Effects of the hydroxyl value of polyol in rigid polyurethane foams

Rigid polyurethane foams (RPUFs) have been fabricated from crude MDI (CMDI) and polypropylene glycols (PPGs) of various hydroxyl values (OHVs) of 300–600 with an environmentally friendly blowing agent (HFC 365mfc). The closed cell content, compression strength, and dimensional stability of the foam increased with increase in the OHV due to the increased crosslink density, which was evidenced from the increased glass transition temperature (T_g). The cream time, gel time, tack‐free time, and density of the foam showed a minimum at 500OHV. The decrease and increase around the minimum were, respectively, interpreted in terms of increased mixture mobility and extensive allophanate crosslinks, which retard gelling as well as foaming reactions. The thermal conductivity also showed a small minimum at 500OHV. Copyright © 2008 John Wiley & Sons, Ltd.     

Effect of a Nanoclay on the Mechanical,Thermal and Flame Retardant Properties of Rigid Polyurethane Foam

Water blown rigid polyurethane foams (PUF) with organoclay/organically modified nanoclay (ONC) were prepared and their properties such as density, mechanical, morphological, insulation, thermal and flame retardant properties were studied. In this investigation, the ONC content was varied from 1 to 10 parts per hundred of polyol (php) by weight. It was observed that the compressive strength of ONC filled PUF increased up to 3 php of ONC loading and then it decreased. Wide angle X-ray diffraction and transmission electron microscopy studies indicated the exfoliated dispersion of ONC in PUF. The thermal conductivity of ONC filled PUF decreases up to 5 php and then increases. The glass transition temperature (Tg) of PUF decreases on loading of ONC. The TGA analysis shows that there is slight increase in degradation temperature with increase in ONC loading. The flame retardant properties (LOI and flame spread rate) are improved slightly on addition (3 php) of ONC filled PUF.     

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.     

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.     

改性可膨胀石墨的制备及在硬质聚氨酯泡沫中的阻燃性能

采用表面接枝硅烷偶联剂法将硼酸负载在可膨胀石墨(EG)表面制得了改性EG(MEG), 并考察了MEG在硬质聚氨酯泡沫(RPUF)中的阻燃性能. 利用扫描电子显微镜、 X射线光电子能谱、 傅里叶变换红外光谱、 膨胀试验及热失重分析对MEG进行了形貌、 元素组成及结构性能表征, 通过热失重分析、 极限氧指数(LOI)及锥形量热仪考察了RPUF/MEG的热稳定性及燃烧性能. 结果表明, 硼硅化合物作为硅硼陶瓷前驱体已负载在EG表面; MEG及RPUF/MEG体系膨胀炭层更为致密, 800 ℃时的残余量分别较EG和RPUF/EG提高了8.7%和3.7%; RPUF/MEG体系的LOI较RPUF/EG有所提高, 热释放速率峰值降低了10%, 产烟速率及CO生成速率均显著降低. RPUF/MEG阻燃性能的提高与MEG负载的硅硼陶瓷前驱体促进了阻燃RPUF各组分间的相互作用及增强了炭层的阻隔性有关.     

Effect of blowing agent content on the structure and flame-retardant properties of rigid polyurethane foam/expanded graphite composites

Driven by global environmental issues, the development of green building materials has become an immediate focus. In this work, n-pentane was used as an environmentally friendly blowing agent to prepare flame-retardant rigid polyurethane foam (RPUF) with the addition of expandable graphite (EG) successfully, and the effect of n-pentane content on flame retardancy and compressive properties of RPUF/EG composites was investigated through limit oxygen index (LOI), vertical burning test (UL-94), scanning electron microscope (SEM), thermogravimetric analysis (TGA), and compressive properties test. SEM results show that the content of EG and n-pentane causes a change in the cell structure of RPUF. The change of the n-pentane content has also an obvious effect on the thermal stability, flame retardancy, and specific compressive strength of RPUF/EG composites. In addition, the cell structure of RPUF matrix has an obvious influence on the distribution of EG in the composites, which indirectly affects the flame-retardant efficiency of EG. This research explores the conditions for the application of environmentally friendly RPUF and expands its application prospects.     

以乙烯基酯树脂为多元醇制备聚氨酯硬质泡沫塑料的研究

研究了用乙烯基酯树脂（ＶＥＲ）直接代替通常的聚醚或聚酯型多元醇制备聚氨酯（ＰＵ）硬质泡沫塑料的可能性。实验结果表明,发泡配方中促进氨酯化反应的催化剂Ｎ,Ｎ－二甲基环己胺能与ＢＰＯ复合形成室温引发体系,加速ＶＢＲ的共聚合反应,影响了ＰＵ硬质泡沫塑料形成过程中的发泡与凝胶反应,导致泡了孔骨架基材的交联密度较低,泡孔结构不规整,并显示出较差的物理性能。以ＡＩＢＮ为引发剂时,反应初期主要进行氨酯化反应;仅     

Preparation of Boron-coated Expandable Graphite and Its Application in Flame Retardant Rigid Polyurethane Foam

A novel boron-coated expandable graphite(BEG) material was prepared by first wrapping polyvinyl alcohol(PVA) onto expandable graphite(EG) and then condensing with boric acid. The obtained BEG was characterized by scanning electron microscopy(SEM), Fourier transform infrared(FTIR) spectroscopy, X-ray photoelectron spectroscopy(XPS), and thermogravimetric analysis(TGA). The fire performance and mechanical properties of the rigid polyurethane foam(RPUF) filled with BEG were investigated by limiting oxygen index(LOI), horizontal and vertical burning, cone calorimetry(CONE), and electronic tensile tests. BEG shows an improved compactness of the char layers upon thermal expansion, which is effective for the flame retardancy of RPUF. With a loading of 10%, RPUF/BEG exhibited a higher LOI, >10% reduction in heat release rate and carbon monoxide release, as well as a decrease in smoke release during the beginning of combustion compared to RPUF/EG. Moreover, the compressive strength and modulus of RPUF/BEG were increased. The improved flame retardancy of BEG on RPUF can be attributed to the suppression of the "popcorn effect" of EG by PVA-boric acid, and the improved mechanical property can be attributed to the presence of PVA.     

聚氨酯泡沫塑料中氯的测定

研究了氧瓶燃烧-分光光度法测定聚氨酯泡沫塑料中氯含量的方法．采用氧瓶燃烧法分解聚氨酯泡沫塑料,然后用硫氰酸汞分光光度法测定其中氯含量．实验结果表明,氧瓶燃烧-分光光度法能有效地测定聚氨醣泡沫塑料中氯元索的含量,该方法简便、准确、实用性强、灵敏度高,适合快速分析。     

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.     

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…     

热塑性聚氨酯微孔发泡材料的表观密度与其力学性能的关系

用高压CO2流体通过升温发泡法制备了一系列不同表观密度的热塑性聚氨酯(TPU)微孔发泡材料,探究了TPU发泡材料的表观密度与其力学性能的关系.微孔发泡材料的泡孔结构和表皮结构由扫描电子显微镜表征;不同表观密度材料的力学性能利用万能材料试验机和旋转流变仪表征.研究发现:TPU微孔发泡材料的表观密度主要是由材料皮层厚度占比和泡孔层密度决定的,皮层厚度占比越小和泡孔面积占有率越高,泡沫的表观密度越小;微孔发泡材料在线性应变区的压缩模量E与材料表观密度ρ的关系为:E∝ρ1.7,符合泡沫材料压缩模量与表观密度呈指数关系的基本结论;循环压缩实验中,随微孔发泡材料表观密度减小,损耗百分比增大,残余应变减小;流变实验中,微孔发泡材料的模量随表观密度变化没有明显的变化,阻尼因子tanδ随泡沫表观密度变化不呈单一的规律性.同时,阐明了微孔发泡材料的压缩模量E和损耗百分比随表观密度变化的机理.     

Lignin as a Partial Polyol Replacement in Polyurethane Flexible Foam

This study was focused on evaluating the suitability of a wide range of lignins, a natural polymer isolated from different plant sources and chemical extractions, in replacing 20 wt.% of petroleum-based polyol in the formulation of PU flexible foams. The main goal was to investigate the effect of unmodified lignin incorporation on the foam’s structural, mechanical, and thermal properties. The hydroxyl contents of the commercial lignins were measured using phosphorus nuclear magnetic resonance (³¹P NMR) spectroscopy, molar mass distributions with gel permeation chromatography (GPC), and thermal properties with differential scanning calorimetry (DSC) techniques. The results showed that incorporating 20 wt.% lignin increased tensile, compression, tear propagation strengths, thermal stability, and the support factor of the developed PU flexible foams. Additionally, statistical analysis of the results showed that foam properties such as density and compression force deflection were positively correlated with lignin’s total hydroxyl content. Studying correlations between lignin properties and the performance of the developed lignin-based PU foams showed that lignins with low hydroxyl content, high flexibility (low T_g), and high solubility in the co-polyol are better candidates for partially substituting petroleum-based polyols in the formulation of flexible PU foams intended for the automotive applications.     

SiO2/炭泡沫和SiC/炭泡沫复合材料的制备及表征

对炭泡沫为支撑骨架的氧化硅气凝胶(SiO₂/炭泡沫)和碳化硅(SiC/炭泡沫)复合材料分别采用XRD、SEM、激光导热仪、万能力学试验机进行物相、微观结构、热学及力学性能方面的表征.结果表明:所制备的SiO₂/炭泡沫与原炭泡沫相比,具备更高的抗压强度(14.95 MPa)和更低的室温热导率(0.44 W·m^-1·K^-1).SiC/炭泡沫材料则保持了较高的抗压强度值(14.66 MPa),其在 1 200 ℃下具备极低的高温热导率(2.18W·m^-1·K^-1).热重分析表明,SiC/炭泡沫在氧化氛围中到610 ℃才发生质量的损失,而内部炭发生完全烧蚀的温度高达844 ℃,这表明该材料的抗氧化性能远好于纯的炭泡沫材料.     

SiO2/炭泡沫和SiC/炭泡沫复合材料的制备及表征

对炭泡沫为支撑骨架的氧化硅气凝胶(SiO₂/炭泡沫)和碳化硅(SiC/炭泡沫)复合材料分别采用XRD、SEM、激光导热仪、万能力学试验机进行物相、微观结构、热学及力学性能方面的表征。结果表明:所制备的SiO₂/炭泡沫与原炭泡沫相比,具备更高的抗压强度(14.95MPa)和更低的室温热导率(0.44W·m^-1·K^-1)。SiC/炭泡沫材料则保持了较高的抗压强度值(14.66MPa),其在1200℃下具备极低的高温热导率(2.18W·m^-1·K^-1)。热重分析表明,SiC/炭泡沫在氧化氛围中到610℃才发生质量的损失,而内部炭发生完全烧蚀的温度高达844℃,这表明该材料的抗氧化性能远好于纯的炭泡沫材料。     

Indirect Determination of Phosphate by X-ray Fluorescence Spectrometry Using Polyurethane Foam

Abstract

An indirect X-ray fluorescence method for phosphate has been established based on the extraction of phosphomolybdate by polyurethane foam. The molybdenum, which is associated in a fixed ratio with phosphorus, is determined directly on foam, by X-ray fluorescence spectrometry.     

Preconcentration Systems Using Polyurethane Foam/Me-BDBD for Determination of Copper in Food Samples

A new reagent, 6-[2′-(6′-methyl-benzothiazolylazo)]-1,2-dihydroxy-3,5-benzenedisulfonic acid (Me-BDBD), was synthesised and used in on-line and off-line systems for copper preconcentration by solid-phase extraction. Spectrophotometry and Flame Atomic Absorption Spectrometry (FAAS) were the detection techniques. Polyurethane foam loaded with Me-BDBD packed in a minicolumn was used as sorbent in both systems. The spectral characteristics of Me-BDBD were investigated. The optimum pH values for maximum sorption of the metal are between 7.0 and 8.5. Copper was desorbed with 0.05 and 0.50 mol L⁻¹ hydrochloric acid solutions, for on-line and off-line systems, respectively. The effects of several foreign substances on the adsorption of copper are reported. The enrichment factors obtained were 7 (on-line) and 26 (off-line) for the systems. The proposed procedures allowed the determination of copper with detection limits of 3.4 and 1.4 μg L⁻¹ (0.85 and 0.35 μg per gram of sample) for on-line and off-line systems, respectively. The precision of the procedures was also calculated: 3.2 (on-line) and 1.9% (off-line). The validation of the procedures was carried out by analysis of certified reference material. The copper contents in corn and rice flour and black tea samples were determined by applying the proposed procedures.     

Flame-Retarded Rigid Polyurethane Foam Composites with the Incorporation of Steel Slag/Dimelamine Pyrophosphate System: A New Strategy for Utilizing Metallurgical Solid Waste

Rigid polyurethane (RPUF) was widely used in external wall insulation materials due to its good thermal insulation performance. In this study, a series of RPUF and RPUF-R composites were prepared using steel slag (SS) and dimelamine pyrophosphate (DMPY) as flame retardants. The RPUF composites were characterized by thermogravimetric (TG), limiting oxygen index (LOI), cone calorimetry (CCT), and thermogravimetric infrared coupling (TG-FTIR). The results showed that the LOI of the RPUF-R composites with DMPY/SS loading all reached the combustible material level (22.0 vol%~27.0 vol%) and passed UL-94 V0. RPUF-3 with DMPY/SS system loading exhibited the lowest pHRR and THR values of 134.9 kW/m² and 16.16 MJ/m², which were 54.5% and 42.7% lower than those of unmodified RPUF, respectively. Additionally, PO· and PO₂· free radicals produced by pyrolysis of DMPY could capture high energy free radicals, such as H·, O·, and OH·, produced by degradation of RPUF matrix, effectively blocking the free radical chain reaction of composite materials. The metal oxides in SS reacted with the polymetaphosphoric acid produced by the pyrolysis of DMPY in combustion. It covered the surface of the carbon layer, significantly insulating heat and mass transport in the combustion area, endowing RPUF composites with excellent fire performance. This work not only provides a novel strategy for the fabrication of high-performance RPUF composites, but also elucidates a method of utilizing metallurgical solid waste.     

泡沫塑料富集-原子吸收光谱法测定铅精矿中的金

主要研究了铅精矿特别是高铅矿中金的溶解、富集分离,吸附富集条件、解吸条件。通过用泡沫塑料富集,原子吸收光谱法测定铅精矿中的金,测定方法的相对标准偏差小于5%,准确度满足生产需求。泡沫塑料富集分离金操作简便,无需特殊装置,可达到分离的目的,且选择性高,在保证分析结果质量的基础上加快了分析速度、降低了分析成本。