sol fraction due to unreacted oligomers. The microscopic alterations in polymeric phase reduce the elastic recovery of partially substituted castor oil foams compared to its viscous dissipation under an applied stress. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40668.