羟化乙氧基化改性磷脂的合成与性能研究

以大豆磷脂为原料,利用两步合成了羟化乙氧基化改性磷脂,改进了磷脂的乳化性和分散性。     

脂肪醇的乙氧基化

本文综述了脂肪醇（或烷基醇）与环氧乙烷乙氧基化的反应过程。分析了在酸性或碱性催化剂的作用下，乙氧基化强化的可能性及其途径，以及主要反应器类型等。结果表明，分散进料和连续反应的管式反应器有益于产率的提高。     

乙氧基化脂肪酸甲酯的性能及丙氧基化改性研究

以单碳酸或混合酸甲酯为原料，通过一步法乙氧基化反应合成了不同链长的脂肪酸和不同EO数的乙氧基化脂肪酸甲酯(EFME)，测定了EFME的物化性能和应用性能。结果表明，EFME具有低成本、低泡等特殊优点，性能依赖EO加成数变化连续可调整，EFME中的封端甲基是导致其性能不同于AEO的最重要的结构因素。用PO对EFME进行化学改性，先加成PO的产品的起泡力更低、流变性更好，与不改性产品相比起泡力降为原先的29％；稳泡性降为原先的22％；黏度降低为原先的44％。说明PO位于分子的亲水端侧较处于疏水端侧对产品的泡沫性和流变性的影响程度更大，通过PO改性可以进一步开发EFME的新用途。     

乙氧基化反应釜的设计

本文叙述了传统乙氧基化搅拌反应釜的操作工艺过程以及所产生的弊病,借鉴国内外经验,提出改善反应条件,将引发剂雾化恒定地分散到气相的环氧化物中去的外循环工艺方法,就可以避免传统反应釜所产生的弊病。同时,也对反应系统提出相应要求。     

乙氧基化反应的发展

近年来,世界150多个厂家年产乙氧基化物200万t,估计在以后的几年里,其年产量将以4～5倍的速率增长。在我国,乙氧基化物也逐渐受到用户的青睐,乙氧基化生产的聚醚越来越受到关注。所以对乙氧基化的反应进行研究无论是从理论上还是从实践的观点来看都很有必要。     

乙氧基化反应的发展

近年来，世界150多个厂家年产乙氧基化物200万t，估计在以后的几年里，其年产量将以4～5倍的速率增长。在我国，乙氧基化物也逐渐受到用户的青睐，乙氧基化生产的聚醚越来越受到关注。所以对乙氧基化的反应进行研究无论是从理论上还是从实践的观点来看都很有必要。     

典型乙氧基化工艺对比

乙氧基化反应是生产非离子表面活性剂最重要的技术,乙氧基化物由环氧乙烷（EO）在催化剂的作用下与含活泼氢的有机化合物反应制得。在乙氧基化领域,从起初的搅拌釜式反应器开始,反应器安全性、产品多样性及可选择性等方面的要求迫使设计师们不断改进设计,使得各种各样的新式反应器不断涌现,本文主要对目前国际国内典型乙氧基化反应器及工艺技术进行对比分析,指出各自所具有的特点     

乙氧基化反应新型催化剂工业小试研究

采用新型窄分布固体催化剂，应用在醇醚反应中，探讨该催化剂的工业应用条件：诱发温度、反应温度、反应压力、反应时间、熟化时间、催化剂用量等，从而找出该催化剂的工艺操作参数，为工业应用提供依据。     

静态混合器在乙氧基化反应中的应用

介绍了静态混合器在乙氧基化反应中的应用。采用具有较强传热效果的夹套式静态混合器作为反应器。在反应条件ｔ＝１００℃,ｐ＝３．６ＭＰａ在一定量的有机碱催化下,得到无色透明的液体乙二醇苯醚产品,主组分含量大于９７％,二甘醇苯醚含量只有０．６％。无需精制就可使用,极大地降低了成本,较高的反应压力使环氧乙烷处于液相中反应,解决了釜式反应器气液分布不均,产品质量不稳定的问题。     

外循环反应釜在乙氧基化反应中的应用

外循环喷雾式反应器是目前最先进的乙氧基化反应器之一,但反应釜式(含外循环式)反应器仍是中小型企业的主流,如何设计出最适合企业及产品的工艺参数是关键。通过对比釜式与外循环釜式反应器在环氧乙烷(丙烷)实际加成制备非离子表面活性剂过程中的效率、产品质量、安全性,得出带外循环器的反应釜更适合企业发展的结论,而针对不同产品选择不同的工艺步骤及智能化是今后发展的方向。     

乙氧基化催化剂进展及发展方向

非离子表面活性剂的研究在精细化工领域及表面活性剂体系中占有重要地位。而乙氧基化催化剂的研究是这一领域较为活跃的一个研究方向。结合近年来国内外相关的研究工作，从乙氧基化催化剂的发展过程、催化机理、反应动力学等几个方面综述了乙氧基化催化剂研究的最新进展，分析了影响催化活性及催化性能的各种因素，探讨了未来的发展趋势。     

Epoxidation,hydroxylation, acrylation and urethanation of Linum usitatissimum seed oil and its derivatives

Some preliminary studies on epoxidation, hydroxylation, acrylation and urethanation of Linum usitatissimum seed oil (LO) and its derivatives have been carried out. Epoxidation and hydroxylation were performed in situ using H₂O₂ and acetic acid to develop epoxidized oil (LOE) and epoxy polyol (EP). EP was modified with synthetic monomers, viz. acrylonitrile (AN) and methylmethacrylate (MMA), in the presence of benzoyl peroxide in an inert environment to develop acrylic grafted epoxy polyols (AEPs). EP and AEPs were further treated with an isocyanate, resulting in the formation of plain and acrylic grafted epoxy polyurethanes (EPU and AEPUs). The mechanism of the reaction as well as the structural aspects of LO, LOE, EP, AEPs, EPU and AEPUs were investigated by ¹H‐NMR and ¹³C‐NMR spectroscopic techniques, which also confirmed the incorporation of the acrylic monomers – AN and MMA – on the EP backbone Spectral analyses further demonstrated that, depending on its structure (substituent), each acrylic monomer follows a different grafting mechanism. Physico‐chemical characterization of AEPs and AEPUs was carried out by standard laboratory methods, and thermal analyses were accomplished by TGA and DSC. Physico‐mechanical characterization of AEPUs coatings further showed considerable improvement compared to the pristine (EPU) resin, due to the introduction of stiff acrylic moieties. The aforementioned studies as well as the coating characteristics of AEPU confirmed that AN and MMA have been incorporated in the EP backbone. These systems can be safely employed at up to 210–220 °C.     

醋酸丁酯一步法乙氧基化合成聚乙二醇丁醚醋酸酯

通过共沉淀法合成出水滑石类的LDH复合氧化物材料,经过三乙胺改性后,发现其在XRD、FT-IR、NH_3-TPD、CO_2-TPD及TEM的表征中与改性前相比有显著差别。研究表明,改性后的催化剂有弱酸和弱碱双活性中心。和改性前相比,使用三乙胺改性后的催化剂在醋酸丁酯的乙氧基化反应中,反应活性明显提高,1EO产物含量显著增大,产品分布变窄。     

Kinetics and mechanism of homogeneous catalytic hydroxylation of maleic acid by hydrogen peroxide. Part II: Analysis of material balance conformities and the mathematical model

The general kinetic laws relating the changes in reactants and products ratios with changes in the operating conditions of the catalytic epoxidation and hydroxylation reaction of maleic acid by hydrogen peroxide have been analyzed. In the course of the hydroxylation reaction, the formation of epoxysuccinic and tartaric acids, and the decomposition of hydrogen peroxide to molecular oxygen have been observed to take place in parallel. The catalytic complex (Cat.2H₂T) formed between sodium tungstate (catalyst) and tartaric acid in the course of the reaction is found to be inactive in the epoxidation reaction but active in the catalysis of the decomposition of hydrogen peroxide. This fact explains the non-formation of tartaric acid at high maleic acid conversion. The mathematical model for the overall process has been developed.     

Kinetics and mechanism of maleic acid hydroxylation by hydrogen peroxide. Part I: Formal kinetic studies by immobilized catalysis in a pseudo-homogeneous system

Formal kinetic studies of the epoxidation and hydroxylation of maleic acid by hydrogen peroxide (H₂O₂) have been carried out in the presence of a molybdenum salt, as catalyst, immobilized on Amberlite IRA-400 polymer resin in the chloride form. Immobilization of the catalyst on the resin was by a sorption process. Hydroxylation by immobilized catalysis afforded higher H₂O₂ selectivity and increased product yield in excess of 85%. Analysis of kinetic results shows that the reaction in the pseudo-homogeneous system follows the typical pseudo-zero order dependence on H₂O₂ concentration and is first order with respect to maleic acid concentration. However, the rate model developed for the immobilized catalyst fits the experimental data smoothly and parameter estimation using the Lineweaver–Burk plot fulfils the kinetic consistency tests without additional mathematical manipulation. The problem of activity and stability of the present catalyst was also investigated.     

科技创新助推中国乙氧基化产业转型发展

总结了十二五期间中国乙氧基化产业发展情况、产业布局及产品结构,阐述了乙氧基化产业的技术创新亮点及产业目前存在的问题,提出了中国乙氧基化产业及技术未来发展方向的建议。     

The study of epoxidized rapeseed oil used as a potential biodegradable lubricant

The application of epoxidized rapeseed oil as a biodegradable lubricant is described. The epoxidation treatment has no adverse effect on the biodegradability of the base stock. Epoxidized rapeseed oil has superior oxidative stability compared to rapeseed oil based on the results of both oven tests and rotary oxygen bomb tests. Moreover, the oxidative stability can be dramatically promoted by the addition of a package of antioxidants. The epoxidized rapeseed oil has better friction-reducing and extreme pressure abilities according to tribological investigations. Formation of a tribopolymerization film is proposed as explanation of the tribological performance of epoxidized rapeseed oil.     

磷酸化技术及其在皮革加脂剂中的应用

综述了在制备磷酸酯皮革加脂剂中使用的磷酸化试剂如三氯氧磷、三氯化磷、磷酸、多聚磷酸及五氧化二磷各自的优缺点，指出P2O5是皮革工业中应用最广泛、最重要的磷酸化试剂；简述了磷酸酯的组成分析方法及其注意的问题；介绍了合成磷酸酯在皮革加脂中的研究进展，并强调为了更好地提高磷酸酯加脂剂的加脂性能，要从皮革工业对于加脂剂的多功能和绿色化的要求来对磷酸酯的分子进行设计。     

Effect of process variables,degree of ethoxylation and alcohol structure on relative ethoxylation rate constants

Supercritical fluid chromatographic determinations of ethylene oxide distributions in ethoxylated alcohols with subsequent computer calculations of relative propagation to initiation ethoxylation rate constants for each ethoxylated oligomer have been carried out for normal octanol under varying reaction conditions. A number of other alcohols were also ethoxylated under essentially constant conditions. In the normal octanol studies, within an approximately fifteen-fold change in absolute ethoxylation rates due to variations in temperature, pressure, and potassium hydroxide catalyst concentration, the data indicate that such changes do not affect ethylene oxide distributions. Suggestions by earlier workers of changes in relative ethoxylation rate constants with the average degree of ethoxylation were verified. Chain length for normal alcohol feeds does not affect distributions in the C-8 to C-13 range, but branching at the carbon α to the hydroxyl carbon increases the relative propagation to initiation rate constants, and a secondary alcohol exhibits an even higher ratio. Presented in part at the 80th and 81st National Meetings of the American Oil Chemists’ Society, May 1989, Cincinnati, Ohio; and April 1990; Baltimore, MD.     

Synthesis of Fe-MCM-48 and its catalytic performance in phenol hydroxylation

Highly ordered Fe-MCM-48 was synthesized by a mixed templation method under low molar ratio (0.17:1) of mixed surfactants to silica and characterized by XRD, ²⁹Si-MAS NMR, ESR, and UV-Visible. Its catalytic activity and selectivity was studied for phenol hydroxylation using H₂O₂ (30%). The substituting element (Fe³⁺) is partially incorporated into the framework position forming a new type of active site which raises the phenol conversion to 43.6% and the diphenol (the mixture of catechol (CAT) and hydroquinone (HQ)) selectivity to 97.7%.