Chemical degradation of polyurethanes. II. Degradation of microporous polyurethane elastomer by phosphoric acid esters

Microporous polyurethane elastomer, based on 4,4′‐diphenylmethane diisocyanate and polyester polyol Bayflex 2003 (Bayer AG), was degraded by phosphoric acid esters  (CH₃CH₂O)₃P(O) and (ClCH₂CH₂O)₃P(O) at 180°C. Structure of degraded products was investigated by means of ¹H‐, ¹³C‐, and ³¹P‐NMR spectroscopy. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 76: 886–893, 2000     

Modeling of glycolysis of flexible polyurethane foam wastes by artificial neural network methodology

The glycolysis process as a useful approach to recycling flexible polyurethane foam wastes is modeled in this work. To obtain high quality recycled polyol, the effects of influential processing and material parameters, i.e. process time, process temperature, catalyst‐to‐solvent (Cat/Sol) and solvent‐to‐foam (Sol/Foam) ratios, on the efficiency of the glycolysis reaction were investigated individually and simultaneously. For the continuous prediction of process behavior and interactive effects of parameters, an artificial neural network (ANN) model as an efficient statistical‐mathematical method has been developed. The results of modeling for the criteria that determine the glycolysis process efficiency including the hydroxyl value of the recycled polyol and isocyanate functional group conversion prove that the adopted ANN model successfully anticipates the recycling process responses over the whole range of experimental conditions. The Cat/Sol ratio showed the strongest influence on the quality of the recycled polyol among the studied parameters, where the minimum hydroxyl value was obtained at a medium amount of the assigned ratio. For the consumed polyurethane foam, a higher value of this ratio led to an increase in the hydroxyl value and isocyanate conversion. © 2015 Society of Chemical Industry     

Water-blown flexible polyurethane foam extended with biomass materials

Soy protein isolate, soy fiber, and cornstarch (0–40% polyether polyol) were incorporated into a flexible polyurethane foam formulation. Stress–strain curves of the control foam and foams containing 10–20% biomass material exhibit a considerable plateau stress region but not for foams extended with 30–40% biomass materials. An increase in biomass material percentage increases foam density. An increase in initial water content decreases foam density. Foams extended with 30% soy protein isolate, as well as foams extended with 30% soy fiber, have notably greater resilience values than all other extended foams. The comfort factor increases with increasing percentage of biomass material in foam formulation. Foams containing 10–40% biomass materials display significantly lower values in compression-set than the control foam. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 65: 695–703, 1997     

Exceptionally flame-retardant flexible polyurethane foam composites: synergistic effect of the silicone resin/graphene oxide coating

A facile strategy was developed to fabricate flexible polyurethane (PU) foam composites with exceptional flame retardancy. The approach involves the incorporation of graphene oxide (GO) into a silicone resin (SiR) solution, which is then deposited onto a PU foam surface via the dip-coating technique and cured. Fourier-transform infrared spectroscopy, scanning electron microscopy, and Raman spectroscopy measurements demonstrated that the SiR and GO were successfully coated onto the PU skeleton and the intrinsic porous structure of the PU foam remained intact. The effects of SiR and GO on the mechanical and thermal stability and flame retardancy of PU composites were evaluated through compression tests, thermogravimetric analysis, vertical combustion tests, and the limiting oxygen index. The measurement results revealed that the composites (PU@SiR-GO) showed superior flame retardancy and thermal and mechanical stability compared to pristine PU or PU coated with SiR alone. The mechanical and thermal stability and the flame-retardant properties of the PU composites were enhanced significantly with increasing GO content. Based on the composition, microstructure, and surface morphology of PU@SiR-GO composites before and after combustion tests, a possible flame-retardance mechanism is proposed. This work provides a simple and effective strategy for fabricating flame-retardant composites with improved mechanical performance.     

Dynamic mechanical properties of SBR and EPDM vulcanisates filled with cryogenically pulverized flexible polyurethane foam particles

The dynamic mechanical properties of rubber vulcanisates filled with cryogenically pulverized polyurethane foam particles, used as a reinforcing filler, were investigated with respect to storage modulus (E′), loss modulus, and the variation of glass transition temperature. Two rubbers were using styrene–butadiene rubber (SBR) and ethylene–propylene copolymer (EPDM). The effects of filler concentration and filler characteristics (such as particle size and moisture content) were also monitored. It was found that the optimum dynamic mechanical properties of the compounds were obtained when introducing the PU particles of 40–50 parts per hundred (pph) rubber in the SBR and 30 pph in the EPDM, the properties being affected by the size of PU particles and moisture content. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 1129–1139, 1999     

Effect of monomer temperature on foaming and properties of flexible polyurethane foams

Polyurethane foam formation involves simultaneous polymerization and expansion. In an open cell foam, foam lamellae rupture at some stage of foam formation, resulting in a foam with continuous air channels. Experiments are carried out to study the effect of initial temperature of monomers on the open cell content of water‐blown flexible polyurethane foams. The change in kinetics of the polymerization and blowing with initial monomer temperature is noted by measuring the gel and rise times during foaming. Both polymerization and blowing reactions are found to be faster with increasing monomer temperature. The cell size is found to increase with initial monomer temperature, and the height of the cured free rise foam is found to decrease. The open cell content of the foam increased considerably with initial monomer temperature, leading finally to the collapse of the foam at the highest temperatures studied. The mechanical properties of the foam at different monomer temperatures are determined by making molded foams. The indentation load deflection decreased with increasing monomer temperature indicating the formation of softer foams, but showed a slight increase near the temperature of collapse. Other mechanical properties showed a small degradation with increase in initial monomer temperatures. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Role of two stage pyrolysis in fire growth on flexible polyurethane foam slabs

A series of experiments designed to characterize fire behavior on flat 1.2 m × 1.2 m samples of commercial non‐fire‐retarded flexible polyurethane foam were performed. Time‐resolved heat release and mass loss rates were measured. Experimental parameters varied, including foam thickness (5.1 and 10.2 cm) and burning angle (+25°, +12.5°, 0°, ?12.5°, and ?25°). Polyurethane foam is typically produced by reacting a multifunctional isocyanate with a polyol. The foam used here was formed by reacting toluene diisocyanate and a polyol based on a condensed polyether of polypropylene oxide. Earlier cone calorimeter studies of this foam had revealed a clear two stage pyrolysis behavior in which the heated foam first released a gaseous fuel derived from the isocyanate component, while leaving behind a liquid produced primarily from the polyol, which only gasified and burned following additional heating. The subsequent burning behavior of the polyol‐derived liquid is shown in this work to play a crucial role in the maximum heat release rate and total heat released by the fires spreading across the foam slabs. Published 2013. This article is a U.S. Government work and is in the public domain in the USA.     

Controlled degradation of natural rubber and modification of the obtained telechelic oligoisoprenes: Preliminary study of their potentiality as polyurethane foam precursors

Telechelic oligoisoprenes were successfully prepared by the selective controlled degradation of natural rubber, a renewable source, via epoxidation and cleavage reactions. The molar mass of the oligoisoprene product obtained depends on the degree of epoxidation of the starting materials. The chemically modified structures obtained via epoxidation, hydrogenation, and ring opening of epoxide groups were also studied, and the chemical structures and thermal properties of the oligoisoprene products were determined. Moreover, the preliminary study of preparation of hydroxytelechelic natural rubber (HTNR)‐based polyurethane foam was performed. A novel HTNR‐based polyurethane foam was successfully prepared and its thermal properties were investigated and the results indicated that the HTNR‐based polyurethane foam has a good low temperature flexibility. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

慢回弹聚氨酯软泡组合料的制备及应用研究

以慢回弹聚醚、普通聚醚、催化剂、泡沫稳定剂、开孔剂,异氰酸酯等为原料,制备慢回弹聚氨酯聚醚组合料及慢回弹聚氨酯软泡,并检测其性能.结果表明,水用量在2份,L598催化剂在4.5份,模具温度在45℃,异氰酸酯指数在75时,慢回弹聚氨酯软泡具有较好的发泡工艺及泡孔结构,密度与力学性能较好.     

软质聚氨酯泡沫塑料无卤阻燃技术研究进展

软质聚氨酯泡沫(FPUF)是聚氨酯材料的主要产品之一,由于其较低的密度和热传导率而易燃,在燃烧过程中会放出大量烟雾和有毒气体,对FPUF进行阻燃处理尤为重要。卤系阻燃剂由于存在潜在的毒性和环境问题而受到限制,因此FPUF的无卤阻燃技术是今后主要的研究方向。本文综述了近年有关软质聚氨酯泡沫无卤阻燃技术的研究进展,包括添加型无卤阻燃剂法、反应型无卤阻燃剂法、层层组装涂层法。指出开发高相对分子质量、含多种阻燃元素的有机添加型阻燃剂和膨胀型阻燃剂以及复配型阻燃剂,解决层层组装涂层法的组装慢等问题将是FPUF无卤阻燃技术的发展趋势。     

Recycling of rigid polyurethane foam: Micro-milled powder used as active filler in polyurethane adhesives

Rigid polyurethane (PUR) foams are widely used as heat insulation material in construction industry or for electronic appliances manufacturing. After finishing their life-time, it is necessary to eliminate foam wastes. The aim of this study was to prepare a pair of industrial PUR adhesives of medium viscosity containing recycled rigid PUR foam. Three methods of milling were tested: knife-milling, two-roll milling, and ball-milling. Only two-roll milling gives the PUR micro-powder usable for following adhesives modification. The micro-powder was used as passive filler in PUR adhesives and potential reactivity for polyol pack replacement was studied. Hydroxyl and amine numbers were determined in mixture with virgin polyol. One-component PUR prepolymer adhesive was prepared using various dosages of the micro powder and the tensile strength of bound wood was measured. As additional parameters, also free film adhesive mechanical parameters were tested and particle size distribution of the micro powder was analyzed. Two adhesive formulations were prepared for independent evaluation of the micro powder reactivity. The results showed growing of the mechanical strength of wood bonding with growing dosage of the micro powder.     

纳米二氧化硅改性硬质聚氨酯泡沫塑料的研究

采用浇注成型法合成密度为250 mg/cm3的纳米SiO2改性硬质聚氨酯泡沫塑料(PUR-R),研究了纳米SiO2含量及偶联剂处理对纳米SiO2改性PUR-R的各种力学性能的影响。结果表明:直接使用纳米SiO2,可使PUR-R的某些力学性能得到提高,而偶联剂处理可进一步改善纳米SiO2对PUR-R的增强作用,用偶联剂改性过的纳米SiO2增强PUR-R与纯PUR-R相比,除断裂伸长率降低外,其他力学性能如拉伸强度、压缩强度、弯曲强度、冲击强度及弯曲模量等均有所提高。     

小桐子油脂肪酸聚酯多元醇及聚氨酯泡沫的制备和性能

研究了脂肪酸环氧-开环-酯化三步反应制备聚酯多元醇,比较了3种不同碘值的脂肪酸原料制备的聚酯多元醇及其聚氨酯泡沫（PUF）性能。脂肪酸碘值越高多元醇的羟值也越高：1#、2#和3#聚酯多元醇羟值分别为：261.47 mgKOH/g、370.28 mgKOH/g和434.49 mgKOH/g。3种多元醇的相对分子量为600～2000。3种泡沫的压缩和弯曲性能与泡沫密度成正比。泡沫SEM分析显示：羟值较高的多元醇泡沫2#和3#泡沫孔结构较规则,以正五边形和正六边形居多;1#泡沫泡孔不规则,易变形。对3种泡沫的TG-DSC、DTG分析结果表明：3种泡沫的热分解温度都约为300 ℃,具有较好热稳定性。     

组合多元醇对硬质聚氨酯泡沫塑料力学性能的影响

将中等羟值聚醚多元醇、低羟值聚醚多元醇、聚合物多元醇和苯酐聚酯多元醇分别与基础聚醚多元醇复配,制备了全水发泡硬质聚氨酯泡沫塑料,研究了4种不同组合多元醇对制品力学性能的影响,发现低羟值多元醇的加入使泡孔直径明显减小;过低羟值的TMN3050的加入对力学性能的提高不利;TMN700使泡沫体的压缩强度略为增加,冲击强度大幅提高,弯曲强度略为下降;聚合物多元醇TPOP36/28在低添加量下,制得硬泡泡孔直径明显减小,压缩强度和冲击强度大幅增加,弯曲强度降低;苯酐聚酯多元醇PS400A,使泡孔直径减小,制得硬泡的密度和力学性能大幅降低。     

醇-磷酸酯法降解废旧聚氨酯的研究

选用不同的降解剂,采用醇-磷酸酯法降解废旧聚氨酯泡沫,对降解产物进行性能测试。结果表明：以一缩二乙二醇和磷酸三正丁酯为降解剂降解聚氨酯软质泡沫效果较好。以降解产物作为部分原料制备聚氨酯硬质泡沫塑料体,对其性能测试并与不加降解产物制备的聚氨酯硬质泡沫体比较,结果表明：降解产物作为部分原料对聚氨酯硬质泡沫塑料的性能影响不大。     

Environment‐friendly chemical recycling of aliphatic polyurethanes by hydrolysis in a CO2‐water system

In order to develop a chemical recycling system of polyurethanes (PUs), environment‐friendly hydrolysis of two types of aliphatic PUs was studied under pressured CO₂ in water, in which the carbonic acid generated from CO₂ acted as an acid catalyst. Two PUs, namely H‐PU or I‐PU, were synthesized starting from 1,4‐butanediol and 1,6‐hexamethylene diisocyanate or isophorone diisocyanate, respectively. The hydrolysis of PUs depended on the experimental conditions, such as the temperature and CO₂ pressure. As a result, 98% of H‐PU and 91% of I‐PU were successfully hydrolyzed under the typical conditions of 190 °C for 24 h at 8.0 MPa CO₂. The reaction mixtures afforded 1,4‐butanediol and diamines without the formation of any byproducts. Both of these raw materials generated from the originated PUs by selective hydrolytic cleavage of the urethane linkages, and they were easily isolated in high yields simply by evaporation of the water‐soluble components within the reaction mixture. By comparing the results of the two aliphatic PUs with those of an aromatic PU (M‐PU), the hydrolyzability was found to decrease in the order H‐PU, I‐PU, and M‐PU. The difference can be ascribed to the hydrophilicity of the aliphatic or aromatic groups connected to the urethane moieties at the terminals of PUs. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45897.     

Acoustic characterization of natural areca catechu fiber-reinforced flexible polyurethane foam composites

The development of acoustic absorbers from natural resources is a novel approach in acoustics. In the current study, the effect of unprocessed raw areca fiber (AF) particle reinforcement on the sound absorption (SA) behavior of polyurethane (PU) foam composites is investigated. Influences of fiber weight percentage and graded distribution of fiber with varying fiber weight percentage on the SA coefficient (SAC) of the composite foams are examined through the impedance tube approach. Morphological studies are carried out with the help of FESEM images to investigate the acoustic energy dissipation mechanism of PU foam and its composites. It is found that the SA capability of the composite foam is enhanced by increased fiber weight percentage, graded distribution of fiber wt%, varying sample thickness, and air cavity length. In general, PU-AF composite specimens show a peak SA value of 0.95 around 450 Hz, which is not the case for other natural fiber results available in the literature. Theoretical results predicted using the JCA (Johnson-Champoux Allard) model agree with the experimental results.     

Modification of unsaturated polyester resin by polyurethane prepolymers

Unsaturated polyester resins (UPRs) are extensively used by the fiber‐reinforced plastic (FRPs) industry. These resins have the disadvantages of brittleness and poor resistance to crack propagation. In this study, UPRs were chemically modified by reactive blending with polyurethane prepolymers having terminal isocyanate groups. Hybrid networks were formed by copolymerisation of unsaturated polyesters with styrene and simultaneous reaction between terminal hydroxyl groups of unsaturated polyester and isocyanate groups of polyurethane prepolymer. The prepolymers were based on toluene diisocyanate (TDI) and each of hydroxy‐terminated natural rubber (HTNR), hydroxy‐terminated polybutadiene (HTPB), polyethylene glycol (PEG), and castor oil. Properties like tensile strength, toughness, impact resistance, and elongation‐at‐break of the modified UPRs show considerable improvement by this modification. The thermal stability of the copolymer is also marginally better. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 449–456, 2006     

Cell distributions in and sound absorption characteristics of flexible polyurethane foams

In this article, the two-dimensional distributions of cells from the cross section of some flexible polyurethane foams were cleared, and the three-dimensional distributions of cells based on Saltykov's theory were estimated further. As a result, it was found that a mean of the two-dimensional distributions of cells was a good linear relation with a mean of the three-dimensional distributions of cells, and it was confirmed that cell structure of the foams which should have been analyzed in the three-dimensional distributions was evaluated by analysis of the two-dimensional distributions fully. It was also found that not only cell number but also cell distribution was necessary in the evaluation of flexible polyurethane foams, and cell diameter was closely related to the sound absorption coefficient in polyester-based flexible polyurethane foams. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 65: 1395–1402, 1997     

原位聚合法制备聚酯聚氨脂SiO2纳米复合涂料及性能测试

论述用原位聚合法制备了聚酯聚氨酯/SiO_2纳米复合涂料,并利用动态力学分析仪(DMA)、傅立叶变换红外光谱(FT-IR)、紫外可见光谱(UV-VIS)、透射电子显微镜(TEM)、原子力显微镜(AFM)、电子拉力机(Instron Tester)测试了涂膜的性能。结果表明,纳米SiO_2粒子均匀分布在涂膜中,并与聚酯通过化学键结合。纳米SiO_2粒子的加入提高了涂膜的摆杆硬度、玻璃化转变温度及附着力,并极大地改变了界面形貌,但本文研究的纳米SiO_2对聚酯聚氨酯紫外线吸收性和耐磨性没有明显影响。