Preparation and characterization of polyurethane/silica aerogel nanocomposite materials

In this investigation, silica aerogel (SA)/Rigid Polyurethane (PUR) foam composites and silica aerogel/Polyurethane (PU) composites were prepared by dry mixing of granular and grinded silica aerogels with polyol part. They were then combined with diisocyanate part. Three different types of PUR foams and an elastomeric coating grade of PU were studied as well. Results show that thermal conductivity of foams did not decrease by adding silica aerogel. It even increased for some grades which is assumed to be due to the change in cell configuration of these foams. It was also found that sound insulation performance of these cellular composites did not improve significantly. Unlike foam composites, addition of silica aerogel into elastomeric PU improved its thermal and acoustic insulation properties. Because of the more promising properties of elastomeric PU composites, further examinations including measurements of compression strength and water contact angle of silica aerogel/PU composites were also taken. Final results showed a significant improvement in general properties of PU coatings by adding little amounts of silica aerogel (1–4 wt %). © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44521.     

Pulverized polyurethane foam particles reinforced rigid polyurethane foam and phenolic foam

Polyurethane consumption has been increasing in recent years, raising concerns about how to deal with the polymer waste. Post‐consumer rigid polyurethane foams or polyurethane foam scraps (PPU) ground into particles were utilized to strengthen mechanical properties of rigid polyurethane foam (PUF) and phenolic foam (PF). Viscosity of prepolymer with PUF was measured and PPU was well dispersed in prepolymer, as observed by optical microscope. Microstructures and morphologies of the reinforced foam were examined with scanning electron microscope (SEM) while cell diameter and density were measured by Scion Image software. Universal testing machine was employed to optimize compressive properties at various weight ratios of PPU. Both PUF and PF with 5 wt % PPU, respectively, exhibited considerable improvement in mechanical properties especially compressive property. The compressive modulus of PUF with 5 wt % PPU was 12.07 MPa, almost 20% higher than pure PUF while compressive strength of PF with 5 wt % PPU reached 0.48 MPa. The thermal stability of the reinforced foam was tested by thermal gravity analysis (TGA) and the result shows no obvious impact with PPU. The decomposition temperatures of PUF with PPU and PF with PPU were 280°C, because PPU has relatively weak thermal stability. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39734.     

Modification of tung oil–based polyurethane foam by anhydrides and inorganic content through esterification process

In this study, we have reported the synthesis of modified polyol from tung oil. The synthesis involves three steps: first, conversion of tung oil to hydroxylated tung oil by hydroxylation; second, alcoholysis with triethanolamine; and finally, the esterification of polyester polyol when reacted with phthalic anhydride (PA) or maleic anhydride (MA). Boric acid is also introduced into the polyol by chemical modification, which enhances the thermal properties of polyurethane foam (PUF). PUF is formulated by the reaction between polyol and isocyanate. A systematic comparison of flame retardancy and mechanical and thermal properties of modified PUF has been examined. The structural properties of modified polyol were characterized by Fourier transform infrared spectroscopy, proton NMR spectroscopy, and gel permeation chromatography, while the thermal and mechanical properties of the formulated PUF were studied by scanning electron microscopy, limiting oxygen index, differential scanning calorimetry, Izod impact, and flexural and compression strength. Thus PUF prepared from modified polyol with a proper distribution of soft and hard segments possesses better mechanical and thermal properties. The PA‐modified foams show better properties compared to unmodified and MA‐modified foams due to the aromaticity and crosslinking behavior of PA. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45786.     

Processing and properties of an ethylene–vinyl acetate blend foam incorporating ethylene–vinyl acetate and polyurethane waste foams

Waste polyurethane foam (w‐PU) and waste ethylene–vinyl acetate foam (w‐EVA) were used as fillers for the production of an ethylene–vinyl acetate (EVA) blend foam. Two different foaming techniques (single‐stage and heat–chill processes) were used for this purpose. The waste foam concentration was varied up to 30 wt % of the original EVA. The physical, mechanical, and morphological properties of the filled foam were studied. The single‐stage process produced blend foams with a lower density and a greater cell size than the foams obtained by the heat–chill process. The density and compression strength of the blend foam increased as the percentage of w‐PU foam increased. However, for the w‐EVA/EVA blend foams, the addition of w‐EVA foam did not significantly affect the density or compression strength compared to the original EVA foams. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44708.     

疏水花生壳/聚氨酯复合泡沫的制备与油水分离性能

为提高聚氨酯泡沫（PUF）的疏水性能，首先，采用十六烷基三甲氧基硅烷（HDTMS）对花生壳粉末（PSP）进行改性，得到疏水改性花生壳粉末（H-PSP）。水接触角测试结果表明，改性后H-PSP的水接触角由PSP的0°提高至145.2°。然后，采用预聚体法制备了PUF负载H-PSP复合材料[H-PSP-PUF-n,n为H-PSP占聚氨酯预聚体（PPU）质量的百分数]。对H-PSP-PUF-n的结构和性能进行了表征与测试。结果表明，H-PSP的负载提高了泡沫材料的表面粗糙度和力学性能，H-PSP的最佳负载量为PPU质量的10%（标记为H-PSP-PUF-10）。与PUF相比，H-PSP-PUF-10的静态水接触角达到142.4°，较PUF提高了50.4°。对二氯甲烷、石油醚、煤油、二甲苯、环己烷进行油水分离实验，结果表明，H-PSP-PUF-10对石油醚、煤油、二甲苯、环己烷的吸油倍率在7～9 g/g，而且具有良好的油水选择性。经15次吸附-脱附循环后，H-PSP-PUF-10对各油品的吸油倍率在6.5～8.0 g/g，具有良好的循环利用性。     

疏水花生壳/聚氨酯复合泡沫的制备与油水分离性能

为提高聚氨酯泡沫（PUF）的疏水性能,首先采用十六烷基三甲氧基硅烷（HDTMS）对花生壳粉末（PSP）进行改性,得到疏水改性花生壳粉末（H-PSP）。水接触角测试结果表明,改性后H-PSP的水接触角由PSP的0°提高至145.2°。然后采用预聚体法制备了PUF负载H-PSP复合材料（H-PSP-PUF-n,n为H-PSP占聚氨酯预聚体PPU的质量分数）。对H-PSP-PUF-n的结构和性能进行了表征与测试。结果表明,H-PSP的负载提高了泡沫材料的表面粗糙度和力学性能,H-PSP的最佳负载量为PPU质量的10%（H-PSP-PUF-10）。与PUF相比,H-PSP-PUF-10的静态水接触角达到142.4°,较PUF提高了50.4°。对二氯甲烷、石油醚、煤油、二甲苯、环己烷五种油品进行油水分离实验,结果表明,H-PSP-PUF-10对不同油品的吸油倍率在7~9 g/g,而且具有良好的油水选择性。经15次吸附-脱附循环后,H-PSP-PUF-10对各油品的吸油倍率在6.5~8.0 g/g,具有良好的循环利用性。     

Synthesis of a novel sulfonated poly(amide‐imide) and its application in preparation of ultrafiltration PES membranes as a modifier

Sulfonated poly(amide‐imide) (SPAI) copolymer was synthesized, characterized, and blended into poly(ether sulfone) (PES)/dimethylacetamide casting solutions to prepare ultrafiltration membranes. Different weight ratios of the copolymer (0–10 wt %) were mixed in the PES casting solution. The analyses of contact angle and attenuated total reflection‐Fourier transform infrared spectra were used to study hydrophilicity and physicochemical properties of the membrane surface, respectively. The membranes were further characterized by scanning electron microscopy images, ultrafiltration performance, and fouling analyses. The outcomes showed that addition of the SPAI in the PES matrix improved considerably the membranes hydrophilicity. Moreover, with increasing SPAI concentration, the porosity, flux recovery ratio, and pure water permeability of the modified membranes were improved. The pure water flux was increased from 3.6 to 12.4 kg/m² h by increasing 2 wt % SPAI. The antifouling property of the modified PES membranes against bovine serum albumin, tested by a dead‐end filtration setup revealed that bovine serum albumin rejection of the obtained membrane was also enhanced and the antifouling properties of the blending membranes were improved. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46477.     

Application of recycled polyol and benzimidazole to the enhancement of antifungal activity of polyurethane

Recycled polyol and benzimidazole were both grafted onto polyurethane (PU) to enhance the surface hydrophilicity and antifungal activity, respectively. The two grafted groups affected the viscosity, crosslink density, soft segment glass transition, breaking stress, flexibility at freezing temperature, shape recovery at ?10 °C, surface hydrophilicity, and antifungal activity. The glass transition temperature increased from ?67.5 °C for plain PU up to ?60.8 °C after the grafting of polyol. The breaking stress and shape recovery of the grafted PU increased up to 425% and 200%, respectively, relative to plain PU because of the chemical linking by the grafted polyol. The hydrophilicity of PU, evaluated by the water contact angle and water swelling ratio, increased with increasing polyol content. A PU sample demonstrated excellent low‐temperature flexibility in comparison to plain PU and control sample. Finally, the PUs modified with grafted polyol and benzimidazole completely suppressed fungal growth. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46600.     

蒸馏水含量对三明治结构硬质聚氨酯泡沫性能的影响

采用异氰酸酯、聚酯多元醇、发泡剂（水）等原料通过一体发泡成型技术制备出一种新型的三明治泡沫夹心复合材料。利用热重分析、扫描电子显微镜等对不同水含量（质量分数分别为0、0.5 %和1.0 %）的硬质聚氨酯泡沫材料的泡孔直径、密度、热导率、压缩性能、三点弯曲和热力学性能等做了研究,进而确定提高硬质聚氨酯性能的最佳工艺。结果表明,随着水含量的增加,硬质聚氨酯泡沫材料泡孔直径增大,密度变小,热导率降低,保温性能提高,而压缩性能和三点弯曲却呈下降趋势;综合考虑硬质聚氨酯泡沫材料泡孔结构和良好的保温隔热及弯曲等力学性能,其最佳含水量为0.5 %。     

Highly flame‐retardant bio‐based polyurethanes using novel reactive polyols

Poor flame retardancy of polyurethanes (PU) is a global issue as it limits their applications particularly in construction, automobile, and household appliances industries. The global challenge of high flammability of PU can be addressed by incorporating flame‐retardant materials. However, additive flame‐retardants are non‐compatible and depreciate the properties of PU. Hence, reactive flame‐retardants (RFR) based on aliphatic (Ali‐1 and Ali‐2) and aromatic (Ar‐1 and Ar‐2) structured bromine compounds were synthesized and used to prepare bio‐based PU using limonene dimercaptan. The aromatic bromine containing foams showed higher close cell content (average 97 and 100%) and compressive strength (230 and 325 kPa) to that of aliphatic bromine containing foams. Similar behavior was observed for a horizontal burning test where with a low concentration of bromine (5 wt %) in the foams for Ar‐1 and Ar‐2 displayed a burning time of 12.5 and 11.8 s while, Ali‐1 and Ali‐2 displayed burning time of 25.7 and 37 s, respectively. Neat foam showed a burning time of 74 s. The percentage weight loss for neat PU foam was 26.5%, while foams containing 5 wt % bromine in Ali‐1, Ali‐2, Ar‐1, and Ar‐2 foams displayed weight loss of 11.3, 14, 7.9, and 14%, respectively. Our results suggest that flame retardant PU foams could be prepared effectively by using RFR materials. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46027.     

Physicomechanical,friction, and abrasion properties of EVA/PU blend foams foamed by supercritical nitrogen

Elastomer foams based on EVA, PU, and EVA/PU blends formulated for shoe‐sole applications were prepared by a supercritical N₂ batch foaming process and characterized for physicomechanical, friction and abrasion properties. The blending of EVA with PU was aimed for improving the friction and wear characteristics of the EVA based foams. All of the foams prepared showed spherical cells with closed‐cell morphology and the cell sizes varied with varying the EVA/PU blend ratio and CaCO₃ content of the foams. The properties such as hardness and resilience, friction coefficients and abrasion resistance improved for the EVA/PU blend foams compared to the EVA foam, but their compression set, tensile strength, and tear strength were inferior to the EVA foam. The incorporation of CaCO₃ filler increased density, hardness, tensile strength, and tear strength of the EVA/PU blend foams but decreased resilience, compression set, friction coefficients, and abrasion resistance. The improvement in friction coefficients and wear resistance obtained in the EVA/PU blend foams was significant for shoe‐sole applications. POLYM. ENG. SCI., 2017. © 2017 Society of Plastics Engineers     

Oxidation resistant ceramic foam from a silicone preceramic polymer/polyurethane blend

Silicon oxycarbide (SiOC) ceramic foams, produced by the pyrolysis of a foamed blend of a methylsilicone preceramic polymer and polyurethane (PU) in a 1/1 wt.% ratio, exhibit excellent physical and mechanical properties. The proposed process allows to easily modify the density and morphology of the foams, making them suitable for several engineering applications. However, it has been shown that, due to residual carbon present in the oxycarbide phase after pyrolysis, the foams are subjected to an oxidation process that reduces their strength after high temperature exposure to air (12 h 1200°C). A modified process, employing the same silicone resin preceramic polymer but a much lower PU content (silicone resin/PU=5.25/1 wt.% ratio), has been developed and is reported in this paper. Microstructural investigations showed that carbon rich regions deriving from the decomposition of the polyurethane template are still present in the SiOC foam, but have a much smaller dimension than those found in foams with a higher PU content. Thermal gravimetric studies performed in air or oxygen showed that the low-PU containing ceramic foams display an excellent oxidation resistance, because the carbon-rich areas are embedded inside the struts or cell walls and are thus protected by the dense silicon oxycarbide matrix surrounding them. SiOC foams obtained with the novel process are capable to maintain their mechanical strength after oxidation treatments at 800 and 1200°C (12 h), while SiOC foams obtained with a higher amount of PU show about a 30% strength decrease after oxidation at 1200°C (12 h).     

High-density polyethylene membranes embedded with carboxylated and polyethylene glycol-grafted nanodiamond to be used in membrane bioreactors

In this work, neat and modified nanodiamond (ND) particles were embedded into high-density polyethylene (HDPE) membranes to improve hydrophilicity and antifouling properties. The membranes were prepared via thermally induced phase separation (TIPS) method and used for pharmaceutical wastewater treatment in membrane bioreactors (MBR) system. To prevent the agglomeration of ND, it was modified using two methods: thermal carboxylation (ND-COOH) and grafting with polyethylene glycol (ND-PEG). Membranes with different concentration of ND-COOH and ND-PEG nanoparticles ranging from 0.00 to 1.00 wt % were prepared and characterized using a set of analyses including water contact angle, pure water flux, tensile strength, differential scanning calorimeter, field emission scanning electron microscopy, and energy dispersive X-ray spectroscopy. It was found that the optimum contents of ND-COOH and ND-PEG nanoparticles were 0.50 wt % and 0.75 wt %, respectively. The interfacial interaction between nanoparticles and HDPE matrix was studied based on Pukanzsky model. To examine the performance of membranes, critical flux, filtration experiment in the MBR, and fouling analysis of membranes were carried out. The results showed that among the fabricated membranes, 0.75 wt % HDPE/ND-PEG membrane had the highest water flux and the best antifouling properties. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47914.     

可再生聚酯多元醇的合成及其在聚氨酯材料中的应用

采用油酸为主要原料合成了羟值为236mgKOH／g、酸值为2．8mgKOH／g的可再生聚酯多元醇,并以此聚酯多元醇为原料制备了聚氨酯硬质泡沫。研究了该聚酯多元醇用量对泡沫发泡和力学性能的影响。结果表明,随着聚酯多元醇加入量的增加,形成聚氨酯硬质泡沫的反应速度增加;与纯聚醚多元醇制备的聚氨酯硬质泡沫相比,加入20％～30％的该聚酯多元醇制备的聚氨酯泡沫的尺寸稳定性和压缩强度增加。     

Structures and physical properties of rigid polyurethane foam prepared with rosin‐based polyol

Rosin‐based polyester polyols were synthesized from a rosin–maleic anhydride adduct, diethylene glycol, and ethylene glycol with and without adding adipic acid and phthelic anhydride, in the presence of catalyst. Rigid polyurethane (PU) foams were prepared with these rosin‐based polyols and compared with foam made with an industrial polyester Daltolac? P744. The experimental results show that the foaming behavior for the foams prepared from such rosin‐based polyols is similar to that of industrial products, but their 10% compression strength, both parallel and vertical to foaming rise direction, is higher and the dimensional stability at 100 and ?30°C is similar or somewhat better than that of a comparable system. Furthermore, the rosin‐modified PU foams exhibit even lower thermal conductivity and much higher activation energies during the pyrolysis process. All these unique physical properties of the rosin‐modified rigid PU foams were correlated to the structures of these PU foams. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 598–604, 2002; DOI 10.1002/app.10312     

催化剂对废旧PU硬泡回收再利用的影响

用含有小分子醇的交联剂和催化剂使废旧聚氨酯（PU）硬泡进行降解能够获得多元醇,将降解料与聚醚多元醇、催化剂和发泡剂共混以制备白料,然后与黑料异氰酸酯混合均匀,得到再生PU硬泡。通过对降解产物的黏度、羟值以及获得的再生PU硬泡材料的密度、强度、吸水率、热稳定性、扫描电子显微镜、红外光谱和热失重等进行测试分析,得出了催化剂添加量对废旧PU材料回收再利用的影响因素。结果表明,催化剂（KOH）用量为0.9 g时废旧PU的降解效果最好,获得的再生PU硬泡的密度为37.6 kg/cm³,压缩强度为164.2 kPa,热导率为0.015 24 W/（m·K）,吸水率为0.429 5 %。     

Preparation and characterization of microencapsulated ammonium polyphosphate and its synergistic flame‐retarded polyurethane rigid foams with expandable graphite

A facile and effective method for the preparation of microencapsulated ammonium polyphosphate (MAPP) by in situ surface polymerization was introduced. The ‘polyurethane‐like’ shell structure on the surface of MAPP was characterized by using Fourier transform infrared spectroscopy. The hydrophobicity and thermal behavior of MAPP were studied by using water contact angle tests and thermogravimetric analysis. The foam density and mechanical properties of polyurethane (PU) rigid foams were investigated. The flame retardancy of PU rigid foams formulated with MAPP was evaluated by using limiting oxygen index and cone calorimetry. The results show that MAPP can greatly increase the flame retardancy of PU materials. Also, there is a synergistic effect between MAPP and expandable graphite in flame retarding PU rigid foams. Moreover, the water resistance property of PU/MAPP composites is better than that of PU/ammonium polyphosphate. The morphology and chemical structure of PU/MAPP rigid foams after burning were systematically investigated. © 2013 Society of Chemical Industry     

Effect of auxiliary blowing agents on properties of rigid polyurethane foams based on liquefied products from peanut shell

The bio‐based rigid polyurethane (PU) foams were successfully prepared based on liquefied products from peanut shell with water as the blowing agent. The influence of reaction parameters on properties of rigid PU foams was investigated. Rigid PU foams showed excellent compressive strength and low shrinkage ratio, whereas their open‐cell ratio and water absorption were higher. Therefore, rigid PU foams were synthesized with petroleum ether, diethyl ether, and acetone as auxiliary blowing agents and their inner temperature, shrinkage performance, density, compressive strength, water absorption, and open‐cell ratio were determined. The results indicated that above rigid PU foams showed lower compressive strength than the original foam but their water absorption and close‐cell ratio were improved. Compared with the original foam, the highest inner temperature of rigid PU foams with petroleum ether, diethyl ether, and acetone as auxiliary blowing agents was reduced by 11, 19, and 23 °C, respectively. Typically, foams with petroleum ether as auxiliary blowing agent displayed better water absorption and swelling ratio in water and exhibited obvious improvement in close‐cell ratio. These foams were preferable for application in thermal insulation materials because of low thermal conductivity and better corrosion resistance. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45582.     

Eco-friendly foams of castor oil based-polyurethane with Artemisia residue fillers for discarded vegetable oil sorption

In this article, a new approach is applied to reuse Artemisia residue (AR) as filler in polyurethane (PU) foam for vegetable oil sorption for discarded cooking oil applications. The pristine PU and PU/X%AR foams (X stands for AR content of 5–20%wt/wt) were characterized by SEM, density, contact angle (CA), thermogravimetric analysis, and Fourier transform infrared spectroscopy. The influence of two experimental factors, such as contact time (30–180 s) and initial vegetable oil concentration (20–200 g/L), was investigated in vegetable oil and vegetable oil/mineral water systems. The AR loading of the foams increased the foams' density and influenced the morphological, physical, thermal, and sorption properties. The PU/20%AR sample presented the highest CA (122.5°) and the best sorption capacity and efficiency in both systems due to the small pores size and higher frequency of pores. Langmuir and Freundlich isotherm models well defined the sorption mechanisms. The Langmuir model represented the best fit of experimental data for PU/20%AR with a maximum adsorption capacity of 16.86 g/g. The PU/20%AR presented reusability of 7 cycles, conserving their hydrophobicity after the process. Therefore, AR is an innovative route as fillers in PU foams for discarded vegetable oil sorption, and the circular economy can benefit from the reuse of discarded vegetable cooking oil.     

Water‐blown polyurethane–clay nanocomposite foams from biopolyol—effect of nanoclay on the properties

The present work deals with the development of polyurethane–clay nanocomposite foams by replacing part of the synthetic polyol with castor oil derivative. Hydroxylated castor oil was converted into diethanol amide by transamidation and the resulting polyol was formulated into water‐blown foams. Modified montmorillonite clay was used as nanofiller in different amounts viz. 0.5%, 1.0%, 2.0%, and 5.0% by total weight of the foam formulation. Rheological measurements on the polyol–clay mixtures indicated that up to 1% clay loading there is no significant change in the viscosity with shear rate and beyond 2%, shear thinning occurred. X‐ray diffraction studies further substantiated these results. The effect of the modified clay on the density, mechanical properties such as compression strength, compression modulus, and microstructure of the foams were investigated. The filler thus added had a reinforcing effect on the foam as observed in the density and compression strength measurements. Differential scanning calorimetric studies on T_g and dynamic mechanical analyses on the modulus clearly indicated that 1% clay loading and above led to exfoliation and plasticizing effect. Exfoliated nanocomposites in compositions containing 1% clay and more yielded a much higher nucleation rate than intercalated ones leading to reduced cell size as observed by optical and scanning electron microscopy. Thus, castor oil, which is readily available, relatively inexpensive, and environmentally benign nonedible oil, has been successfully used to prepare filled semirigid foams which can find application in insulation and packing. POLYM. COMPOS. 34:1306–1312, 2013. © 2013 Society of Plastics Engineers