Bio‐Based,Self‐Condensed Polyols

A new method for the synthesis of high‐molar‐mass (MM), bio‐based polyols for elastic polyurethanes is developed. This process is based on the self‐condensation of low MM polyols (M_n ≈ 1000) and vacuum removal of the resulting glycerol. Self‐condensation products are hyperbranched estolide polyols with average MMs close to 3000 and hydroxyl numbers in the range of 40–95 mg KOH g^?1. Three polyols, one with primary and two with secondary hydroxyls and different functionalities, are studied. The transesterification proceeded much faster with primary hydroxyls, leading to high‐viscosity products. The effect of functionality and reactivity of starting polyols on properties is discussed. Practical applications: The process is useful for upgrading the existing natural oil‐based polyols to higher MM, lower OH number and variable‐functionality polyols, for expanding application in the urethane field. The process is simple, involving just an oil‐based polyol, a catalyst, and heating under vacuum.     

基于环三磷腈磷氮阻燃剂的合成及其在聚氨酯泡沫的应用

以六氯环三磷腈、对羟基苯甲醛、苯胺及亚磷酸二乙酯等原料，成功合成阻燃剂六（4-苯胺基次甲基苯氧基-亚磷酸二乙酯基）环三磷腈（HADPPCP），用于阻燃基于苹果酸多元醇的聚氨酯硬泡。HADPPCP具有良好的热稳定性和成炭性，氮气气氛下的初始分解温度为191.9℃，700℃时的残炭量高到46.8%（质量）。HADPPCP的加入可以改善聚氨酯硬泡的热稳定性、阻燃性能和燃烧行为。添加25%(质量)的HADPPCP可以将聚氨酯泡沫的氧指数从18%提高到25%，最大热释放速率和总热释放量分别从230 kW/m²和20.1 MJ/m²降低至213 kW/m²和16.6 MJ/m²，总产烟量从10.5 m²下降到5.3 m²。     

Sugar replacement in sweetened bakery goods

This review presents the state‐of‐the‐art concerning the application of natural and artificial high‐intensity sweeteners, fructans and bulking agents such as polyols as sugar replacers in sweet‐baked goods and their effects on product characteristics. The recent much publicised attention given to weight gain of the population and its consequences on the occurrence of diet‐related diseases in developed countries has influenced the food manufacturers attempts to provide the consumer with reduced energy products. The replacement of sucrose in sweet bakery products by alternative natural or artificial sweeteners can be a challenging issue. Sucrose as a main ingredient in sweet bakery products contributes, aside from providing sweetness, to numerous processing and product characteristics. Intense sweeteners have a high sweetness compared with sucrose but lack in their contribution to the body of the product, whereas the replacement of sucrose with bulking sweeteners may result in products with a similar body but a lack in taste and flavour.     

Lyophilized flutamide dispersions with polyols and amino acids: preparation and in vitro evaluation

Context: Flutamide (FLT) has poor aqueous solubility and low oral bioavailability. Objective: Lyophilization monophase solution was used for preparing lyophilized dispersions of FLT with polyols and amino acids to increase its poor dissolution. Methods: Physical properties and dissolution behavior of their physical mixtures and lyophilized dispersions were investigated. Results and discussion: The carriers increased the aqueous solubility of FLT but to a limited extent with arginine and glycine showing a linear A_L-phase solubility diagrams. Gas chromatography indicated that residual tertiary butyl alcohol was in range of 0.007?0.023% (w/w) in the dispersions. In all dispersions, the crystal structure of FLT was confirmed using differential scanning calorimetry, X-ray diffractometry, and scanning electron microscopy. However, the percent drug crystallinity was found to decrease with increasing the carrier content. Infrared spectroscopy revealed no interaction between drug and carriers. The particle size of FLT dispersions ranged between 0.61 and 1.81 μm, with a high surface area (293.93?465.37 m²/g) and porosity (447.69?754.33 e^-3 mL/g). In addition, the poor flow properties of FLT were improved but to a limited extent. FLT dissolution from the dispersions was enhanced with 46.35% and 36.43% of FLT dissolved after 30 minutes from 1:5 FLT–mannitol and FLT–trehalose dispersions, respectively, compared with only 13.45% of pure FLT. On the other hand, after 30 minutes 38.57% and 46.78% of FLT was dissolved from 1:3 FLT–arginine and FLT–glycine dispersions, respectively. Conclusion: These data suggest that polyols and amino acids might be useful adjuncts in preparation of immediate-release formulations of FLT.     

多元醇对PVC热稳定和色泽的影响

测试PVC静态热稳定性和PVC白度值,研究多元醇分子的羟基结构、数目和位置对PVC加工热稳定性和色泽变化的影响,研究结果表明:伯醇,尤其季戊四醇和双季戊四醇对PVC热稳定性和保持初期色泽有利;多元醇对PVC热稳定性好于多元醇酯,但通过酯化多元醇,可以抑制多元醇从PVC中析出;糖醇对PVC具有一定的稳定作用,但是在酸作用下分子内发生环化,使PVC初期色泽变差.     

Urethanes and polyurethanes based on oxypropylated cork: 1. Appraisal and reactivity of products

The reaction of various polyols derived from the oxypropylation of cork with aliphatic and aromatic mono‐ and diisocyanates was studied in solution at room temperature. In all instances, good second‐order kinetics were observed and the corresponding rate constant determined. The reactivity of the aromatic isocyanate was found to be much higher than that of aliphatic counterparts. The ensuing urethanes and polyurethanes were characterised by FTIR and ¹H NMR spectroscopy, DSC and sol/gel distribution. © 2001 Society of Chemical Industry     

Click‐ligation of coumarin to polyether polyols for polyurethane foams

A simple strategy for the synthesis and functionalization of polyurethanes is described. Anionic ring‐opening polymerization was combined with ‘click’ chemistry to synthesize polyols with fluorescent properties. This route allows the incorporation of a wide range of functionalities in the polyols with an easy, clean and highly selective process compatible with several types of functional groups. The proposed strategy opens the way to the production, in a cost‐effective way, of ‘smart’ polyurethanes with non‐conventional properties like fire retardancy, antimite properties, antibacterial properties, etc. Alkynyl groups were introduced into the polyol chains by the controlled addition of glycidyl propargyl ether as co‐monomer during a conventional anionic ring‐opening copolymerization with propylene oxide. Subsequently 4‐azidomethyl‐7‐methoxycoumarin molecules were introduced onto the alkynyl‐polyether polyols by copper‐catalysed cycloaddition reactions to produce end‐functionalized polyols. The chemical structure of the novel polyols was characterized using infrared spectroscopy, nuclear magnetic resonance spectroscopy, gel permeation chromatography with triple detection and matrix‐assisted laser desorption/ionization time‐of‐flight mass spectroscopy. These characterization techniques confirmed the presence of a considerable amount of functional groups in the structure of the polyols. Finally, various fluorescent rigid foams, based on the functionalized polyols, were synthesized. Copyright © 2012 Society of Chemical Industry     

Self-emulsifiable soybean oil phosphate ester polyols for low-VOC corrosion resistant coatings

A series of soybean oil phosphate ester polyols (SOPEP) was prepared by reaction of fully epoxidized soybean oil with phosphoric acid and simultanoeous hydrolysis in the presence of a polar solvent. The polyols were characterized by determination of acid value, oxirane number, hydroxyl value, molecular weight (GPC), and FTIR spectra. These polyols with varying amounts of acid phosphate groups could be self-emulsified to form aqueous dispersions after neutralization with organic base. These aqueous dispersion showed varying degrees of stability and their appearance ranged from opaque dispersions to translucent to clear solutions. Waterborne coating compositions were prepared using these aqueous dispersions as principal components and their thermally cured film properties were studied. it was found that by careful selection and formulation, SOPEPs can be successfully used for low-VOC waterborne coating formulations. SOPEPs with 3.5% phosphate ester content showed visibly superior corrosion resistance properties.     

混杂增强聚氨酯复合硬质泡沫塑料的研制

系统介绍混杂增强聚氨酯复合硬质泡沫塑料的制备情况，详细分析聚氨酯硬质泡沫塑料制备过程中的工艺问题，表征与分析其结构与性能，着重分析偶联剂对填充物增强性能的影响以及填充物含量对聚氨酯硬质泡沫塑料吸水性能的影响，介绍聚氨酯硬质泡沫塑料的应用，最后指出其发展前景。     

聚醚多元醇中环状齐聚物的去除(续)

(接上期第 2 3页 )3　膜分离Doraietal[16] 通过超滤除去低相对分子质量级份 ,使聚醚多元醇 ,尤其是聚四氢呋喃多元醇 ,具有较窄的分布 (Mw∶Mn=1 .2～ 1 .8)。该方法通过对多分散的熔融聚合物实施物理分级 ,达到降低相对分子质量分布的目的 ,可使最终产物的相对分子质量为 40 0～ 40 0 0 ,分散度为 1 .2～ 1 .8。该方法首先需要准备 1套交叉流动的膜分离系统 ,采用渗透膜或半渗透膜 ,膜的一边是滞留物 ,另一边是超滤液。然后 ,在起始聚合物的熔点以上 ,分解温度以下 ,且温度不大于膜的熔融和分解温度 ,将起始聚合物熔融 ,并流入该系统中…