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.     

Role of additives in fabrication of soy-based rigid polyurethane foam for structural and thermal insulation applications

Environmental concerns continue to pose the challenge to replace petroleum-based products with renewable ones completely or at least partially while maintaining comparable properties. Herein, rigid polyurethane (PU) foams were prepared using soy-based polyol for structural and thermal insulation applications. Cell size, density, thermal resistivity, and compression force deflection (CFD) values were evaluated and compared with that of petroleum-based PU foam Baydur 683. The roles of different additives, that is, catalyst, blowing agent, surfactants, and different functionalities of polyol on the properties of fabricated foam were also investigated. For this study, dibutyltin dilaurate was employed as catalyst and water as environment friendly blowing agent. Their competitive effect on density and cell size of the PU foams were evaluated. Five different silicone-based surfactants were employed to study the effect of surface tension on cell size of foam. It was also found that 5 g of surfactant per 100 g of polyol produced a foam with minimum surface tension and highest thermal resistivity (R value: 26.11 m²·K/W). However, CFD values were compromised for higher surfactant loading. Additionally, blending of 5 g of higher functionality soy-based polyol improved the CFD values to 328.19 kPa, which was comparable to that of petroleum-based foam Baydur 683.     

Polyurethane foams from soyoil‐based polyols

The focus of this work was to synthesize bio‐based polyurethane (PU) foams from soybean oil (SO). Different polyols from SO were produced as follows: soybean oil monoglyceride (SOMG), hydroxylated soybean oil (HSO), and soybean oil methanol polyol (SOMP). The SOMG was a mixture of 90.1% of monoglyceride, 1.3% of diglyceride, and 8.6% of glycerol. The effect of various variables (polyol reactivity, water content curing temperature, type of catalyst, isocyanate, and surfactant) on the foam structure and properties were analyzed. SOMG had the highest reactivity because it was the only polyol‐containing primary hydroxyl (? OH) groups in addition to a secondary ? OH group. PU foams made with SOMG and synthetic polyol contained small uniform cells, whereas the other SO polyols produced foams with a mixture of larger and less uniform cells. The type of isocyanate also had an influence on the morphology, especially on the type of cells produced. The foam structure was found to be affected by the water and catalyst content, which controlled the foam density and the cure rate of the PU polymer. We observed that the glass transition (T_g) increased with the OH value and the type of diisocyanate. Also, we found that the degree of solvent swelling (DS) decreased as T_g increased with crosslink density. These results are consistent with the Twinkling Fractal Theory of T_g. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

高固含量丙烯酸酯改性聚氨酯胶粘剂的研制

以聚醚多元醇、聚酯多元醇和蓖麻油为混合多元醇,以改性MDI(4,4′-二苯基甲烷二异氰酸酯)及PAPI(多亚甲基多苯基多异氰酸酯)为混合异氰酸酯,合成了聚氨酯(PU)胶粘剂预聚体;然后以PA(羟基丙烯酸酯树脂)作为PU预聚体的改性剂,制得高固含量的PUA(聚丙烯酸酯改性聚氨酯)胶粘剂。结果表明:当m(改性MDI)∶m(PAPI)=1∶1、n(-NCO)∶n(-OH)=2.2∶1、w(PA)=8%(相对于PU质量而言)和w(丙烯酸羟乙酯)=3%(相对于PU质量而言)时,PUA胶粘剂的综合性能较好。     

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.     

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     

Physical properties of new polyurethanes foams from benzene polyols synthesized from erucic acid

High density triol‐based polyurethane (PU) foams were developed from aromatic triol isomers prepared from erucic acid. The triol monomers were crosslinked with 4,4′‐diphenylmethane diisocyanate (MDI) into PU foams. The foam's properties were studied by Fourier transform infrared (FTIR) spectroscopy, X‐ray diffraction (XRD), differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), scanning electron microscopy (SEM), and thermogravimetric analysis (TGA). The foams were analyzed for closed cell content and compression strength. The effect of the benzene ring in the polyol structure on the physical properties of these new PU foams was compared with high density foams made from aliphatic polyols originating from canola oil. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

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。     

一种利用大豆油合成的硬质聚氨酯泡沫塑料

以大豆油与环氧化剂反应,生成环氧大豆油;在催化剂的存在下与含活泼氢的亲核试剂发生环氧键开环反应,生成混合羟基脂肪酸甘油酯;加入醇并升温进行醇解反应,生成混合羟基脂肪酸单酯,即大豆油基多元醇。将大豆油基多元醇与异氰酸酯(MDI)等反应即可制得硬质聚氨酯泡沫塑料,具体配方为100份大豆油基多元醇,80~150份MDI、0.3~4份三乙醇胺、0.5~4份匀泡剂、0.5~3份蒸馏水。     

A novel synthesis of reactive nano‐clay polyurethane and its physical and dyeing properties

This study is about polyurea prepolymer, which was synthesized from the extender (N‐(2‐hydroxyethyl) ethylene diamine, HEDA or ethylene diamine, EDA) with 4,4′‐diphenylmethane diisocyanate (MDI), as an intercalative agent to intercalate the organic modified montmorillonite clay. Then, it is further reacted with the polyurethane prepolymer, which is polymerized from the polytetramethylene glycol (PTMG) and MDI, to proceed the intercalative polymerization to form a polyurethane/clay nanocomposite polymer. The experimental parameters contain the use of polyurea intercalative prepolymer extender and also the contents of organo‐clay in the prepolymer etc. We expect to get better mechanical property and also to improve the dyeing properties of nano‐clay polyurethane. The polyurethane/clay polymer is synthesized using two‐step method: synthesizing the polyurethane prepolymer from PTMG and MDI and then extended with the polyurea prepolymer modified with the organo‐clay. Because the extender HEDA contains side chain of hydroxyl groups, the modified PU can further react with the reactive dye. From the experimental results of the fine structure (X‐ray and FT‐IR) and mechanical analysis, it is found that the intercalation is successfully achieved. Thedistance of interlayer spacing is manifestly enlarged. The mechanical properties are significantly improved as the content of organo‐clay is increased. Besides, although thedye up‐take is decreased with the increasing content oforgano‐clay, but the water‐resistant fastness is improved. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

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.     

聚氨酯/三聚氰胺甲醛树脂复合泡沫热降解动力学研究

三聚氰胺甲醛树脂脱水后和多元醇混合,然后用异氰酸酯与混合物进行交联反应,生成聚氨酯/三聚氰胺甲醛树脂复合泡沫.热重分析结果表明,复合泡沫失重分为3个阶段,二苯基甲烷二异氰酸酯(MDI)型三聚氰胺甲醛树脂复合泡沫的第2阶段的失重峰温比甲苯二异氰酸酯(TDI)型三聚氰胺甲醛树脂复合泡沫的高.采用Kissinger法研究了该...     

Preparation and characterization of polyurethane/silica aerogel nanocomposite materials

In this investigation, silica aerogel (SA)/Rigid Polyurethane (PUR) foam composites and silica aerogel/Polyurethane (PU) composites were prepared by dry mixing of granular and grinded silica aerogels with polyol part. They were then combined with diisocyanate part. Three different types of PUR foams and an elastomeric coating grade of PU were studied as well. Results show that thermal conductivity of foams did not decrease by adding silica aerogel. It even increased for some grades which is assumed to be due to the change in cell configuration of these foams. It was also found that sound insulation performance of these cellular composites did not improve significantly. Unlike foam composites, addition of silica aerogel into elastomeric PU improved its thermal and acoustic insulation properties. Because of the more promising properties of elastomeric PU composites, further examinations including measurements of compression strength and water contact angle of silica aerogel/PU composites were also taken. Final results showed a significant improvement in general properties of PU coatings by adding little amounts of silica aerogel (1–4 wt %). © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44521.     

Preparation,characterization, and influence of polyurea coatings on their layered composite materials based on flexible rebonded polyurethane

Preparation and characterization of a series of polyurea (PU) coatings and their influences on layered composite materials based on rebonded polyurethane (PUr) for floor application are described in terms of the raw materials, formulation, and application performance. While PU coatings show almost the same FTIR peaks, thermogravimetric analyses results reveal that thermal stabilities of the PU coatings are slightly enhanced with the use of trifunctional polyamine compound and one step degradation takes place beyond 300°C. All PU coatings have very dense, smooth, and bubble-free surfaces whereas the cross-sectional SEM images exhibit pores of different sizes. Contact angle values of all PU coatings are bigger than 90° indicating that the surfaces are hydrophobic. Using propylene carbonate in the preparation of methylene diphenyl diisocyanate (MDI) prepolymer and the chain extender in the PU coating formulation impacts the mechanical and electrical properties of the PU coatings as well as layered PU/PUr composite materials. In conclusion, not only the controllable physicochemical and mechanical properties of layered PUr/PU composites but also the usage potential of recycled PU scraps in these layered composites are very promising for better floor applications.     

Preparation and properties of rigid polyurethane foam based on modified castor oil

Castor oil polyol (COP) having a hydroxyl number of 400?mg?KOH/g was prepared through the transesterification reaction of castor oil with glycerol. The effect of reaction temperature on the composition, hydroxyl number and viscosity of the COP products was studied. A series of rigid polyurethane foams were synthesised using the mixtures comprising COP and a petroleum-based polyol with various proportions as polyol component. It was found that the foaming rate, compressive strength and dimensional stability and morphology of resulting foams were dominated by the foam formulation, in a more accurate way, COP content in the polyol mixtures. The combination of expandable graphite and dimethyl methyl phosphonate exhibited stronger flame retardant function which was ascribed to the synergistic effect associated with the simultaneous presence of the two additives. An improvement in thermal stability was observed due to the inclusion of the flame retardants.     

Fabrication,characterization and low‐velocity impact testing of hybrid sandwich composites with polyurethane/layered silicate foam cores

A series of nanophased hybrid sandwich composites based on polyurethane/montmorillonite (PU/MMT) has been fabricated and characterized. Polyaddition reaction of the polyol premix with 4,4′‐diphenylmethane diisocyanate was applied to obtain nanophased PU foams, which were then used for fabrication of sandwich panels. It has been found that the incorporation of MMT resulted in higher number of PU cells with smaller dimensions and higher anisotropy index (cross sections RI and RII). The obtained materials exhibited improved parameters in terms of thermal insulation properties. The results also show that nanophased sandwich structures are capable of withstanding higher peak loads than those made of neat PU foam cores when subject to low‐velocity impact despite their lower density than that of neat PU foams. This is especially significant for multi‐impact recurrences within the threshold loads and energies studied. POLYM. COMPOS., 2011. © 2010 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     

喷涂聚脲弹性体耐水性能的研究

以不同种类多元醇与二苯基甲烷二异氰酸酯（MDI）和液化MDI合成预聚物作为A组分,端胺基聚醚、胺类扩链剂为R组份,制成喷涂聚脲弹性体。讨论了多元醇种类及其相对分子质量、A组分的NCO含量、扩链剂等对喷涂聚脲弹性体耐水性能的影响。结果表明,由二聚体聚酯二醇制得的喷涂聚脲弹性体耐水性能最好,其次是聚四氢呋喃多元醇,聚氧化丙烯醚二醇的耐水性最差;随着多元醇相对分子质量的增加,聚氧化丙烯醚二醇和聚四氢呋喃醚二醇的耐水性提高,而二聚体聚酯二醇的耐水性能变化不大;A组分的NCO含量增加,耐水性提高;不同扩链剂的耐水性有很大差异,依次为3,3’．二氯4,4’-二苯基甲烷二胺〉二乙基甲苯二胺〉3,5-二甲硫基甲苯二胺〉4,4’-双仲丁胺基二苯基甲烷。     

Polyurethane Foam Wastes Recycling under Microwave Irradiation

Microwave-assisted (MW-assisted) glycolysis of waste-flexible polyurethane (PU) foams using pentaerythritol in combination with glycerin and sodium hydroxide as a PU bond degradation reagent is reported. Split phases appeared after complete foam digestion. The upper phase contained recycled polyol, and the lower phase was a brown liquid with highly functionalized oligomers, amines and unreacted degradation reagents and showed potential for application in rigid polyurethane foam formulation. Our studies showed the dependence of recovered polyol assay to the additional MW irradiation and amine-free polyol were achieved in high yields and purities.