Ammonium Salts with Polyether-Tail: New Ionic Liquids for Rhodium Catalyzed Two-Phase Hydroformylation of 1-Tetradecene

By attaching the polyether chains to ammonium salts, a novel class of ionic liquid termed polyether melt is prepared. Such polyether melt contains no fluoride and hence is environmentally more benign. Applying this polyether melt as a polar phase, the hydroformylation of 1-tetradecene catalyzed by Rh complex catalyst in two-phase medium was investigated. The rhodium catalyst immobilized in this polyether melt is readily separated from the aldehyde product phase by decantation and has been reused for seven times without obvious loss of activity.     

聚醚多元醇新型催化剂的研究

专题采用两种金属盐合成出聚醚用双金属高效催化剂,该催化剂完全可以取代传统的KOH催化 剂。用其合成聚醚可提高单体转化率、缩短反应时间、简化工艺,所得产品具有不饱和度低、分子量分布窄并 可自行设计等特点。     

A novel synthesis of reactive polyethers with pendant chloromethyl group by polyaddition of bis(epoxide)s with aromatic dichlorides

New polyethers with pendant chloromethyl groups were successfully synthesized by a polyaddition of bisepoxides with 4,4′-dichloro-3,3′-dinitrodiphenyl sulfone (DCNS) using quaternary onium salts or crown ether complexes as catalysts. The polyaddition of DCNS with diglycidyl ether of bisphenol A (DGEBA) was enhanced efficiently by the addition of tetrabutylammonium chloride (TBAC), tetrabutylammonium bromide (TBAB), or tetrabutylphosphonium chloride (TBPC) as catalysts. It was also found that the reaction proceeded smoothly in amide-type polar solvents such as N,N-dimethylacetamide (DMAc) and N-methyl-2-pyrrolidone (NMP) to give a high molecular weight polyether P-1. The polyaddition of DCNS with diglycidyl ether of ethylene glycol (DGEEG) using TBAB in DMAc also proceeded to give the polyether P-2 in good yield. The resulting polyethers contain reactive chloromethyl groups in a side chain, which was introduced during main chain formation.     

阴离子水性聚氨酯的合成及性能研究

采用甲苯二异氰酸酯、聚醚二元醇和二羟甲基丙酸为主要原料,用预聚体方法合成了阴离子聚醚型水性聚氨酯乳液。探讨了NCO/OH（R值）对水性聚氨酯性能的影响。结果表明,R值为1.4时得到的阴离子聚醚型水性聚氨酯乳液及涂膜性能较好。     

MDI固化剂的合成

以二苯甲烷二异氰酸酯(MDI)单体、三羟甲基丙烷(TMP)及聚醚为原材料,采用加成-三聚聚合工艺合成聚氨酯固化剂。讨论了m(TMP)∶m(聚醚)及n(—NCO)∶n(—OH)对固化剂性能的影响。结果表明,在m(TMP)∶m(聚醚)为9∶1,n(—NCO)∶n(—OH)为3.5∶1的合成条件下,可得到相容性好、贮存稳定的聚氨酯固化剂。     

用于环戊烷发泡的组合聚醚的开发

开发了一种能单独用于环戊烷发泡体系的聚醚多元醇ZS-8118,以ZS-8118、匀泡剂、叔胺催化剂、环戊烷、水等原料配制了硬泡组合聚醚。简单讨论了聚醚多元醇品种、匀泡剂及催化剂对发泡体系的影响。结果表明,该组合聚醚贮存稳定性好,制得的泡沫塑料性能优良,能满足冰箱、冷柜等产品的生产要求。     

Lithium-conducting ionic melt electrolytes from polyether-functionalized fluorosulfonimide anions

Solvent-free lithium-conducting ionic melt (IM) electrolytes were synthesized and characterized with respect to chemical structure, purity, and ion transport properties. The melts consist of lithium (perfluorovinylether)sulfonimide salts attached covalently to a lithium-solvating polyether chain. Ionic conductivities are relatively high which is a consequence of the favorable combination of the low lattice energy of the lithium fluorosulfonimide salt (low basicity of the fluorosulfonimide anion), the relatively low viscosity of the polyether matrix, and the relatively high salt content of the melts. Galvanostatic dc polarization experiments, using cells with non-blocking Li electrodes, indicate that salt concentration polarization does not occur in these electrolytes as dc current is passed through them.     

Ionic conduction in polyether-based lithium arylfluorosulfonimide ionic melt electrolytes

We report synthesis, characterization and ion transport in polyether-based ionic melt electrolytes consisting of Li salts of low-basicity anions covalently attached to polyether oligomers. Purity of the materials was investigated by HPLC analysis and electrospray ionization mass spectrometry. The highest ionic conductivity of 7.1 × 10⁻⁶ S/cm at 30 °C was obtained for the sample consisting of a lithium salt of an arylfluorosulfonimide anion attached to a polyether oligomer with an ethyleneoxide (EO) to lithium ratio of 12. The conductivity order of various ionic melts having different polyether chain lengths suggests that at higher EO:Li ratios the conductivity of the electrolytes at room temperature is determined in part by the amount of crystallization of the polyether portion of the ionic melt.     

煤热解焦油化学破乳脱盐试验研究

为减少煤焦油乳状液水中大量无机盐对分馏塔冷凝器等设备的腐蚀,促进煤焦油与水分离,利用化学破乳方法对煤焦油进行了脱盐试验,探讨了煤焦油化学破乳的可行性,考察了破乳剂类型、破乳剂添加量、注水量、脱盐温度及停留时间等试验条件对煤焦油脱盐效果的影响。结果表明,自制聚醚破乳剂脱盐效果较佳,破乳剂添加量100×10~(-6),注水量15%,脱盐温度110℃,脱后煤焦油中盐含量均出现明显拐点,停留时间在一定范围内对脱盐效果影响甚微。因此,自制聚醚破乳剂较其他2种较广泛应用于煤焦油脱水的破乳剂具有更好的脱盐效果,这主要归因于其特殊结构与煤焦油中沥青质有很强的相互作用。     

Segmented polyether ester copolymers—A new generation of high performance thermoplastic elastomers

This paper reviews a series of high-melting thermoplastic polyether esters prepared by transesterification from dimethyl terephthalate, polytetramethylene ether glycol (MW 600–2000), and 1,4-butanediol. The resulting copolyesters exhibit a two-phase domain structure consisting of amorphous polyether ester soft segments and crystalline tetramethylene terephthalate hard segments. By proper selection of the relative amounts of soft and hard segments, polymers ranging from relatively soft elastomers to impact resistant elastoplastics may be obtained. The preparation, polymer structure as well as the physical and environmental properties of polyether esters are discussed. The combination of good melt flow properties, excellent melt stability, and rapid hardening rates permits the processing of these polymers by a wide variety of methods. The excellent processing characteristics in conjunction with the unusual physical and mechanical properties of segmented polyether esters has led to their wide acceptance.     

高铁专线用混凝土桥梁聚氨酯防水涂料工艺研究

将聚醚多元醇与MOCA制成交联剂,采用甲苯二异氰酸酯(TDI)与聚醚多元醇制成异氰酸酯预聚体,制备双组分无溶剂高强型聚氨酯防水涂料。分析了预聚体的用量、填料类型与聚醚类型、聚醚多元醇的配比、异氰酸根含量(-NCO)对涂膜力学性能的作用。通过此方式所制备的防水涂料效果良好,可以满足高铁专线混凝土桥梁防水层的相关要求。     

Synthesis and Properties of a Novel Branched Polyether Surfactant

A novel branched polyether surfactant (TPE) was prepared by anion polymerization with different proportions of propylene oxide (PO) and ethylene oxide (EO) using 1,1,2,2-tetrakis(4-hydroxyphenyl)ethane as a core. The structures and average molecular weight (M _n ) of the TPE were characterized by ¹H NMR and GPC. The cloud point was determined by turbidimetry in the presence of inorganic salts. Inorganic salts decreased the cloud point of TPE polyether in the following order: Na₂CO₃ > Na₂SO₄ > NaCl > CaCl₂ > MgCl₂. The effects of inorganic salts (NaCl, MgCl₂, CaCl₂, and NaSCN) and temperature on the surface activity of TPE in aqueous solution were investigated by surface tension measurements. The surface activity parameters and the thermodynamic parameters were calculated from surface tension data. Similar to the effect of increasing temperature, the salting-out inorganic salts such as NaCl, MgCl₂, and CaCl₂ favor the micellization and increase the maximum surface excess concentration, while the salting-in NaSCN has the opposite effect. The influence of NaCl on the morphology of micelles was investigated by TEM. The micellization is entropy-driven at low temperature and enthalpy-driven at higher temperature. The TPE polyether has large surface activity and can be used as a demulsifier to break up crude oil emulsions.     

线性聚醚氨基嵌段有机硅柔软剂的应用特点

以端环氧基硅油、聚醚胺和端环氧基聚醚为主要原料,合成了线性聚醚氨基嵌段有机硅柔软剂;乳化后用于织物的整理。考察了线性聚醚氨基嵌段有机硅柔软剂对织物的白度、摩擦牢度、防水性能和撕破强力等的影响,并用FT-IR表征了产物结构。结果表明,与采用传统有机硅柔软剂氨基硅油和亲水聚醚改性硅油整理的织物相比,经线性聚醚氨基嵌段有机硅柔软剂整理织物的白度、摩擦牢度、防水性能和撕破强力等具有明显的优势,并可很好地平衡手感和亲水性之间的矛盾,具有优良的性能。     

Effect of the drying temperature on sulfonated polyether sulfone nanofiltration membranes prepared by a coating method

This study reports on the preparation of a novel sulfonated polyether sulfone nanofiltration membrane via a manual coating method. The as-prepared membrane was modified by changing the drying temperature and utilizing additives. As the drying temperature was increased, the rejection performance of the as-prepared nanofiltration membrane increased, while flux decreased. The nanofiltration membrane dried at 40°C had relatively high permeation flux and good rejection performance for divalent ions and dyes; therefore, it is suitable for dye wastewater treatment. The nanofiltration membrane dried at 50°C had relatively low permeation flux and relatively good rejection performance for inorganic salts. The pore size of the skin layer was reduced as the drying temperature was increased. The average diameters of the as-prepared nanofiltration membranes dried at 40 and 50°C were 5.08 and 1.51 nm, respectively. Due to excellent hydrophilicity and relatively low roughness, the as-prepared nanofiltration membranes dried at 40 and 50°C had superior antipollution characteristics.     

具有对称与不对称封头的聚醚型汽车压缩机润滑油性能对比研究

对比研究了具有对称和不对称封头的两类聚醚型润滑油的性能。结果表明,两类聚醚型压缩机润滑油吸湿性小,两者的相溶性好;聚醚型润滑油封头率越高,吸湿性越小;相比而言,具有不对称封头的聚醚型润滑油比具有对称封头的吸湿性低,润滑性好。这为今后聚醚型润滑油向提高封头率以及聚醚的不对称封头方向发展提供参考。     

4min快速脱模环戊烷型组合聚醚

开发了一种以聚醚多元醇、泡沫稳定剂、叔胺催化剂、环戊烷、水等原料配置的组合聚醚,可用于4 min快速脱模冰箱组合料的生产.讨论了聚醚多元醇、催化剂、泡沫稳定剂、环戊烷等对快速脱模的影响.结果表明,该组合聚醚贮存稳定性好,制得的的泡沫性能优良,能满足4 min快速脱模冰箱组合料的生产.     

薄膜扩散梯度系数的研究

薄膜扩散梯度技术是一种新型的原位采集并测量重金属有效态或生物可给性的方法。本实验研究的是不同pH对同种聚醚砜膜的扩散系数的影响以及重复使用次数对同一种聚醚砜膜扩散系数的影响。不同pH对膜扩散系数影响的研究可以看出这种聚醚砜膜的使用范围在pH=2~9,在强碱性条件下会严重影响膜的性能。同一张聚醚砜膜不同实验次数的研究说明此种聚醚砜膜的合理使用次数为1次,重复使用会影响它的扩散性能。     

聚醚改性聚硅氧烷消泡剂的合成及复配

在聚硅氧烷链段上引入聚醚链段而得到的聚醚改性聚硅氧烷消泡剂是一种性能优良的消泡剂。综述了聚醚改性聚硅氧烷的合成方法及其复配,简要介绍了其应用情况。     

Liquid Membrane Separations of Potassium Iodide from Mixed Brines

Abstract

Liquid membranes containing the polyether dibenzo-18-crown-6 dissolved in chlorinated hydrocarbons were used to separate potassium iodide from brines of sodium chloride and other salts. Product purity is 95% or better. The separatations largely proceed via the transport of polyether-potassium iodied complexes; transport of other species is much less important. These systems can be formulated as emulsion liquid membranes to give the rapid fluxes required for practical application.