大豆油基聚氨酯的研究及应用进展

综述了大豆油基聚氨酯的制备方法及应用,以大豆油为绿色原料,通过环氧化得到环氧大豆油,利用环氧大豆油开环制得大豆油基多元醇,再用此多元醇与异氰酸酯反应得到大豆油基聚氨酯泡沫、大豆油基聚氨酯乳液以及溶剂型大豆油基聚氨酯树脂。同时介绍了大豆油基聚氨酯在泡沫、涂料、胶粘剂等领域的具体应用。     

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。     

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。     

Physical Properties of Polyurethanes Produced from Polyols from Seed Oils: II. Foams

Rigid polyurethane (PU) foams were prepared using three North American seed oil starting materials. Polyol with terminal primary hydroxyl groups synthesized from canola oil by ozonolysis and hydrogenation based technology, commercially available soybean based polyol and crude castor oil were reacted with aromatic diphenylmethane diisocyanate to prepare the foams. Their physical and thermal properties were studied and compared using dynamic mechanical analysis and thermogravimetric analysis techniques, and their cellular structures were investigated by scanning electron microscope. The chemical diversity of the starting materials allowed the evaluation of the effect of dangling chain on the properties of the foams. The reactivity of soybean oil-derived polyols and of unrefined crude castor oil were found to be lower than that of the canola based polyol as shown by their processing parameters (cream, rising and gel times) and FTIR. Canola-PU foam demonstrated better compressive properties than Soybean-PU foam but less than Castor-PU foam. The differences in performance were found to be related to the differences in the number and position of OH-groups and dangling chains in the starting materials, and to the differences in cellular structure.     

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...     

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     

蓖麻油聚醚多元醇在聚氨酯软泡中的应用

利用双金属催化剂(DMC)制备了相对分子质量在2000～5600之间的聚氨酯(PU)软泡用蓖麻油聚醚多元醇,并通过发泡实验与常用软泡聚醚多元醇H-330进行了性能比较。结果表明,相对分子质量2000的蓖麻油聚醚多元醇制备的泡沫拉伸强度、伸长率和压陷硬度等均优于H-330聚醚,表明蓖麻油聚醚多元醇完全可以取代普通聚醚多元醇用于普通软泡生产。     

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     

Synthesis of Transesterified Palm Olein‐Based Polyol and Rigid Polyurethanes from this Polyol

Transesterification of palm olein with glycerol can increase the functionality by introducing additional hydroxyl groups to the triglyceride structure, an advantage compared to using palm olein directly as feedstock for producing palm‐based polyol. The objective of this study was to synthesize transesterified palm olein‐based polyol via a three‐step reaction: (1) transesterification of palm olein, (2) epoxidation and (3) epoxide ring opening. Transesterification of palm olein yielded approximately 78 % monoglyceride and has an hydroxyl value of approximately 164 mg KOH g^?1. The effect of formic acid and hydrogen peroxide concentrations on the epoxidation reaction was studied. The relationships between epoxide ring‐opening reaction time and residual oxirane oxygen content and hydroxyl value were monitored. The synthesized transesterified palm olein‐based polyol has hydroxyl value between 300 and 330 mg KOH g^?1 and average molecular weight between 1,000 and 1,100 Da. On the basis of the hydroxyl value and average molecular weight of the polyol, the transesterified palm olein‐based polyol is suitable for producing rigid polyurethane foam, which can be designed to exhibit desirable properties. Rigid polyurethane foams were synthesized by substituting a portion of petroleum‐based polyol with the transesterified palm olein‐based polyol. It was observed that by increasing the amount of transesterified palm olein‐based polyol, the core density and compressive strength were reduced but at the same time the insulation properties of the rigid polyurethane foam were improved.     

Polyols and Polyurethanes from Crude Algal Oil

The composition of crude algal oil was analyzed and determined by several methods. Oil was converted to polyols by ozonolysis, epoxidation, and hydroformylation. Ozonolysis gave a polyol with lighter color but a low OH number and was unsuitable for polyurethane applications. Epoxidation also improved the color and gave a polyol with an OH number around 150 mg KOH/g, which with diphenylmethane diisocyanate gave a homogeneous, rubbery, transparent sheet. Desirable rigid foams were prepared with the addition of water to the formulation. Hydroformylation was carried out successfully giving an OH number of about 150 mg KOH/g, but the polyol was black. Casting the polyurethane sheet was difficult due to the very high reactivity of the polyol. Polyurethane foam of lower quality than from epoxidation polyol was obtained. More work on optimization of the foaming system would improve the foam. Crude algal oil is a viable starting material for the production of polyols. Better results would be obtained from refined algal oils.     

高回弹块状泡沫塑料的试制

以自产聚醚多元醇为主要原料,试制成高回弹块状聚氨酯软泡。讨论了聚合物多元醇和水用量、低不饱和度聚醚等因素对泡沫性能的影响。     

Use of a Mixture of Polyols Based on Metasilicic Acid and Recycled PLA for Synthesis of Rigid Polyurethane Foams Susceptible to Biodegradation

Two polyol raw materials were obtained in the conducted research, one based on metasilicic acid (MSA), the other based on poly(lactic acid) (PLA) waste. The obtained polyols were characterized in terms of their applicability for the production of rigid polyurethane foams (RPUFs). Their basic analytical properties (hydroxyl number, acid number, elemental analysis) and physicochemical properties (density, viscosity) were determined. The assumed chemical structure of the obtained new compounds was confirmed by performing FTIR and ¹H NMR spectroscopic tests. Formulations for the synthesis of RPUFs were developed on the basis of the obtained research results. A mixture of polyols based on MSA and PLA in a weight ratio of 1:1 was used as the polyol component in the polyurethane formulation. The reference foam in these tests was a foam that was synthesized only on the basis of MSA-polyol. The obtained RPUFs were tested for basic functional properties (apparent density, compressive strength, water absorption, thermal conductivity coefficient etc.). Susceptibility to biodegradation in soil environment was also tested. It was found that the use of mixture of polyols based on MSA and PLA positively affected the properties of the obtained foam. The polyurethane foam based on this polyol mixture showed good thermal resistance and significantly reduced flammability in comparison with the foam based MSA-polyol. Moreover, it showed higher compressive strength, lower thermal conductivity and biodegradability in soil. The results of the conducted tests confirmed that the new foam was characterized by very good performance properties. In addition, this research provides information on new waste management opportunities and fits into the doctrine of sustainable resource management offered by the circular economy.     

大豆油多元醇的制备及其在聚氨酯硬泡中的应用

通过实验制备出大豆油多元醇Soy-450,并应用于聚氨酯硬泡中,通过改变Soy-450的替代用量来研究其对硬泡性能的影响。随着Soy-450替代量的增加,发泡性能和尺寸稳定性有所下降,密度增大;当替代量为10~50份时,具有更高的垂直压缩强度;与石油基硬泡相比,大豆油基硬泡具有更好的热稳定性。     

Viscoelastic changes and cell opening of reacting polyurethane foams from soy oil

The modulus development of reacting polyurethane foams from modified soy oil (soy polyol) was studied. The reaction and buildup of rheological properties were monitored using vane geometry in a strain‐controlled rheometer. Normal force exerted on the vanes by the expanding foam was measured as a function of time to study the phenomenon of cell opening. The effect of foam ingredients and process parameters on the modulus development was investigated. The morphology of the cured foam was studied using scanning electron microscope (SEM). Experiments were carried out to elucidate the effect of water and addition of petroleum‐based polyol on the modulus development of the reacting foam and the morphology of the cured product. The effect of frequency and thermal history on the modulus development of the reacting foam was also studied. Ozonolysis of soybean oil was carried out to study the effect of adding OH groups on the modulus development during the foaming reaction. Four stages of modulus development, similar to those observed for synthetic polyol (voranol, Aldrich Chemicals) foams, were observed. Increase in water content led to an earlier stiffening of the polymer and a higher modulus. Addition of voranol in soy polyol reduced the liquid foam plateau and significantly reduced the reaction time. Ozonolysis of soy oil led to an earlier phase separation as compared with foams from soy polyol. The temperature at which the foaming reaction takes place dominated the rate of modulus buildup. Higher texture (urea aggregates) and an increase in the cell size were observed with an increase in water content for soy polyol foams. Addition of voranol increased the number of open cells. Polym. Eng. Sci. 44:1977–1986, 2004. © 2004 Society of Plastics Engineers.     

Development of a rigid polyurethane foam from palm oil

The reactions between polymeric diphenyl methane diisocyanate (polymeric MDI) and conventional polyols to produce foamed polyurethane products are well documented and published. Current polyurethane foams are predominantly produced from these reactions whereby the polyol components are usually obtained from petrochemical processes. This article describes a new development in polyurethane foam technology whereby a renewable source of polyol derived from refined–bleached–deodorized (RBD) palm oil is used to produce polyurethane foams. Using very basic foam formulation, rigid polyurethane foams were produced with carbon dioxide as the blowing agent generated from the reaction between excess polymeric MDI with water. The foams produced from this derivatized RBD palm oil have densities in excess of 200 kg/m³ and with compression strengths greater than 1 MPa. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 68: 509–515, 1998     

Preparation and application of phosphorous‐containing bio‐polyols in polyurethane foams

A bio‐polyol phosphonate acting as the polyol component in the preparation of polyurethane foam was synthesized from the liquefaction product of bagasse by the halogenation of the liquefaction product followed by the Michaelis–Arbuzov rearrangement. The FT‐IR spectra showed that phosphorus‐containing groups were introduced into the polyol chain. The data of the viscosity and the hydroxyl number suggested that the bio‐polyol phosphonate would be a good polyol component in the preparation of polyurethane foam. The limiting oxygen index of polyurethane foam containing bio‐polyol phosphonate varied in the range of 24–28, while that of polyurethane foam without bio‐polyol phosphonate was 23, demonstrating that the introduction of the phosphorus‐containing group into the polymer helped to improve the flame retardancy. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40422.     

Noncatalytic polymerization of ethylene glycol and epoxy molecules for rigid polyurethane foam applications

The study investigated an approach to incorporate modified epoxidized soy‐based vegetable oil polyol as a replacement for petroleum‐based polyether polyol and to substantially reduce the isocyanate loading in the rigid foam formulation. Noncatalytic polymerization of epoxidized bodied soybean oil and ethylene glycol (EG) was carried out in a closed batch reaction. Cleavage of the oxirane rings and hydroxyl group attachment at optimum conditions provided the desired polyol products. The polyols were characterized based on its hydroxyl numbers, acidity, viscosity, iodine number, and Gardner color index for quality purposes. Reactions of oxirane ring and EG were verified by spectroscopic FTIR. Crosslinking performance was evaluated by extractability analysis on the polyurethane (PU) elastomer wafers. Rigid foaming performed at 50 and 75% petroleum‐based polyether polyol replacements have shown excellent thermoinsulating and mechanical properties compared with epoxidized soybean oil (ESBO) alone or petroleum‐based polyether polyol alone. A reduction of up to 8% of the polymeric diphenylmethane diisocyanate was achieved using the synthesized ESBO‐EG‐based polyols. A higher average functionality polyol is key component to the reduction of isocyanate in PU synthesis. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

聚合物多元醇（POP）合成工艺研究进展

聚合物多元醇是生产聚氨酯原料之一。本文从聚醚多元醇合成工艺入手,重点阐述不燃级聚氨酯泡沫用聚合物多元醇（ POP）和高固含量聚合物多元醇（ POP）的制造工艺发展,其中不燃级聚氨酯泡沫用POP的制造分为外加法和内加法。最后,对聚醚多元醇工艺进行了总结和展望,国内聚醚生产企业应加快先进合成工艺的开发和引进。     

Recent Advancement in Plant Oil Derived Polyol‐Based Polyurethane Foam for Future Perspective: A Review

Polyurethane foams (PUFs) are widely used materials because of their wide range of applications, particularly, thermal and sound insulation, mattresses, furniture, construction, cushioning, packaging, transportation of goods, etc. Recently, commercial PUF products fabricated from plant oil (PO)‐based polyols have gained increasing popularity, because of their low cost and eco‐friendly nature in comparison to petroleum‐based PUF. To date, insufficient reviews have been reported in the area of modification of plant oils for synthesizing polyol for foam synthesis. Due to abundant availability, low‐cost, and renewable nature of plant oils, they are being used as precursors for modern polyurethane industry use. There is a need for versatile and economical methods for conversion of plant oils such as castor oil (CO) and soybean oil (SO) into useful polyols for industry use. This review is an overview of the most recent advanced methods for the conversion of plant oils into polyol and further utilization of it for commercial PUF products. Since the last decade, many researchers have shown that plant‐polyol‐derived PUF can compete with conventional PUF. Practical Applications: Practical applications of the PO‐based polyurethane foams include thermal insulation, sound insulation, packaging, and waste water treatment.     

Synthesis and Thermal Characterization of Polyurethane/Clay Nanocomposites Based on Palm Oil Polyol

Polyurethanes (PUs) are very versatile polymeric materials with a wide range of physical and chemical properties. PUs also have desirable properties, such as high abrasion resistance, tear strength, shock absorption, flexibility, and elasticity. Although they have poor thermal stability, it can be improved by using treated clay.

The objective of the present work is to study the thermal stability of polyurethane, polyurethane/montmorillonite (PU CTAB-mont 3% wt), and polyurethane/montmorillonite containing moca (PU Moca CTAB-mont 3% wt) nanocomposites based on palm oil polyol.

The interest of investigating the synthesis of polyurethane/clay nanocomposites based on palm oil polyol is to explore the use of palm oil polyol to partially replace petrochemical-based polyol.

Polyurethane/clay nanocomposites were prepared by a pre-polymer method and evaluated by Fourier Transform Infrared Spectra (FTIR) to determine micro-domain structures of segmented PU, PU CTAB-mont 3% wt, and PU Moca CTAB-mont 3% wt. The morphology of the nanocomposites was characterized by X-ray diffraction (X-RD), and flame retardant was investigated with thermogravimetric analysis (TGA). The result showed that in comparison with the virgin polyurethane, adding clay and moca demonstrated better thermal stability.