Reinforcement of agricultural wastes liquefied polyols based polyurethane foams by agricultural wastes particles

Four kinds of agricultural wastes particles (XS: oilseed rape straw [OS], rice straw [RS], wheat straw [WS], and corn stover [CS]) were used to reinforce agricultural wastes liquefied polyol (P-XS) based polyurethane (PU) foam. Different XS loading dosages (0% ~ 15%) are investigated to confirm suitable filler concentrations for modifying foams. RS particles show great promoting ability, OS particles reveal complex influence, while WS and CS particles display mild effect on foaming process. With 1% of OS, 6% of RS, 3% of WS, or 1% of CS incorporating in matrix materials, the reinforced foam could keep applicable density, reach better physical and mechanical property, display more uniform cellular structure, and show higher thermal stability with more excellent water absorption ability. Using of agricultural wastes as polymer filler is economical, simple, environmental, and wide applicable for biomass utilization and biopolymer preparation.     

Preparation and Characterization of Sustainable Polyurethane Foams from Soybean Oils

Polyol derived from soybean oil was made from crude soybean oil by epoxidization and hydroxylation. Soy-based polyurethane (PU) foams were prepared by the in-situ reaction of methylene diphenyl diisocyanate (MDI) polyurea prepolymer and soy-based polyol. A free-rise method was developed to prepare the sustainable PU foams for use in automotive and bedding cushions. In this study, three petroleum-based PU foams were compared with two soy-based PU foams in terms of their foam characterizations and properties. Soy-based PU foams were made with soy-based polyols with different hydroxyl values. Soy-based PU foams had higher T _g (glass transition temperature) and worse cryogenic properties than petroleum-based PU foams. Bio-foams had lower thermal degradation temperatures in the urethane degradation due to natural molecular chains with lower thermal stability than petroleum skeletons. However, these foams had good thermal degradation at a high temperature stage because of MDI polyurea prepolymer, which had superior thermal stability than toluene diisocyanate adducts in petroleum-based PU foams. In addition, soy-based polyol, with high hydroxyl value, contributed PU foam with superior tensile and higher elongation, but lower compressive strength and modulus. Nonetheless, bio-foam made with high hydroxyl valued soy-based polyol had smaller and better distributed cell size than that using low hydroxyl soy-based polyol. Soy-based polyol with high hydroxyl value also contributed the bio-foam with thinner cell walls compared to that with low hydroxyl value, whereas, petroleum-based PU foams had no variations in cell thickness and cell distributions.     

Thermal Stability and Flame Retardancy of Rigid Polyurethane Foams/Organoclay Nanocomposites

The thermal stability and flame retardancy of a new kind of rigid polyurethane (PU) foams/organoclay nanocomposites developed by our research group were investigated by using thermogravimetry analysis (TGA) and cone calorimeter test. Results indicate that compared with pure PU foams, rigid PU foams/organoclay composites show significantly enhanced thermal stability and flame retardancy. The reasons leading to the results were discussed in detail by relating with the morphology of the composites. The discussion suggests that the enhancement degree of thermal stability and flame retardancy of composites compared with that of PU foams coincides well with the sequences of gallery spacing of organoclay in the PU matrix.     

Rigid polyurethane foams made from high viscosity soy‐polyols

This study investigated the physical properties of water‐blown rigid polyurethane (PU) foams made from VORANOL®490 (petroleum‐based polyether polyol) mixed with 0–50% high viscosity (13,000–31,000 cP at 22°C) soy‐polyols. The density of these foams decreased as the soy‐polyol percentage increased. The compressive strength decreased, decreased and then increased, or remained unchanged and then increased with increasing soy‐polyol percentage depending on the viscosity of the soy‐polyol. Foams made from high viscosity (21,000–31,000 cP) soy‐polyols exhibited similar or superior density‐compressive strength properties to the control foam made from 100% VORNAOL® 490. The thermal conductivity of foams containing soy‐polyols was slightly higher than the control foam. The maximal foaming temperatures of foams slightly decreased with increasing soy‐polyol percentage. Micrographs of foams showed that they had many cells in the shape of sphere or polyhedra. With increasing soy‐polyol percentage, the cell size decreased, and the cell number increased. Based on the analysis of isocyanate content and compressive strength of foams, it was concluded that rigid PU foams could be made by replacing 50% petroleum‐based polyol with a high viscosity soy‐polyol resulting in a 30% reduction in the isocyanate content. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

制备工艺对聚氨酯酰亚胺泡沫性能的影响

以均苯四甲酸二酐(PMDA)、多苯基多亚甲基多异氰酸酯(PAPI)、聚醚多元醇为主要原料,分别采用聚酰亚胺(PI)预聚法、聚氨酯(PU)预聚法和一步法制备聚氨酯酰亚胺泡沫,从微观形貌、力学性能、热稳定性能以及阻燃性能方面对上述3种制备工艺进行对比和评估。实验结果表明,采用一步法制备PUI泡沫时,PU链段和PI链段同时增长,容易造成泡孔缺陷,导致泡沫的力学性能较差;在采用PU预聚法制备的PUI泡沫中,PU链段含量较高,因此,泡孔孔径分布较宽且平均泡孔直径较大,对应的热稳定性和阻燃性能较差;采用PI预聚法制备的PUI泡沫的泡孔孔径分布窄且平均泡孔直径较小,对应的压缩性能、热稳定性以及阻燃性能均达到最佳。     

Preparation and insulation property studies of thermoplastic PMMA-silica nanocomposite foams

The comparative studies for the effect of vinyl-modified silica (VMS) and raw silica (RS) particles on the cell structure, insulation (dielectric and thermal transport) properties, and thermal stability of thermoplastic PMMA-silica nanocomposite (PSN) foams are described. The VMS particles were synthesized by the conventional acid-catalyzed sol-gel reactions of tetraethyl orthosilicate (TEOS) in the presence of 3-(trimethoxysilyl)propyl methacrylate (MSMA) molecules. The as-prepared VMS particles were then characterized through fourier transform infrared (FTIR), solid-state ¹³C-nuclear magnetic resonance (¹³C-NMR) and ²⁹Si-NMR spectroscopy. Subsequently, the PSN materials were prepared via in-situ bulk polymerization. The dispersion of silica particles in PMMA matrix was observed by transmission electron microscopy (TEM) studies. Gel permeation chromatography (GPC) was used to determine the molecular weights of as-prepared samples. The PSN materials were used to produce foams by a batch process in an autoclave using nitrogen as foaming agent. The effect of VMS and RS particles on the cell structure, insulation properties and thermal stability of PSN foams were investigated by scanning electron microscopy (SEM), LCR meter, Transient plane source (TPS) technique and thermal gravimetric analysis (TGA), respectively. The better dispersion capability of VMS particles in PSN foams was found to lead enhanced nucleation efficiency, thermal stability and decreased dielectric constant (ε′), dielectric loss (ε″) and thermal conductivity (k). POLYM. COMPOS., 2009. © 2008 Society of Plastics Engineers     

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 %。     

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.     

In situ polymerization of polyurethane‐silver nanocomposite foams with intact thermal stability,improved mechanical performance,and induced antimicrobial properties

Silver nanoparticle‐reinforced thermoplastic polyurethane (PU/AgNP) nanocomposite foams were prepared using in situ polymerization techniques in accordance with DOW chemicals’ industrial standards. The foams exhibited improved mechanical performance, induced antimicrobial properties, and intact stability when subjected to a thermal degradation treatment. Scanning electron microscopy (SEM) indicated a homogeneous dispersion of the silver nanoparticle (AgNP) within the polymeric matrix at low filler loadings and a cluster formation at higher loadings. SEM also indicated the agglomeration of the silver nanofiller particles as a result of the thermal degradation treatment, which caused them to lose their nanoscopic characteristics and act as ordinary silver metal. Molecular modeling techniques were used to explain these observations and confirmed the higher repulsive interactions between the polymer chains and the silver nanoparticles with the increase in the nanofiller content. Stress relaxation of the nanocomposites showed optimum mechanical performance and lowest hysteresis for the 0.1% AgNP nanocomposites due to the confinement of the PU chains between the large number of the nanoparticles. Incubation with 0.1% foam inhibited the growth of Klebseilla spp. and Escherichia coli and to some extent Staphylococcus spp. This is very interesting as the same nanocomposite loaded with 0.1% AgNp has also shown the best mechanical performance highlighting the strong action of this “unclustered” low concentration on both the material and biomedical sides. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43125.     

Influence of structure of hydroxyl-terminated maleopimaric acid ester on thermal stability of rigid polyurethane foams

A series of hydroxyl-terminated maleopimaric acid esters (HTMAEs) and rigid polyurethane (PU) foams based on these HTMAEs were synthesized using chemically modified natural gum rosin and its derivative maleopimaric acid as raw materials. Thermal stability of these polyols and their corresponding rigid PU foams was studied by a thermogravimetric method and a dimensional stability measurement. It was shown that the thermal stability of the final foams was strongly dependent on the structure of their corresponding polyols. The thermogravimetric analysis curves of these rosin-based rigid PU foams displayed two distinct regions of weight loss. It has been shown that at the initial stage of weight loss the process was dominated by polyol component degradation; the second stage was governed by isocyanate component degradation. © 1995 John Wiley & Sons, Inc.     

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     

天然植物原料改性聚氨酯及其应用

综述了含天然纤维素的植物原料在聚乙二醇和聚酯多元醇中进行液化及制备改性聚氨酯(PU)。介绍了植物纤维改性PU、玉米秸杆改性PU、稻草改性PU、甘蔗渣改性PU、树皮改性PU的性能及应用。重点介绍了树皮的主要成分单宁改性淀粉PU的耐水性、抗菌性和热稳定性。这些植物原料通过液化改性可替代部分石油多元醇,以满足性能各异的高附加值聚氨酯的要求及在卫生、家具、食品包装和保温隔热等领域中的应用。     

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     

废旧聚氨酯硬质泡沫塑料的降解回收及再利用

采用双组分醇解剂乙二醇（EG）和丙二醇（PG）对废旧聚氨酯（PU）硬质泡沫塑料进行降解,获得了降解产物低聚物多元醇,并将其与木质素为原料制备出再生聚氨酯（r?PU）硬质泡沫塑料复合材料。利用导热系数测定仪、扫描电子显微镜、热重分析仪、傅里叶变换红外光谱仪等对废旧PU的降解效果和r?PU硬质泡沫复合材料的压缩强度、吸水率、导热系数、微观形貌及热稳定性等进行了分析和表征。结果表明,双组分醇解剂EG和PG质量比（m_EG：m_PG）为2：3时,废旧PU的降解效果最佳;当木质素添加量为6 %（质量分数,下同）时制备r?PU硬质泡沫复合材料的泡沫孔壁较厚且比较均匀,骨架几何构型完整,其压缩强度为185.3 kPa、导热系数为0.021 5 W/（m·K）,均能够达到国家标准要求。     

Rigid polyurethane foams from a soybean oil-based Polyol

Polyurethane (PU) rigid foams were synthesized by substituting a polypropylene-based polyol with soybean oil-based polyol (SBOP). All the soy-based foams maintained a regular cell structure and had even smaller average cell size than the control foams. The density of soy-based foams was within 5% of the controls, except that the density of foams from 100% SBOP was 17% higher. Soy-based foams also had comparable initial thermal conductivity (k value) and closed cell content, higher T_g and compressive strength. However, while foams from 50% SBOP showed similar increase in k value to the 0% SBOP foams, under accelerated aging conditions, the 100% SBOP foams aged faster. Gas permeation tests performed on PU thin films showed higher N₂ permeation for PU thin films made from SBOP which is believed to be the cause of accelerated thermal aging.     

Effects of a silane coupling agent on the exfoliation of organoclay layers in polyurethane/organoclay nanocomposite foams?

An attempt was made to synthesize polyurethane (PU)/organoclay nanocomposite foams with high thermal insulation properties. The organoclay was modified by polymeric 4,4′‐diphenylmethane diisocyanate (PMDI) with a silane coupling agent. The structure of the organoclay‐modified PMDI with the silane coupling agent was determined by Fourier transform infrared spectroscopy and nuclear magnetic resonance. Transmission electron micrographs and wide‐angle X‐ray diffraction patterns showed that the interlayer distance increased for the PU/organoclay nanocomposites with the addition of the silane coupling agent. It was expected that the distance between the organoclay layers would increase and that the organoclay would be dispersed on a nanoscale in the PU matrix because of the organic/inorganic hybrid bond formation between the organoclay and silane coupling agent. Compressive and flexural strengths of the PU/silane coupling agent/organoclay nanocomposite foams were similar to those of the PU/organoclay nanocomposite foams. However, the thermal conductivity appreciably decreased from 0.0250 to 0.0230 W/m h °C in the PU/silane coupling agent/organoclay nanocomposite foams. Scanning electron micrographs showed that the cell size of the PU/silane coupling agent/clay nanocomposite foams also decreased. On the basis of these results, it is suggested that the smaller cell size and lower thermal conductivity of the PU/silane coupling agent/organoclay nanocomposite foams were mainly due to enhanced exfoliation of the organoclay layers by the silane coupling reaction. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Fabrication and characterization of novel foaming polyurethane hollow fiber membrane

Foam-like materials had attracted great interest as promising absorbent. In this study, thermoplastic polyurethane(TPU) block sponge was synthesized. Polyester(PET) braid tubular reinforced polyurethane(PU) spongy hollow fiber membrane was prepared by a concentric circular spinning method. The method was woven from an outer coated water-blown PU separation layer and inner PET braid tubular. We have developed a simple and useful preparation technique for the PU spongy hollow fiber membrane. For the first time, the PU spongy hollow fiber membrane was prepared using a coating and controlled foaming technique. The influence of toluene isocyanate index on the physical properties, morphology, and structure of flexible PU sponge was discussed in terms of water contact angle(CA), pure water flux(PWF), Fourier Transform Infrared Analysis(FTIR),pressure-responsive property, and pull-out strength. The morphologies of the membranes were investigated by scanning electron microscopy. We have characterized the foams from an intuitive point of view and demonstrated that the dimensional morphology of the membrane was closely related to isocyanate index. The result showed that the surface cell size of the PU sponge hollow fiber membrane gradually decreased with an increase of the isocyanate index. Due to the elasticity of PU at room temperature, the pressure responsive characteristic of the membrane was prepared. When isocyanate index was 1.05, the interface bonding strength of PU spongy hollow fiber membranes reached as high as 0.37 MPa, porosity and PWF were 71.5% and 415.5 L·m~(-2)·h~(-1),respectively.     

秸秆的自加热及自燃特性研究

针对秸秆堆积储存和制粉过程中的自燃问题,采用杜瓦瓶自加热装置对稻草(RS)、麦秸(WS)、玉米秸秆(CS)堆积储存的自加热过程进行研究,并考察含水量对自加热的影响;同时,采用慢速升温的热重分析方法对3种秸秆的低温氧化特性进行研究.自加热实验结果显示:3种秸秆的自加热过程遵循相同的规律(均分为诱导期、温度上升期和温度下降...     

Effect of incorporation of crop residues and organic manures on adsorption/desorption and bio-availability of phosphate

Transformations of applied phosphorus (P) to unavailable residual soil P is the major cause of limited P supply in most of the P-deficient soils. The effect of the incorporation of crop residues (rice straw [RS] and wheat straw [WS]) and organic manures (farmyard manure [FYM] and green manure [GM]) on P release in soil and its bio-availability to various summer and winter crops was investigated in laboratory and screen house experiments. Surface (0–0.15 m) soil samples collected after 32 years of differential fertilization to maize–wheat–cowpea fodder crop rotation, were examined for adsorption/desorption behavior of P, after incubating with organics of varying C:P ratios. Incorporation of crop residues increased P adsorption maxima as well as resistance to P release in soils. Increased buffering capacities in crop residue-incorporated treatments decreased P desorption in soil, whereas the incorporation of organic manures decreased P sorption, maximum buffering capacity (MBC), bonding energy, and increased P concentration in soil solution. Although the incorporation of crop residues decreased P release in soil its bio-availability in the soil–plant system was crop-specific and varied with the time of incorporation of organics. Raya showed increased P uptake with incorporation of both RS and WS, whereas in the case of berseem increased P uptake occurred only with wheat straw. Phosphorus uptake in rice, maize, and soybean decreased with the incorporation of both RS and WS. Incorporation of crop residues 1 day before the sowing of summer crops decreased P uptake, whereas incorporation 3 weeks prior to the sowing of winter crops improved P bio-availability. Incorporation of organic manures with a narrow C:P ratio, however, improved P uptake in all the crops under investigation, in both the seasons. The results thus emphasized that adsorption parameters calculated from the examination of soil samples should not be used independently for making fertilizer P recommendations. Crop effects (root exudates) and their interaction with P reaction products in soil and synchronization in P release from organics and crop uptake need to be considered to understand the virtual behavior of P bio-availability in the soil–plant system.     

Glass bubble reinforced polyurethane foams with high mechanical strength for cryogenic temperature insulation

In this study, glass bubble (GB) is added to polyurethane (PU) foams at different weight ratios—0, 0.25, 0.5, 0.75, and 1 wt% —to investigate the changes in the mechanical and thermal properties of the foam. By conducting several tests and measurements, the density, cell morphology, compressive strength, and thermal conductivity of the foam are studied. In particular, the effect of GB additives is examined by conducting compression tests at various temperatures (−163, −100, −40, and 20°C). Scanning electron microscopy and X-ray microscope reveal that the foams exhibit higher stability below 0.5 wt%, which improves the thermal performance. On the other hand, the compressive strength of the foams increases for all weight ratios of GB, and it increases sharply at 0.75 wt%. In addition, the chemical interactions and the dispersion of additives in the PU matrix are investigated through Fourier transform infrared and X-ray diffractions analysis. It is found that the synthesis of PU foams with GB nanoparticles is an efficient method for improving the mechanical properties and insulation performance of the foam for LNG insulation technology.