环氧增塑剂产品色泽问题的技术探讨

针对环氧植物油类增塑剂生产中出现的产品色泽不合格问题,分析了植物油精制、环氧化反应等五个过程中存在问题的原因,并提出了切实可行的解决方案。     

植物油多元醇开发的技术进展

介绍了国内外市场上的聚氨酯用植物油多元醇产品,综述了醇解、烷氧基化、植物油臭氧氧化、植物油环氧化和羟基化、植物油氢甲酰化5种工艺路线合成植物油多元醇的研究进展,并对我国植物油多元醇的发展提出建议。     

环氧生物质油在合成润滑油基础油的研究进展

衍生于植物油和动物脂肪的生物质油是生物润滑油的重要原料。与矿物油相比,生物质油具有低毒性、高生物降解性、高润滑性和良好的黏温性等优点,但其含双键和甘油酯基导致低温流动性和氧化稳定性差。因此,生物质油不宜直接作为润滑油基础油使用。生物质油经环氧化改性增加了氧化稳定性,加强了对金属表面的吸附,提高了润滑性。但是,单纯进行环氧化改性,也会导致油品的黏温性和低温流动性变差。因此,需要对环氧生物质油进一步开环改性。对比选择性氢化、异构化等改性方法,环氧化-开环方法反应条件温和,分子设计空间大。本文总结了由环氧植物油通过开环醚构化、酰化合成生物基础油的现状和发展趋势, 重点阐述了环氧植物油及其衍生物环氧脂肪酸甲酯与有机醇、羧酸和酸酐合成润滑油的研究进展,分析了改性分子结构对润滑油性能的影响,讨论了合成生物润滑油研究中尚存的问题, 并认为优化改性工艺、开发绿色高效的催化剂是未来的发展方向。     

双氧水氧化环己烯反应液有机相精馏分离提纯研究

针对无溶剂法双氧水氧化环己烯合成环氧环己烷的有机相反应液,本文采用常压连续精馏的方法对其进行了分离纯化,并得到了精馏回收环己烯和环氧环己烷的较佳工艺条件。实验考察了精馏过程中影响回收环己烯和环氧环己烷纯度和回收率的各种因素,优化得到了较佳的精馏操作条件。实验结果表明,在优化精馏操作条件下,环己烯和环氧环己烷的纯度都达99%以上,收率分别为90.56%和83.41%。为双氧水氧化环己烯合成环氧环己烷工业化生产分离工艺和工程设计提供实验基础。     

植物油基多元醇的合成研究进展

介绍了植物油基多元醇的合成方法:过渡金属催化羰基化法、氧化法、酯交换法、醇解法、氨解法、环氧开环法,其中环氧开环法是最为成熟的一种方法,并概述了国内外近年来在植物油基多元醇工业化方面的情况。     

环己烯的环氧化研究进展

综述了以环己烯环氧化为代表的烯烃的环氧化研究进展 ,并介绍了有机过氧化物体系、分子氧体系及电化学合成等工艺的优缺点     

来自植物油的多羟基脂肪酸及其衍生物

对于多羟基脂肪酸工业生产的一种新型方法包括植物油及其衍生物的环氧化，然后在水或其他氢供体，如一元醇类，二元醇类和胺类参与下催化开环（环氧环）环氧化，然后打开环氧乙烷环，引起脂肪酸含有邻位的二元醇基或其他取代羟基脂肪酸衍生物，以决于初始原料，例如，介绍了环氧化菜子油与作为氢供体的单丁胺反应，制备一种羟基取代脂肪酸衍生物，此外，还介绍酯化合物的部分氨解，另一个例子介绍了环氧化菜子油与作为氢供体的不同摩     

乌桕籽油制备环氧脂肪酸异辛酯的工艺

选用具有丰富不饱和键的乌桕籽油为原料,采用了水解、酯化、环氧化等一系列反应合成了环保型增塑剂环氧脂肪酸异辛酯。并通过正交试验研究了脂肪酸异辛酯的环氧化工艺,确定了合成最佳工艺为:每百克脂肪酸异辛酯,甲酸30.37g,双氧水131.49g,反应温度65℃,反应4h后环氧值可达5.71。通过红外确定了产物的构成并考察了拉伸、热稳定性等性能,结果表明环氧脂肪酸异辛酯较邻苯二甲酸二辛酯(DOP)具有更好的热稳定性和挥发迁移性。     

植物油基润滑油应用研究现状

植物油具有生物可降解性、低挥发性、优良的润滑性和良好的黏温性,但植物油存在热氧化安定性差、低温性能差等缺陷,不能直接作润滑油和润滑添加剂应用,需要对其进行改性。常用化学改性方法有选择性氢化、酯交换和环氧化等,其中环氧化-开环反应引入活性基团和双键上的自由基加成反应是合成植物基润滑油添加剂的两种有效的改性方法。最后,就改性植物油用作可降解润滑油基础油和添加剂提出了研究方向并做了展望。     

以树脂为催化剂制备环氧大豆油的研究

本文研究了在酸性离子交换树脂催化下大豆油的环氧化,研究了树脂用量及交联度、反应时间、反应温度等因素对产品环氧值的影响,并得出了环氧化、碱洗、水洗、减压蒸馏等过程的优惠工艺条件.     

Comparison of Different Possible Technologies for Epoxidation of Cynara cardunculus Seed Oil

The world production of epoxidized vegetable oil, mainly epoxidized soybean oil, is continuously increasing because this product can have a wide range of applications. Non‐edible vegetable oils, recovered by the plants growing on marginal and polluted lands, represent a possible answer to industry versus food chain debate. Cardoon (Cynara cardunculus L.) seed oil can be considered as an interesting and sustainable alternative to edible soybean oil to make plasticizers. In this work, a comparison between different epoxidation methods of cardoon oil is depicted and argued, focusing on strong points and weaknesses for each of them. It is found that cardoon seed oil can be successfully epoxidized through feasible existing technologies, by peracids and hydrogen peroxide equally. Moreover, it is demonstrated that a “greener” cardoon oil epoxidation process is possible, by using hydrogen peroxide in the presence of commercial γ‐alumina as heterogeneous solid catalyst. Practical Applications: The paper analyzes the advantages and the problems of different epoxidation methods in order to obtain a final product with high quality and answer the environmental, social, and economic sustainability requirements.     

环氧植物油脂的制备及应用研究进展

对植物油脂的环氧化方法进行了综述,介绍了液体酸催化、固体酸催化、相转移催化及酶催化等制备环氧植物油脂的方法,并指出了各种方法的优点以及存在的问题。同时对环氧植物油脂在聚氨酯、环氧树脂、润滑剂等高分子领域的重要应用进行了总结,并对环氧植物油脂的发展进行了展望。     

环氧油脂肪酸组成分析研究

通过薄层色谱、气相色谱、色质联用等技术,首次得到了油脂环氧化反应期间的脂肪酸环氧化反应规律:开始反应阶段,高含量不饱和脂肪酸反应速率高于低含量不饱和脂肪酸;环氧化反应期间,多不饱和脂肪酸首先生成单环氧酸,之后再逐渐生成二环氧酸,最后生成三环氧酸;富含亚麻酸的油脂环氧化反应时有更易于开环反应的趋向,其次是富含亚油酸的油脂,再次是富含油酸的油脂.实验结果表明,不同环氧油原料在进行环氧化反应时需要控制不同的反应条件,以避免开环副产物量的增加,从而制备得优质环氧油产品.     

Effects of Vegetable Oil Composition on Epoxidation Kinetics and Physical Properties

In this article, we investigate the role of triacylglycerol composition on the properties of epoxidized vegetable oils and the kinetics of the epoxidation process under conditions comparable to commercial epoxidation. Commodity soybean oil (24% oleic acid, 50% linoleic acid, and 7% linolenic acid), high‐oleic soybean oil (75% oleic acid, 8% linoleic acid, and 2.5% linolenic acid), and linseed oil (11% oleic acid, 15% linoleic acid, and 64% linolenic acid) were each epoxidized to various extents. Epoxidation rate, viscosity, differential calorimetry, and X‐ray diffraction data are presented for these oils and interpreted in the context of their fatty acid profile (mostly oleic, linoleic, or linolenic). While fully epoxidized soybean oil is widely commercially available and used in an increasing array of industrial applications, information relating to partially epoxidized oils and epoxidized oils of other cultivars is less well known.     

滇产植物油理化指标测定

研究滇产食用植物油的理化特征与储藏期品质变化规律。以两种特色植物油为对照,对云南出产的五种植物油脂的理化指标进行评价和对比。同时使用过氧化值和酸价,对所研究的油脂的储藏期品质变化进行初步探索。结果表明:云南产植物油质量均满足国标要求。但由于其加工工艺原因,植物油级别较低。含有不饱和脂肪酸的植物油在光照情况下过氧化值和酸价明显改变,可作为质量变化的主要指标。云南出产的四种特色植物油脂不饱和脂肪酸含量较高,是良好的食用油产品;但仍需改善加工工艺以提高其级别。葡萄籽油、红花籽油需添加额外抗氧化剂稳定其品质;过氧化值是最适于进行日常油品质量控制的指标。     

Epoxidized vegetable oil and bio‐based materials as PVC plasticizer

Phthalate esters received a considerable attention owing to its various applications and the harmful health effects resulting from phthalate exposure; thus, finding an alternative to phthalate derivatives became a necessity. Phthalate esters are commonly used as plasticizer in polymer formulation; in particular for poly(vinyl chloride) (PVC) formulation. According to the researches in the last 18 years, epoxidized vegetable oils are one of the alternatives that are strongly encouraged to substitute phthalate esters since they were proven to be valid in various applications, eco‐friendly and sustainable resource. However, most of the production practices for epoxidized vegetable oil are via conventional epoxidation that concentrates on a catalyst that is homogeneous and non‐reusable. This type of catalyst, however, causes several problems later in the process. Therefore, the selective epoxidation of vegetable oils process requires new catalytic systems that are more aligned with the green chemistry principles. This article reviews the harmful health effects associated with the exposure to phthalate esters products, explains the usage of oleochemicals resources as a substitute to phthalate esters and describes different approaches for the epoxidation of vegetable oils. Finally, it draws attention to the usage of epoxy and bio‐based compounds as plasticizers in PVC manufacturing. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46270.     

Biobased Epoxidized Vegetable Oils and Its Greener Epoxy Blends: A Review

Epoxidized vegetable oils (EVO) have drawn much attention in recent years, especially in the polymer industry as they are economical, available, environmentally friendly, non-noxious and renewable. Vegetable oils can be transformed into useful polymerizable oxygenated monomers commonly by Prileshajev-epoxidation, catalytic epoxidation using acidic ion exchange resin, chemo-enzymatic epoxidation, or metal-catalyzed epoxidation. Among those epoxidation methods, chemo-enzymatic epoxidation has achieved considerable interest nowadays since this method is safe, environmentally friendly and conversion rate of epoxidation usually exceeds 90%. Bio-based epoxidized vegetable oils from renewable natural resources are potential green materials to partially substitute and toughen petrochemical-based polymers.     

植物油改性技术及在醋纤纺丝油剂中应用

文章综述了天然植物油改性及其衍生物产品开发研究与在化纤纺丝油剂领域应用现状,介绍了植物油深度改性获得的脂肪酸乳酸酯和氢化植物油产品在醋纤工业纺丝油剂中的替代矿物油的应用研究,用作内油时浆液粘度下降,用作外油时纺丝断头率略有下降,并对环境友好的植物油基产品在化纤领域的应用研究进行了展望。     

A new perspective on vegetable oil epoxidation modeling: Reaction and mass transfer in a liquid–liquid–solid system

A rigorous mathematical model was developed for a complex liquid–liquid–solid system in a batch reactor. The approach is general but well applicable for the indirect epoxidation of vegetable oils according to the concept of Nikolaj Prileschajew, implying in situ prepared percarboxylic acids as epoxidation agents. The model considers intra- and interfacial mass transfer effects coupled to reaction kinetics. The liquid phases were described with chemical approach (aqueous phase) and a reaction–diffusion approach (oil phase). The oil droplets were treated as rigid spheres, in which the overall reaction rate is influenced by chemical reactions and molecular diffusion. The model was tested with a generic example, where two reactions proceeded simultaneously in the aqueous and oil phases. The example (i.e., fatty acid epoxidation) illustrated the power of real multiphase model in epoxidation processes. The proposed modeling concept can be used for optimization purposes for applications, which comprise a complex water–oil–solid catalyst system.