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.     

Physical properties of water‐blown rigid polyurethane foams from vegetable oil‐based polyols

Fifty vegetable oil‐based polyols were characterized in terms of their hydroxyl number and their potential of replacing up to 50% of the petroleum‐based polyol in waterborne rigid polyurethane foam applications was evaluated. Polyurethane foams were prepared by reacting isocyanates with polyols containing 50% of vegetable oil‐based polyols and 50% of petroleum‐based polyol and their thermal conductivity, density, and compressive strength were determined. The vegetable oil‐based polyols included epoxidized soybean oil reacted with acetol, commercial soybean oil polyols (soyoils), polyols derived from epoxidized soybean oil and diglycerides, etc. Most of the foams made with polyols containing 50% of vegetable oil‐based polyols were inferior to foams made from 100% petroleum‐based polyol. However, foams made with polyols containing 50% hydroxy soybean oil, epoxidized soybean oil reacted with acetol, and oxidized epoxidized diglyceride of soybean oil not only had superior thermal conductivity, but also better density and compressive strength properties than had foams made from 100% petroleum polyol. Although the epoxidized soybean oil did not have any hydroxyl functional group to react with isocyanate, when used in 50 : 50 blend with the petroleum‐based polyol the resulting polyurethane foams had density versus compressive properties similar to polyurethane foams made from 100% petroleum‐based polyol. The density and compressive strength of foams were affected by the hydroxyl number of polyols, but the thermal conductivity of foams was not. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

生物基阻燃聚酯多元醇聚氨酯硬泡在煤矿中的应用

用生物基阻燃聚酯多元醇替代石油基聚醚多元醇添加于聚氨酯硬泡组合聚醚中,研究了该生物基阻燃聚酯多元醇的替代量,以及在煤矿中阻燃效果。结果表明,生物基聚酯多元醇可替代部分石油基聚醚多元醇使用,当生物基聚酯多元醇在总聚醚多元醇体系中占40%~50%时,聚氨酯泡沫的压缩强度高、尺寸稳定性良好、导热系数低且阻燃效果理想,达到中华人民共和国煤炭行业MT-113—1995标准,保证了煤矿安全使用。     

原材料对聚氨酯硬泡抗压性能的影响

以环氧丙烷聚醚多元醇、苯酐聚酯多元醇、多苯基甲烷多异氰酸酯PM-200、发泡剂一氟二氯乙烷(HCFC-141b)、泡沫稳定剂硅油AK-8801等为主要原料,采用一步法合成了聚氨酯硬泡,考察了不同种类多元醇及其配比、发泡剂、泡沫稳定剂种类及用量等对聚氨酯硬泡抗压性能的影响。结果表明:高羟值、高官能度的环氧丙烷聚醚多元醇可提高泡沫的压缩强度,且当环氧丙烷聚醚多元醇4110为100份,并加入20份左右苯酐聚酯多元醇580及10份左右聚醚403,泡沫稳定剂用量1～2份,发泡剂水用量0.5～1份,HCFC-141b用量30～35份,催化剂用量0.5～1.5份时,所得聚氨酯硬泡性能较好。     

Nanoclay filled soy‐based polyurethane foam

Polyurethane foam was fabricated from polymeric diphenylmethane diisocyanate (pMDI) and soy‐based polyol. Nanoclay Cloisite 30B was incorporated into the foam systems to improve their thermal stabilities and mechanical properties. Neat polyurethane was used as a control. Soy‐based polyurethane foams with 0.5–3 parts per hundred of polyols by weight (php) of nanoclay were prepared. The distribution of nanoclay in the composites was analyzed by X‐ray diffraction (XRD), and the morphology of the composites was analyzed through scanning electron microscopy (SEM). The thermal properties were evaluated through dynamic mechanical thermal analysis (DMTA). Compression and three‐point bending tests were conducted on the composites. The densities of nanoclay soy‐based polyurethane foams were higher than that of the neat soy‐based polyurethane foam. At a loading of 0.5 php nanoclay, the compressive, flexural strength, and modulus of the soy‐based polyurethane foam were increased by 98%, 26%, 22%, and 65%, respectively, as compared to those of the neat soy‐based polyurethane foam. The storage modulus of the soy‐based polyurethane foam was improved by the incorporation of nanoclay. The glass transition temperature of the foam was increased as the nanoclay loading was increased. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

新型含磷阻燃型桐油基聚氨酯硬泡的制备及性能表征

桐油与甘油在甲醇钠为催化剂的条件下发生醇解反应得到桐油醇解产物（GTO）,GTO经环氧化得到环氧化桐油醇解产物（EGTO）,EGTO与9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物（DOPO）发生开环反应生成新型含磷阻燃型桐油基多元醇（PTOP）。PTOP部分取代聚醚多元醇（PPG4110）与异氰酸酯及助剂反应,通过一步法制备聚氨酯硬泡（RPUF）。采用万能试验机、热导率测定仪、热重分析仪和锥形量热仪分别考察RPUF的力学性能、热稳定性和燃烧行为。结果表明：随着PTOP替代石油基多元醇的比率增大,RPUF的压缩强度、密度、热导率先增大后减小,热稳定性提高,极限氧指数（LOI）由18.1%提高至26.0%,而总放热量先减小后增大,这主要是由于PTOP结构中的DOPO基团具有阻燃作用而PTOP结构中含有的桐油基脂肪链易于燃烧且热释放量较大。以上结果表明PTOP部分取代PPG4110制备的RPUF具有良好的阻燃性能和热稳定性。     

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     

新型芳香族聚酯多元醇的合成与性能研究

用对苯二甲酸、苯酐、二元醇、三元醇等多元醇为原料制备新型芳香族聚酯多元醇,考察了聚酯多元醇酸值、羟值与其醇酸摩尔比的关系,以及酸值与反应时间的关系,并将其用于制备硬质聚氨酯泡沫塑料,讨论了新型聚酯多元醇对硬质聚氨酯泡沫塑料的性能影响。     

Bio-based flame-retardant rigid polyurethane foam with high content of soybean oil polyols containing phosphorus

Rigid polyurethane foam (RPUF) is prepared from petroleum-based polyols and isocyanate, which consumes a large amount of petroleum. To alleviate the consumption of petroleum, it is necessary to synthesize green and sustainable polyols. However, the greatest disadvantage of RPUF is its flammability. To reduce the risk of fire caused by RPUF, phosphorylated soybean oil polyol (Polyol-P) and phenyl phospho-soybean oil polyol (Polyol-PPOA) were synthesized by ring-opening reactions of epoxy soybean oil with phosphoric acid and phenylphosphonic acid, respectively. A flame-retardant RPUF was prepared via polymeric 4,4-diphenylmethane diisocyanate (p-MDI), which reacted after mixing Polyol-P and Polyol-PPOA with polyether polyol-330N in different proportions. Scanning electron microscopy (SEM) showed that the cell sizes of the RPUF-P and RPUF-PPOA increased first and then decreased and the cell number decreased first and then increased with the increase in the contents of Polyol-P and Polyol-PPOA. Mechanical property tests showed that the compressive strength of the RPUF-P4 reached 0.1 MPa, and the compressive strength of the RPUF-PPOA4 reached 0.07 MPa. The limiting oxygen index values of the RPUF-P4 and RPUF-PPOA4 were 20.9% and 24.3%, respectively. The UL 94 of the RPUFs indicated that the rating of the RPUF-PPOA3 was improved to V-1. The results showed that the flame-retardancy mechanism of the Polyol-P and Polyol-PPOA in the RPUF was based on the charred surface as a physical barrier, which slowed down the decomposition of RPUF and prevented heat and mass transfer between the gas and the condensed phase.     

Comparative study of physical properties of water‐blown rigid polyurethane foams extended with commercial soy flours

The use of renewable resources (mainly carbohydrates) in rigid polyurethane foam has been known to offer several advantages, such as increased strength, improved flame resistance, and enhanced biodegradability. Less attention has been directed to inexpensive protein‐based materials, such as defatted soy flour. The objectives of this study were to develop water‐blown rigid polyurethane foams, containing defatted soy flour, that have acceptable or improved physical properties which also lower the cost of the foam formulation and to compare the properties of developed foams extended with three kinds of commercial soy flour. Water‐blown low‐density rigid polyurethane foams were prepared with poly(ether polyol)s, polymeric isocyanates, defatted soy flour, water, a catalyst mixture, and a surfactant. Soy flour and the initial water content were varied from 0 to 40% and from 4.5 to 5.5% of the poly(ether polyol) content, respectively. A standard laboratory mixing procedure was followed for making foams using a high‐speed industrial mixer. After mixing, the mixture was poured into boxes and allowed to rise at ambient conditions. Foams were removed from boxes after 1 h and cured at room temperature for 24 h before measurement of the thermal conductivity and for 1 week before other property tests. Foam properties were determined according to ASTM procedures. Measurement of the physical properties (compressive strength, modulus, thermal conductivity, and dimensional stability under thermal and humid aging) of these foams showed that the addition of 10–20% of three kinds of soy flour imparted water‐blown rigid polyurethane foams with similar or improved strength, modulus, insulation, and dimensional stability. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 10–19, 2001     

溴化蓖麻油多元醇合成及其制备的阻燃聚氨酯硬泡性能

采用可再生的醇解蓖麻油多元醇为原料,与液溴进行加成反应制备溴化蓖麻油多元醇,通过红外光谱证实发生了溴化反应,并测定了产物粘度、羟值、酸值.通过发泡实验和氧指数、烟密度、水平燃烧等测试手段,考察了溴化蓖麻油基聚氨酯硬泡发泡参数和阻燃性质,并与工业级阻燃荆雅保RB-79制备的聚氨酯硬泡进行比较.结果表明,由溴化蓖麻油多元醇...     

喷涂缠绕保温管用全水发泡聚氨酯组合聚醚的研制

用聚醚多元醇A、聚醚二醇B、聚酯多元醇PS-2915、三乙醇胺、水和其他助剂制备了喷涂管道用全水发泡聚氨酯硬泡组合聚醚,并对其反应性能、黏度进行评价,对使用该组合聚醚和多异氰酸酯PM-200制得的聚氨酯泡沫材料的性能进行研究。结果表明,在合适的原料用量时,制得的组合聚醚黏度较低,与多异氰酸酯PM-200的反应速度满足喷涂管道生产工艺要求。当喷涂制得的聚氨酯泡沫单层厚度7 mm左右,泡沫体具有较高的粘接强度、较好的韧性和较低的导热系数,密度61 kg/m^3的泡沫压缩强度达到526 kPa。制得的喷涂管道产品满足GB/T 34611—2017要求。     

Biobased flexible polyurethane foams manufactured from lactide-based polyester-ether polyols for automotive applications

In this study, biobased polyester-ether polyols derived from meso-lactide and dimer acids were evaluated for flexible polyurethane foams (PUF) applications. Initially, the catalyst concentration was optimized for the biobased PUF containing 30% of biobased polyol (70% petroleum-based polyol). Then, the same formulation was used for biobased PUF synthesis containing 10%–40% of biobased polyols. The performance of biobased PUF was compared with the performance of the control foam made with 100% petroleum-based polyol. The characteristic times (cream, top of the cup, string gel, rise, tack-free) of biobased PUF were determined. The biobased PUF were evaluated for the mechanical (tensile and compressive) and morphological properties. As the wet compression set is important for automotive applications, it was measured for all biobased PUF. The thermal degradation behavior of biobased PUF was also evaluated and compared with the control foam. The effect of different hydroxyl and acid values of polyols on the mechanical properties of biobased PUF is also discussed. The miscibility of all components of PUF formulations is crucial in order to produce a foam with uniform properties. Thus, the miscibility of biobased polyols with commercial petroleum-based polyol was studied.     

羟甲基木质素磺酸钠/膨胀石墨/次磷酸铝阻燃聚氨酯泡沫的研究

本研究利用木质素磺酸钠对聚氨酯泡沫进行改性,提高其阻燃性能。首先,对木质素磺酸钠进行羟甲基化反应,得到羟甲基木质素磺酸钠（HSL）,再将HSL部分替代聚醚多元醇,与聚合4,4'-二苯基甲烷二异氰酸酯（MDI）混合,制备羟甲基木质素磺酸钠改性聚氨酯泡沫,再添加膨胀石墨（EG）和次磷酸铝（AHP）进一步提高聚氨酯泡沫的阻燃性。制备出样品后分别进行极限氧指数（LOI）、热重分析（TGA）和扫描电子显微镜（SEM）测试。通过极限氧指数测试分析聚氨酯泡沫样品阻燃性能表明：当羟甲基木质素磺酸钠替代量为60%（以HSL质量占HSL和聚醚多元醇总质量的百分比计）时,所得聚氨酯泡沫材料的LOI指数达到21.6%,最大热降解速率降低了1.53 %/min,残炭量提高了15.04个百分点,泡沫试样中泡沫孔隙数量和面积减少。继续添加混合阻燃剂（膨胀石墨和次磷酸铝质量比为3:1）时,所得聚氨酯泡沫材料的LOI指数能达到26.3%,最大热降解速率降低了1.52 %/min,残炭量提高了23.52个百分点,泡沫试样的泡沫孔隙数量和面积进一步减少。因此,本实验制备出一种具有优异阻燃性能的聚氨酯泡沫,其在建筑领域、交通领域、食品保温领域有广阔的应用前景。     

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。     

改性木质素泡沫树脂的合成研究

利用稀酸水解木质素、碱木质素为原料,合成了一系列含羟基的木质素聚脂。该树脂经调配,可与异氰酸酯反应制成聚氨酯硬泡材料。实验结果表明:以稀酸水解木质素、碱木质素为原料所制成的木质素多元醇树脂,其粘度为3000～5000 cP·s/20℃,羟值为380～450 mg/g,酸值小于5 mg/g。经调配发泡所制得的硬质泡沫材料,表观密度为0.03～0.05 g/cm³,抗压强度大于0.15MPa,导热系数为0.023 W/(M·K),吸水率3%。性能可达到工业及日常生活对保温的要求。     

Biodegradable polyurethane foam from liquefied waste paper and its thermal stability,biodegradability, and genotoxicity

Liquefaction of waste paper (WP) was conducted in the presence of polyhydric alcohols to prepare biodegradable polyurethane foam. The liquefied‐WP‐based polyol had suitable characteristics such as apparent molecular weight, hydroxyl value, and viscosity for the preparation of rigid polyurethane foam and was successfully applied to produce polyurethane foam with the appropriate combinations of foaming agents. The obtained foams showed satisfactory densities and mechanical properties as good as those of foams obtained from liquefied wood‐ and starch‐based polyols. The foams had almost the same thermal stability at initial weight loss and seemed to be potentially biodegradable because they were degraded to some extent in leaf mold. There were no mutagens or carcinogens in the water extracts of the foams. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 1482–1489, 2002     

集装箱用组合聚醚的研制与应用

通过对组合聚醚中各种原料的筛选，选出性能互补的聚醚，配以合适的催化剂、泡沫稳定剂，调配出性能良好的集装箱用组合聚醚，其综合性能已达到了国外同类产品水平。     

全水发泡聚氨酯硬泡密度对性能影响的初步研究

研究了全水发泡硬质聚氨酯泡沫塑料的密度对泡沫性能的影响。实验结果表明,在一定密度范围内,随着泡沫密度的上升,泡沫的氧指数、压缩强度逐渐升高,导热系数先升高后降低,尺寸稳定性先变差后变好。     

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。