过氧化氢一步法制备环氧亚麻油工艺

报道了亚麻油在以石油醚为溶剂、磷酸为催化剂的条件下,经甲酸、双氧水环氧化,一步合成增塑剂———环氧亚麻油的一种新方法。该法反应条件温和,操作方法简单,反应时间较短,而且产物各项指标均可达到增塑剂标准:环氧值>7.8,碘值<10,酸值<0.5。     

环氧亚麻油在聚氯乙烯塑料中热稳定性试验

通过环氧亚麻油和环氧大豆油在聚氯乙烯中的静态、动态热稳定性对比,证实环氧亚麻油不仅可替代环氧大豆油,而且制品有更好的透明性、增塑效果,与钙/锌复合稳定剂的协同效应更佳。     

国内信息

环氧亚麻油研制成功 环氧亚麻油是江苏金龙集团公司化工技术开发部最近研制成功的塑料增塑剂。环氧亚麻油环氧值达到 8.0以上,由于其环氧值高,因此与PVC相溶性好,可作主增塑剂使用(增塑效率值低于 DOP,大约为77％左右)。经上海塑料一厂试用,确认该产品完全     

环氧亚麻油的制备工艺研究

通过单因素实验方法催化合成了环氧亚麻油,以产品环氧值为考察指标,研究了催化剂种类、反应时间、催化剂用量、甲酸用量、双氧水用量、反应温度对反应的影响.结果表明,以硫酸为催化剂,反应时间8 h,反应温度为65℃,反应物料质量比m(亚麻油):m(甲酸):m(硫酸):m(双氧水)=1:0.06:0.0015:0.65,硫酸0....     

氧化-磷酸酯化亚麻油加脂剂的制备及其作用机理

以亚麻油、过氧化氢为原料,合成了环氧值分别为1.16、1.52和2.32mmol/g的3种环氧亚麻油,再与定量的磷酸进行酯化反应,合成了3种结合型氧化-磷酸酯亚麻油皮革加脂剂LCF-P1、LCF-P2和LCF-P3。将其应用于皮革加脂,探究了不同环氧化程度对氧化-磷酸酯化皮革加脂剂的加脂性能影响,并与市售磷酸酯加脂剂进行了加脂效果对比。用SEM观察了皮革加脂前后断面胶原纤维形貌变化。结果表明,环氧值1.52mmol/g的加脂剂LCF-P2表现出良好的加脂性能,加脂后坯革柔软度达10 mm,抗张强度为35.91 N/mm2,撕裂强度为49.56N/mm,皮革增厚率为24.36%。加脂剂LCF-P2在皮革增厚率、机械强度提高方面略优于市售磷酸酯加脂剂。     

文摘与题录

活性炭固载磷钨酸催化合成柠檬酸三丁酯,过氧化氢一步法制备环氧亚麻油工艺,新型增塑剂NPBIB的合成,固体超强酸在增塑剂合成中的应用,乙酰柠檬酸三丁酯的催化合成[编者按]     

氧化-磷酸酯化亚麻油加脂剂制备及作用机理

以亚麻油、过氧化氢为原料，首先合成了环氧值分别为1.16mmol/g、1.52mmol/g和2.32mmol/g三种环氧亚麻油，再与定量的磷酸进行酯化反应，合成了LCF-P1、LCF-P2和LCF-P3三种结合型氧化-磷酸酯亚麻油皮革加脂剂。将其应用于皮革加脂，探究了不同环氧化程度对氧化-磷酸酯化皮革加脂剂的加脂性能影响，并与市售磷酸酯加脂剂进行了加脂效果对比；用扫描电镜(SEM)观察了皮革加脂前后断面胶原纤维形貌变化。实验结果表明：环氧值为1.52mmol/g的加脂剂LCF-P2表现出良好的加脂性能，加脂后皮革柔软度达10mm，抗张强度为35.91 N/mm2, 撕裂强度为49.56 N/mm，皮革增厚率为24.36%，在皮革增厚率、机械强度提高方面略优于市售磷酸酯加脂剂。     

亚麻油催化异构化改性研究（I）

以负载型镍催化剂以亚麻油的双键异构化进行了研究，获得了催化剂最佳配方及制备条件。确定了亚麻油异构化的最佳工艺参数，在此条件下，异构化亚麻油的共轭三烯键可达百分之十二，异构化亚麻油涂膜的干性，耐水，耐化学试剂性能均优于“双漂”亚麻油。     

亚麻油改性不饱和聚酯树脂合成工艺研究

研究了采用亚麻油改性的双环戊二烯型不饱和聚酯树脂的合成工艺。实验表明,其最佳反应条件为:一次性混合投料,加成反应温度124℃,反应时间2h,n(饱和酸)∶n(不饱和酸)为7∶93,亚麻油用量为0 06mol。应用上述工艺条件合成的树脂具有良好的气干性、柔韧性。     

二聚酸甲酯的合成研究

以亚麻油经醇解反应得到的亚麻油脂肪酸甲酯为原料,在催化剂存在下,用间歇常压聚合法,合成了二聚酸甲酯。用正交试验设计考察了反应温度,催化剂用量,反应时间对二聚反应产物收率的影响,找到了最佳反应条件。     

Synthesis and photopolymerization of norbornyl epoxidized linseed oil

Norbornyl epoxidized linseed oil was synthesized via Diels-Alder reaction of cyclopentadiene with linseed oil at high pressure (∼200 psi) and high temperature (240 °C), followed by an epoxidation using hydrogen peroxide with a quaternary ammonium tetrakis(diperoxotungsto) phosphate(3−) epoxidation catalyst. The products were characterized using ¹H and ¹³C NMR, FT-IR, and electrospray ionization mass spectroscopy. Photo-induced curing kinetics of norbornyl epoxidized linseed oil coatings was investigated using real-time FT-IR spectroscopy with a fiber optic UV-curing system. The norbornyl epoxidized linseed oil was formulated with three different divinyl ether reactive diluent. The effect of divinyl ether concentration and types of divinyl ether on the curing reaction was investigated. It was found that the curing rate of norbornyl epoxidized linseed oil was lower than that of cycloaliphatic epoxide, but higher than epoxidized linseed oil. The incorporation of divinyl ethers increased the curing rate and overall conversion of the epoxide groups. Of the three divinyl ethers used, coating with triethyleneglycol divinyl ether showed the highest curing rate and coating with cyclohexane dimethanol divinyl ether showed the lowest curing rate.     

Polymerization of linseed oil in an electric discharge

Summary The treatment of linseed oil by the action of electric discharges (voltolization) in a hydrogen atmosphere (80 mm. Hg, 70°C.) is described. It has been known for a long time that voltolization of linseed oil brings about a polymerization of the oil. Now it has been proven that the nature of the polymerization product thus obtained is absolutely different from that of thermally or catalytically polymerized linseed oils. In contrast to the latter, voltolized linseed oils contain only small amounts of cyclic compounds. Their viscosity is relatively low, even at a high polymerization degree, and considerably less than that of thermally polymerized oils of a corresponding degree of polymerization. Atomic hydrogen seems to play an important part in the voltolization process. Coupling of fatty acid chains is made possible by combining radicals, formed primarily by the action of hydrogen atoms. Coupling reaction occurs almost exclusively intermolecularly. The possibility of transforming linseed oil and other drying oils into polymerization products of a completely different chemical structure, depending on the applied polymerization process, opens new possibilities for their manufacture. Compare T. Hoekstra, Thesis, Delft 1958 (in Dutch).     

Stand reaction of linseed oil

Several theories have been proposed concerning the stand oil reaction but no precise reaction scheme has been described. In this work, the stand reaction of linseed oil was characterized in order to determine the nature of the products formed during this reaction. Using complementary analytical techniques (more especially NMR and mass spectrometry), the existence of two different reactions was demonstrated: the Diels–Alder addition between fatty acid chains and the addition of a methylene radical on double bonds, followed by combination or elimination reactions.     

Production of linolenic acid from linseed oil

Linolenic acid of more than 95% purity was produced by liquid-liquid extraction of linseed oil fatty acids with wet furfural and hexane in a Podbielniak centrifugal extractor. The minimum ratio of furfural to linseed acids to obtain this purity was 10 to 1. There was no significant change in product purity for solvent ratios between 10 and 15, operating temperatures from 90° to 110°F., and furfural moisture contents between 1.0 and 2.8%. When the solvent ratio is reduced to 8 or the furfural moisture to 0.2%, purity decreases. Oxidation of linseed acids before extraction also results in decreased separation. An estimate based on pilotplant data indicates a “cost to make” (excluding administrative and selling expenses, profit, income taxes, and interest on investment) of 18.0 cents per pound of 97% linolenic acid for a process which includes hydrolyzing linseed oil, separating the fatty acids by liquid-liquid extraction, recovering solvents by distillation, and distilling the fatty acid products. Potential uses for linolenic acid are reviewed.     

Studies on zinc-containing linseed oil based polyesteramide

For the first time the synthesis of zinc containing linseed oil based polyesteramide resins (Zn-LPEA-1 to Zn-LPERA-5) with different loadings of zinc acetate were carried out by in situ condensation polymerization reaction between linseed oil derived linseed fattyamide diol (HELA), phthalic anhydride and zinc acetate (divalent metal salt, different mole ratios) in the absence of any solvent. By-products such as water and acetic acid were removed by the application of vacuum technique. This approach was employed to overcome the use of volatile organic solvents [VOCs] during processing and application of the resin, that are ecologically harmful. The structure of the resin was confirmed by FT IR, ¹H NMR and ¹³C NMR spectral studies. Physico-chemical properties were studied by standard methods. Thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC) was used to measure the thermal behaviour of the resin. The antibacterial studies of Zn-LPEA resins were carried out by agar diffusion method. Antibacterial activities of Zn-LPEA were compared with reported virgin linseed polyesteramide (LPEA) and zinc incorporated petroleum based polymers.     

Styrenation of castor oil and linseed oil by macromer method

In this study a novel macromer technique has been described for the styrenation of triglyceride oils. Macromers were prepared through the interesterification of castor oil with linseed oil followed by esterification with acrylic acid. In this preparation various castor oil/linseed oil ratios were applied to obtain a macromer which gave a copolymer with good film properties after copolymerization with styrene. Macromers were styrenated at 100°C using benzoyl peroxide as an initiator. The styrenation leads to improved film properties with the related interesterification product although castor oil is a non‐drying oil.     

The triglyceride composition of linseed oil

The triglyceride composition of linseed oils obtained under different ecological conditions and having different fatty acid compositions was determined by a combination of several chromatographic techniques. The triglyceride mixture was first separated in 8 fractions of different polarity by reversed-phase paper chromatography. Each glyceride fraction was then separated in a partition chromatographic system as the triglyceride coordination complexes with silver ions into individual compounds. The fatty acid compositions of the original oil, single glyceride fractions, and individual triglycerides were determined by gas-liquid chromatography. The molar ratio between the two neighboring glyceride fractions was determined by relating the fatty acid composition of each fraction to the fatty acid composition of their sum. The triglyceride composition of the total oil was then calculated from these results. The presence of 18–19 triglycerides was ascertained in the samples studied, and the molar concentration of each glyceride was estimated. Linseed oil contains only triunsaturated and monosaturated-diunsaturated triglycerides. Within each of these types the fatty acid distribution is close to random. At the same time, the content of some triglycerides departed regularly from a random pattern. A method for calculation of linseed oil triglyceride composition from the fatty acid composition is given. The same general pattern of glyceride formation in linseed is followed regardless of ecological conditions; therefore, the qualitative and quantitative triglyceride composition reflects the differences in fatty acid composition of linseed oil.     

Partial hydrogenation of linseed oil by a continuous process

Summary Alkali refined linseed oil was partially hydrogenated, using both continuous and batch processes. The continuous process was carried out in a series of Votator machines, using Rufert nickel catalyst, presures up to 145 psig. and temperatures up to 400°F. The continuous hydrogenation of linseed oil under the most selective conditions possible, using the Votator equipment, shows little selectivity between the linolenic and linoleic acid radicals. A pronounced selectivity is observed between oleic and the more unsaturated acid radicals. Under selective conditions of hydrogenation of linseed oil about 31% of the hydrogenated linolenic acid radical is transformed into 9–15 linoleic acid while the remainder of the linolenic acid goes to oleic acid in either one or two steps. Batch hydrogenation yields oils of superior nonyellowing characteristics over comparable oils prepared by the continuous process. The hydrogenated linseed oils were tested in both clear and pigmented alkyds where they displayed superior non-yellowing characteristics over the original linseed oil and, in many instances, over that of soya bean oil. The yellowing of oils and alkyds appears to be a function of both 1) the quantity of fatty acids more unsaturated than oleic present in the oil and 2) the ratio of the quantity of linolenic acid radicals to linoleic acid radicals present. Presented at 21st fall meeting, American Oil Chemists' Society, Chicago, Oct. 20–22, 1947.     

Cyclic fatty acid yields from linseed oil

Increased yields of saturated cyclic fatty acids which are fluid at −50C have been obtained from linseed oil. Depending on reaction conditions, yields varied from 20–42 g of cyclic acids per 100 g of linseed oil. Solvent ratios of 6, 3, and 1.5∶1; catalyst concentrations of 10, 30, 60, and 100%; and reaction temps of 225, 275, 295, and 325C were evaluated. Ethylene glycol and diethylene glycol were compared as reaction solvents. In general, high solvent ratios favored high cyclic acid yields at the lower reaction temperature, but as the temperature increased the effect of solvent ratio decreased. Increasing the percentage excess of sodium hydroxide increased the cyclic acid yield. Diethylene glycol gave higher yields than ethylene glycol at comparable conditions. Presented at the AOCS meeting in Chicago, Ill., October, 1961. A laboratory of the No. Utiliz. Res. & Dev. Div., ARS, U.S.D.A.