Diels-alder adducts from safflower oil fatty acids: I. Maleic anhydride as dienophile

The Diels-Alder reaction between alkali conjugated and elaidinized safflower oil fatty acids and maleic anhydride was studied under various experimental conditions. The principal product which was obtained in 51–55% yields was a mixture of the adduct of maleic anhydride and maleic acid in 40∶60 proportions. The isolation and properties of this mixed adducts from the reaction mixture and their conversion to trimethyl, tributyl and triallyl esters are described. The trimethyl ester was also obtained in good yield from the methyl esters of the fatty acids and dimethyl maleate.     

Production of alkenyl succinic anhydrides from low‐erucic and low‐linolenic rapeseed oil methyl esters

Fatty acid methyl esters from low‐erucic and low‐linolenic rapeseed oil were used to produce alkenyl succinic anhydrides. A second‐order Doehlert uniform network design was used to investigate the influence of the reaction temperature and the molar ratio between the maleic anhydride and the main unsaturated rapeseed oil methyl esters on the yield of alkenyl succinic anhydride from methyl oleate. Further subjects of investigation were the conversion of methyl oleate, the formation of side reaction products, the Gardner color of the product and its viscosity, and finally the content of maleic anhydride remaining in the medium after the reaction. Alkenyl succinic anhydride from methyl oleate was isolated by column chromatography and analyzed by IR, ¹H‐ and ¹³C‐NMR and MS. The optimal reaction conditions for obtaining the maximum yield of alkenyl succinic anhydride from methyl oleate in the experimental domain (80%) were 210‐220 °C and a maleic anhydride/rapeseed oil methyl ester molar ratio of 1.5. However, the products synthesized in these conditions showed a high degree of viscosity (0.45 kg m^?1 s^?1), a very dark color (18 Gardner color) and a high content of undesirable side products (6%), which could hinder their industrial use. A molar ratio of less than 1.5 led to a clearer and less viscous product, although with a lower alkenyl succinic anhydride content.     

Characteristic properties of cutting fluid additives derived from the reaction products of hydroxyl fatty acids with some acid anhydrides

Several adducts were prepared from the thermal reaction of hydroxyl fatty acids (ricinoleic acid oligomers, 12-hydroxystearic acid oligomers, oleyl alcohol, dehydrated castor oil fatty acids, and dimer acid) with maleic anhydride and screened as water-soluble cutting fluids. For example, aqueous solutions of triethanolamine salts with the products of ricinoleic acid oligomers, 12-hydroxystearic acid dimer, and 12-hydroxysteric acid hexamer showed good antirust properties for waterbased cutting fluids. Various half esters of hydroxyl fatty compounds with acid anhydrides were prepared. Aqueous solutions of triethanolamine salts of half esters of maleic anhydride and succinic anhydride and phthalic anhydride with hydroxyl fatty acids gave good antirust and antiwear properties for waterbased cutting fluids.     

Preparation of alkenyl succinic anhydrides from vegetable oil FAME

Sunflower oil and oleic motif-enriched sunflower oil methyl esters were used to prepare alkenyl succinic anhydrides. A classic batch reactor was selected to carry out the synthesis. The range in which the temperature, reaction time, and molar ratio between the number of moles of maleic anhydride and the equivalent number of double bonds present in the unsaturated vegetable oil methyl esters (the most influential factors in the process) varied was determined in a preliminary study. A secondorder Doehlert uniform network design was used to investigate the influence of the temperature and molar ratio for all the methyl esters on the yield of alkenyl succinic anhydride from methyl oleate, the conversion of methyl oleate, the formation of side reaction products, the Gardner color of the product, and viscosity. The optimal reaction conditions for obtaining the maximal yield (around 95%) of alkenyl succinic anhydride from methyl oleate were 235°C, a molar ratio of 1.5, and a reaction lasting 8 h. However, the products synthesized under these conditions showed high viscosity (215 cP), a very dark color (18+ Gardner color), and a high content of undesirable side products (4%), which hindered their direct industrial use. The increase in the product viscosity was probably due to the formation of side reaction products. A molar ratio of less than 1.5 led to a less viscous product, although with a lower alkenyl succinic anhydride content.     

Grafting maleic anhydride and comonomers onto polyethylene

Grafting dicarboxylic anhydrides onto polyolefins has great practical importance. The process of grafting maleic anhydride onto high-density polyethylene in the presence of various comonomers in an intermeshing corotating twin-screw extruders was studied. Three types of comonomers were investigated: (i) vinyl monomers, including styrene and methacrylic acid; (ii) esters of dicarboxylic acids forming succinic groups after grafting, such as fumaric acid; and (iii) esters of fumaric and maleic acid and ethylenically unsaturated cyclic dicarboxylic anhydrides, such as Diels–Alder adducts of maleic anhydride; and (iv) dienes and dodecenyl succinic anhydride. © 1995 John Wiley & Sons, Inc.     

Improvements of fiberboard properties through fiber activation and subsequent copolymerization with vinyl monomer

High-temperature refined thermomechanical pulp (MDF fiber) was dried, extracted with neutral organic solvent, and reacted with three types of electrophilic reagents (glycidyl methacrylate, maleic anhydride, and succinic anhydride). The adducts formed were further reacted in a hot press with a vinyl monomer in the presence of a free-radical initiator (benzoyl peroxide). Well-conformed boards were produced by the process. Modified boards showed significant improvement in thickness swelling as well as in strength properties compared to control phenol–formaldehyde boards. Glycidyl methacrylate modified/methyl methacrylate boards were the most stable toward the wet-and dry-exposure cycles, whereas succinic anhydride/methyl methacrylate boards showed the lowest water absorption. © 1994 John Wiley & Sons, Inc.     

丁二酸酐性能及各种生产工艺介绍

丁二酸酐是一种重要的精细化工原料,用途广泛,尤其它的衍生物更是附加值高的精细化工产品,全球丁二酸酐的生产工艺主要有丁二酸脱水法、顺丁烯二酸酐催化加氢法。本文章主要介绍了丁二酸酐的性能、用途和生产工艺技术,并对生产工艺技术进行了比较,顺丁烯二酸酐熔融催化加氢法由于生产成本和综合能耗较低,是最具竞争力,发展前景看好的一种方法。     

聚异丁烯丁二酰亚胺合成新工艺

采用络合Ｆ－Ｋ酸作引发剂进行异丁烯阳离子聚合。在过量马来酸酐存在的情况下，与异丁烯低聚物进行热反应，再在引发剂的作用下进行自由基共聚合。将得到的聚异丁烯丁二酸酐与多烯多胺反应得到活性物含量达９５％的最终产品。实验考察了浓度、温度和时间对各步反应影响，确定了最佳工艺条件。     

Kinetics and Mechanism in the Liquid-Phase Hydrogenation of Maleic Anhydride and Intermediates

The influence of zinc oxide on the kinetics and mechanism of the liquid-phase hydrogenation of maleic anhydride (MA) and intermediates was investigated on copper-based catalysts. No influence of zinc oxide on the hydrogenation of maleic anhydride was observed in previous experiments. The discontinuous hydrogenation of succinic anhydride (SA) resulted in the formation of γ-butyrolactone (γ-BL) and 1,4-butanediol (1,4-BD) on a copper/zinc catalyst. On a zinc-free copper catalyst only γ-butyrolactone was formed while the hydrogenation of γ-butyrolactone to 1,4-butanediol was inhibited. It was observed that succinic anhydride which is adsorbed on the copper surface of the catalyst prevents the adsorption of γ-butyrolactone. On copper/zinc catalysts the reversible adsorption of succinic anhydride on the inactive zinc oxide crystallites, which led to a reversible decrease of the carbon balance, is responsible for a decrease of the succinic anhydride coverage of the copper sites. It appears that the decrease of the succinic anhydride coverage of the copper surface is proceeding by surface diffusion of succinic anhydride to the adjacent zinc oxide crystallites. On this basis two different reaction pathways via succinic anhydride adsorbed on the copper surface and via succinic anhydride adsorbed on the zinc oxide crystallites were proposed for the hydrogenation of maleic anhydride and intermediates. Kinetic modeling of the reaction pathway taking into account both reaction pathways led to good agreement of calculated and experimental results.     

改性骨架镍催化马来酸酐加氢制备琥珀酸酐

将骤冷法制备的改性骨架镍用于马来酸酐(MA)的催化加氢,可在温和条件下高选择性地制备琥珀酸酐(SA)。考察了不同反应参数对该反应的影响,当采用1,4-二氧六环为溶剂,在0.2MPa和30℃的温和条件下反应60min,马来酸酐的转化率和琥珀酸酐的选择性均可达到100%。在上述条件下,该反应表现为零级反应,其表观活化能为27.1kJ/mol。     

Reaction of Maleic Anhydride with cis-Isolated Unsaturated Fatty Acid Esters

The structures of maleic anhydride adducts of essentially pure oleic, linoleic and linolenic methyl esters have been determined. The cleavage of the methyl oleate adduct yields a product with a succinyl structure, with or without shift of the double bond; four isomeric structures are possible. The first adduct of maleic anhydride with methyl linoleate is a succinyl derivative followed by a shift into the conjugated isomer with which the second maleic anhydride reacts via a 1–4 Diels Alder addition to yield a second adduct having a cyclohexene structure. The first two moles of maleic anhydride add to methyl linolenate to form di-succinyl derivatives followed by a shift into conjugated diene and triene. The third maleic anhydride adds via a 1–4 addition to yield a disuccinyl and one 1–4 adduct. A number of isomers are possible for the linoleate and linolenate adduct.     

Autoxidation of fats. II. Preparation and oxidation of methyl oleate-maleic anhydride adduct

Summary The adduct of maleic anhydride and methyl oleate has been prepared and characterized. The physical and chemical properties of the adduct indicate that it is composed of one mole of each of the reactants and that the double bond of methyl oleate has not been saturated. Oxidative fission of the adduct showed that the adduct consisted of a mixture of four isomers which yielded octanoic, nonanoic, suberic, and azelaic acids on ozonolysis. Isolation of these four acids from the fission products indicates that the addition reaction probably proceeds by a mechanism analogous to that proposed by Farmer, Koch, and Sutton for autoxidation. In view of the similarity between the reactions of maleic anhydride and oxygen with unsaturated compounds, the foregoing observations appear to support the free radical chain mechanism for the autoxidation of fats. One of the laboratories of the Bureau of the Agricultural and Industrial Chemistry Agricultural Research Administration, U. S. Department of Agriculture.     

甲基乙烯基醚/马来酸酐共聚物合成研究

以过氧化十二酰为引发剂(IN),采用溶液自由基共聚合方法,实现了甲基乙烯基醚(MVE)与马来酸酐(MAN)的交替共聚合。通过详细研究反应温度、引发剂用量、溶剂配比、溶剂用量及反应时间等因素对共聚物产率及产品特性粘度的影响,优化了制备甲基乙烯基醚/马来酸酐共聚物的工艺条件。最后通过FTIR和13CNMR表征了共聚物的结构。     

顺酐液相加氢制备丁二酸酐

一步法顺酐加氢生产丁二酸酐的最佳条件为:加氢压力1~1.6 MPa,反应温度50~100℃,反应时间1~2 h,骨架镍催化剂用量是顺酐用量的4%~6%,搅拌速度300 r/m in,在此条件,丁二酸酐的最高收率可达90%以上。     

Zur Kenntnis der Wachsbaustein des Montanwachses II: Hydroxysäuren

Constituents of Montan Wax II: Hydroxy Acids The group of hydroxy acids which occur in a large number of natural waxes as condensing component of the ester wax part were found in Montan wax as well and were studied closely. The methyl esters of the total acids were treated with succinic anhydride and the resulting hydrogen succinates of the methyl esters of hydroxy acids separated by means of an anion exchanger.     

Miscibility characterization of SMA/SAN and SMA/PMMA blends by differential scanning calorimetry and fluorescence techniques

In this study, styrene‐maleic anhydride (SMA) copolymer was modified by monoesterification method with 9‐(hydroxymethyl)anthracene fluorophore to prepare a fluorescent anthracene labeled SMA (SMA‐An) material. The latter was then characterized by attenuated total reflection (ATR) and thermogravimetric analysis (TGA) techniques. In the second step of this work, SMA‐An was added to SMA/[Styrene‐Acrylonitrile Copolymer (SAN)] and SMA/[Poly(methyl methacrylate) (PMMA)] blends to investigate the miscibility of these blends at the molecular level. The miscibility of SMA/PMMA blends was characterized using fluorescence quenching of anthracene by the succinic anhydride and succinic acid functions on SMA macromolecule itself. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

琥珀酸双酯磺酸钠类反应型表面活性剂的合成

马来酸酐经单酯化、O-烷基化、选择性磺化反应得到了琥珀酸双酯磺酸钠类表面活性剂。马来酸酐与脂肪醇在90℃下反应3 h得到马来酸单酯;在碳酸钠、Et3N和CH3COCH3存在下,单酯与丙烯基氯(50℃)或异丁烯基氯(65℃)反应6 h得到马来酸双酯;双酯与亚硫酸氢钠在120℃下反应3 h得到目标产物。产物经1HNMR和IR表征,符合结构特征。     

无皂微乳液聚合制备加脂型复鞣剂

采用甲基丙烯酸甲酯、丙烯酸丁酯、二乙烯基苯、丙烯酸、反应型乳化剂马来酸酐十二醇单酯钾盐和助乳化剂正戊醇制备得到无皂微乳液。通过正交实验优化出了反应型乳化剂的最佳合成条件:n(马来酸酐):n(十二醇)=1.15:1,反应温度80℃,反应时间3 h,制备出反应型乳化剂———马来酸酐十二醇单酯钾盐,代替外乳化剂十二烷基硫酸钠,进行无皂微乳液聚合制备具有增强作用的加脂型复鞣剂。将制得的加脂型复鞣剂用于猪二层革的复鞣实验,结果表明,反应型乳化剂与混合单体(丙烯酸丁酯、甲基丙烯酸甲酯和二乙烯基苯)的质量分别为120 g和180 g,活性单体丙烯酸质量为10 g时对皮革的复鞣效果最好。成革的物理机械性能得到了提高,其横向撕裂强度提高58.8%,纵向撕裂强度提高37.4%,崩破强度提高54.1%。     

Fettpolymere – Herstellverfahren und Eigenschaften

The radical polymerization of esters of acrylic, methacrylic or crotonic acid with fatty alcohols proved to be an efficient method for production of polymers with hydrophobic moieties. By co-polymerisation with hydrophilic co-monomers - such as maleic anhydride - copolymers with a broad spectrum of properties can be designed. As an example the copolymerisation of fatty crotonates with maleic anhydride was studied in detail. The reaction was carried out as bulk polymerisation in a semi-batch process. By this method the compatibility problems of the two monomers, which have very different hydrophilicities could be overcome. The product acts as a very effective fat liquoring agent in leather treatment: the maleic moieties cause an outstanding fixing of the agent on the leather and the fatty crotonate moieties create a very smooth leather. Terpolymers of fatty acrylates, hydrophilic monomers and terpenes could also be synthesized in a similar way. These terpolymers proved to be useful as dispersing agents for pigments in paints and varnishes.     

Polymeric additives for pour point depression of residual fuel oils

Esters of styrene-maleic anhydride copolymers were synthesised by reacting styrene with maleic anhydride and esterifying the product with fatty alcohols. The resulting copolymers were purified and tested as pour point depressants for residual fuel oils. Comparative evaluation of these esters of styrene-maleic anhydride copolymers with some commercial additives showed their good activity.