Ethoxylated Soybean Polyols for Polyurethanes

Soybean polyols prepared by ring opening reactions of epoxidized soybean oil with hydrogen active compounds (water, alcohols, organic or inorganic acids, thiols, hydrogen etc.) have a low reactivity in the reaction with isocyanates because the hydroxyl groups are secondary. This paper presents a simple and convenient method to increase the reactivity of soybean polyols with secondary hydroxyl groups by ethoxylation reactions with the preservation of triglyceride ester bonds. The method uses mild reaction conditions: low alkoxylation temperature of 35–45 °C, low pressure of 0.1–0.2 MPa (15–30 p.s.i.) and a superacid as catalyst (HBF₄). The new soybean polyols have a higher reactivity toward isocyanates in polyurethane formation due to the high percentage of primary hydroxyl groups. The primary hydroxyl content was determined by the second order kinetics of polyol reaction with phenyl isocyanate.     

Polyols and Polyurethanes from Hydroformylation of Soybean Oil

This paper compares physical and mechanical properties of polyurethanes derived via the hydroformylation approach and is a part of our study on the structure–property relationships in polyurethanes created from vegetable oils. The double bonds of soybean oil are first converted to aldehydes through hydroformylation using either rhodium or cobalt as the catalyst. The aldehydes are hydrogenated by Raney nickel to alcohols, forming a triglyceride polyol. The latter is reacted with polymeric MDI to yield the polyurethane. Depending on the degree of conversion, the materials can behave as hard rubbers or rigid plastics. The rhodium-catalyzed reaction afforded a polyol with a 95% conversion, giving rise to a rigid polyurethane, while the cobalt-catalyzed reaction gives a polyol with a 67% conversion, leading to a hard rubber having lower mechanical strengths. Addition of glycerine as a cross-linker systematically improves the properties of the polyurethanes. The polyols are characterized by DSC. The measured properties of polyurethanes include glass transition temperatures, tensile strengths, flexural moduli, and impact strengths.     

Novel Biobased Polyurethanes Synthesized from Soybean Phosphate Ester Polyols: Thermomechanical Properties Evaluations

Biobased polyurethanes from soybean oil–derived polyols and polymeric diphenylmethane diisocyanate (pMDI) are prepared and their thermomechanical properties are studied and evaluated. The cross-linked biobased polyurethanes being prepared from soy phosphate ester polyols with hydroxyl contents ranging from 122 to 145 mg KOH/g and pMDI within 5 min of reaction time at 150°C in absence of any catalyst show cross-linking densities ranging from 1.8 × 10³ to 3.0 × 10³ M/m³, whereas glass transition temperatures vary from approximately 69 to 82°C. The loss factor (tan ) curves show single peaks for all these biobased polyurethanes, thus indicating a single-phase system. The storage moduli (G) at 30°C range from 4 × 10⁸ to 1.3 × 10⁹ Pa. Upon postcure at 150°C, the thermomechanical properties can be optimized. Cross-link densities are improved significantly for hydroxyl content of 139 and 145 mg KOH/g at curing time of 24 h. Similarly, glass transition temperature (T_g) and storage moduli around and after T_g are increased. Meanwhile, tan intensities decrease as result of restricted chain mobility. Longer exposure time (24 h) induces thermal degradation, as evidenced by thermogravimetric analysis (TGA). The dynamic mechanical (DMA) analysis shows that postcure at 100°C for times exceeding 24 h also leads to improved properties. However, cross-linking densities are lower compared to postcure carried out at 150°C.     

膨胀石墨-ZnO复合材料的制备及其光催化降解原油的性能

采用化学氧化-浸渍法制备出膨胀石墨-ZnO（EG—ZnO）复合材料,采用扫描电镜、X射线衍射仪、紫外-可见分光光度法及傅里叶变换红外光谱仪等表征手段对该复合材料的形貌、结构及其光催化降解水面原油的性能进行了研究。研究结果表明,EG—ZnO复合材料保持了膨胀石墨疏松多孔的蠕虫形貌,六方晶系结构的ZnO晶体均匀地分布于膨胀石墨的层间和表面。经紫外光照射72h后,吸附于EG—ZnO复合材料中的原油发生了显著的光催化降解反应。当该复合材料中ZnO的质量分数为80％时,原油的降解率可达35％,降解产物中有酮、醛及醇类等物质。