KR970007143B1 - Process for the epoxidation of soybean oil - Google Patents
Process for the epoxidation of soybean oil Download PDFInfo
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- KR970007143B1 KR970007143B1 KR1019950020213A KR19950020213A KR970007143B1 KR 970007143 B1 KR970007143 B1 KR 970007143B1 KR 1019950020213 A KR1019950020213 A KR 1019950020213A KR 19950020213 A KR19950020213 A KR 19950020213A KR 970007143 B1 KR970007143 B1 KR 970007143B1
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- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23D—EDIBLE OILS OR FATS, e.g. MARGARINES, SHORTENINGS, COOKING OILS
- A23D9/00—Other edible oils or fats, e.g. shortenings, cooking oils
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Abstract
Description
본 발명은 대두유의 불포화 지방산 이중결합에 에폭시기를 부가하는 에폭시화 대두유의 제조방법에 관한 것이다. 좀 더 상세하게 본 발명은 대두유의 불포화 지방산 이중결합에 과산화수소의 포름산의 혼합용액에서 얻은 과포름산과 인산촉매를 첨가하여 에폭시화 대두유를 제조하는 에폭시화 대두유의 제조방법에 관한 것이다.The present invention relates to a method for producing epoxidized soybean oil by adding an epoxy group to an unsaturated fatty acid double bond of soybean oil. In more detail, the present invention relates to a method for producing epoxidized soybean oil, wherein epoxidized soybean oil is prepared by adding perforic acid and a phosphate catalyst obtained from a mixed solution of formic acid of hydrogen peroxide to an unsaturated fatty acid double bond of soybean oil.
대두유는 리놀렌산계 유지로서 불포화 지방산을 85∼92%로 다량 함유하고 있다. 이 불포화 지방산은 강한 무기산 촉매하에 포름산과 과산화수소로부터 반응시켜 경제적인 에폭시화물을 얻을 수 있다.Soybean oil is a linolenic acid-based fat or oil containing a large amount of unsaturated fatty acid (85-92%). These unsaturated fatty acids can be reacted from formic acid and hydrogen peroxide under a strong inorganic acid catalyst to obtain economical epoxides.
일반적으로 에폭시화 대두유는 폴리염화비닐 제조시 첨가제로 사용되며, 이를 첨가하므로서 우수한 열안정성 및 가소성을 가진 폴리염화비닐을 제조할 수 있다. 그래서, PVC 바닥 장식재, 벽지, 레자, 씨트 및 농약, 도료, 접착제, 유기 화합물의 제조시 사용될 수 있다. 또한, 에폭시화 대두유는 무독성이고 열안정성 및 광안정성이 뛰어나기 때문에 음식물 포장용 푸드 랩(Food Wrap)등 식품저장 용기의 제조에 첨가제로 사용된다.In general, epoxidized soybean oil is used as an additive in the production of polyvinyl chloride, and polyvinyl chloride having excellent thermal stability and plasticity can be prepared by adding it. Thus, it can be used in the production of PVC floor coverings, wallpaper, leather, sheets and pesticides, paints, adhesives, organic compounds. In addition, epoxidized soybean oil is used as an additive in the manufacture of food storage containers such as food wraps because of its non-toxicity and excellent thermal stability and light stability.
에폭시계 가소제로는 에폭시화 대두유, 저분자량 에폭시수지, 에폭시화 아미유가 있으나, 에폭시화 대두유가 불포화 지방산의 함량이 많아 주로 사용되고 있다. 또한, 에폭시화 대두유를 첨가제로 사용하면, 필름등의 생성물질에 존재하거나 또는 그 물질들의 열하의 원인이 되는 염산과 같은 불필요한 산을 매우 효과적으로 제거할 수 있다.Epoxy plasticizers include epoxidized soybean oil, low molecular weight epoxy resin, and epoxidized amine oil, but epoxidized soybean oil is mainly used because of its high content of unsaturated fatty acids. In addition, when epoxidized soybean oil is used as an additive, it is possible to effectively remove unnecessary acids such as hydrochloric acid present in a product such as a film or causing heat of the materials.
미국 특허 제2,458,160호에는 불포화 지방산 에스테르를 이용한 에폭시화 지방 화합물의 제조방법이 기재 되어 있다. 이 방법은 초산, 포름산, 과산화수소 및 유기 용매로서 탄화수소(n-헵탄,n-헥산), 방향족 탄화수소(크실렌,벤젠,톨루엔)등을 사용하고 있다. 그러나, 이 방법은 초산과의 반응성이 떨어지며 또한 유기 용매의 사용으로 인해 비경제적이고, 위험하며 안정성이 떨어진다는 문제점이 있었다. 이 특허에 의해 제조된 생성물의 옥시란 함량(Oxirane content)은 약 6.0% 정도였다.U.S. Patent No. 2,458,160 describes a process for preparing epoxidized fatty compounds using unsaturated fatty acid esters. This method uses acetic acid, formic acid, hydrogen peroxide and hydrocarbons (n-heptane, n-hexane), aromatic hydrocarbons (xylene, benzene, toluene) as organic solvents. However, this method has a problem that the reactivity with acetic acid is less, and because of the use of organic solvents, it is uneconomical, dangerous and poor in stability. The oxirane content of the product produced by this patent was about 6.0%.
미국 특허 제2,801,253호에는 황산 및 아세트산으로 유기 에스테르를 에폭시화하는 방법이 기재되어 있다. 이 발명은 초산, 황산 및 과산화수소를 사용한 제조방법으로서, 이 제조방법에서는 촉매로 황산을 사용했으나 높은 산도로 인해 반응이 불균일하게 일어나며 또한 반응후의 에폭시화물이 분해된다는 문제점이 있었다. 이 특허에 의해 제조된 생성물의 옥시란 콘텐트는 약 5.75% 정도였다.US Pat. No. 2,801,253 describes a process for epoxidizing organic esters with sulfuric acid and acetic acid. The present invention is a manufacturing method using acetic acid, sulfuric acid and hydrogen peroxide. In this manufacturing method, sulfuric acid was used as a catalyst, but there was a problem in that the reaction occurred unevenly due to high acidity and decomposition of the epoxide after the reaction. The oxirane content of the product produced by this patent was about 5.75%.
일본 공개특허공보 제61-161273호에는 올레핀성 불포화 탄화수소계 화합물의 에폭시화 방법이 기재되어 있다. 이 공개특허공보에는 상압에서 초산, 과산화수소를 사용한 제조방법으로서, 반응효율이 낮으며, 과초산 생성을 위해 이온교환수지를 사용하므로, 원료재생이 어렵다는 문제점이 있었다. 이 특허에 의해 제조된 생성물의 옥시란 함량은 약 6.62% 정도였다.Japanese Laid-Open Patent Publication No. 61-161273 describes a method for epoxidation of an olefinically unsaturated hydrocarbon compound. This publication discloses a method of using acetic acid and hydrogen peroxide at normal pressure, having low reaction efficiency, and using ion exchange resins to produce peracetic acid, thus making it difficult to regenerate raw materials. The oxirane content of the product produced by this patent was about 6.62%.
본 발명은 상기에서 언급한 종래의 에폭시화 방법보다 훨씬 낮은 생성물의 요오드값을 제공한다. 즉, 대두유에 존재하는 불포화 지방산 이중결합 (C=C)을 식으로 표시되는 옥시란 그룹, 즉 에폭시기를 함유하는 생성물로 반응시키므로서, 대두유내의 이중결합수를 상당히 감소시키며 따라서, 생성물의 요오드값은 낮아지고 대두유의 산소함량은 증가되는 에폭시화 반응을 효율적으로 진행시키는 에폭시화 반응이다.The present invention provides a much lower iodine value of the product than the conventional epoxidation process mentioned above. That is, the unsaturated fatty acid double bond (C = C) present in soybean oil By reacting with an oxirane group, i.e., a product containing an epoxy group, the number of double bonds in the soybean oil is considerably reduced, and thus the epoxidation reaction proceeds efficiently in which the iodine value of the product is lowered and the oxygen content of the soybean oil is increased. Is an epoxidation reaction.
따라서, 본 발명은 종래의 문제점을 해소하기 위하여 이루어진 것으로써, 본 발명의 목적은 제조코스트가 저렴하며, 제조공정이 간단하고 반응시간이 짧으며 또한 반응효율이 높은 자연 생분해성의 무독한 에폭시화 대두유의 제조방법을 제공하기 위한 것이다.Accordingly, the present invention has been made to solve the conventional problems, and an object of the present invention is a low cost of production, a simple manufacturing process, a short reaction time, and high reaction efficiency. It is to provide a method of manufacturing.
상기 목적을 달성하기 위하여 본 발명은 다량의 불포화 지방산을 함유한 대두유를 과산화수소와 포름산의 혼합용액에서 얻은 과포름산과 인산촉매 존재하에서 반응시켜 에폭시화 대두유를 제조하는 것이다.In order to achieve the above object, the present invention is to prepare epoxidized soybean oil by reacting soybean oil containing a large amount of unsaturated fatty acid in the presence of perforic acid and phosphoric acid catalyst obtained from a mixed solution of hydrogen peroxide and formic acid.
상세하게 설명하면, 본 발명은 온도계, 환류냉각기 및 교반기가 부착된 4구 플라스크에 대두유를 투입하고 서서히 교반하면서 약 70℃로 가열한 후 포름산을 상기 플라스크내에 30분∼1시간에 걸쳐 서서히 적하하면서 동시에 과산화수소와 인산의 혼합용액을 플라스크내에 1시간∼5시간에 걸쳐 서서히 적하하면서 상기 온도를 계속 유지하고, 10시간 동안 반응시킨 후, 유기층을 분리하여 pH가 중성이 될때까지 수세한 후 감압 건조, 여과하여 에폭시화 대두유를 제조하는 것을 특징으로 한다.In detail, the present invention, while the soybean oil is added to a four-necked flask equipped with a thermometer, a reflux condenser and a stirrer and heated slowly to about 70 ℃ while stirring slowly dropping formic acid into the flask over 30 minutes to 1 hour At the same time, the mixed solution of hydrogen peroxide and phosphoric acid was slowly added dropwise into the flask over 1 hour to 5 hours, and kept at the above temperature, reacted for 10 hours, and then the organic layer was separated and washed with water until the pH became neutral, It is characterized by producing epoxidized soybean oil by filtration.
이 방법은 종래의 방법보다 간단한 공정으로 진행되며, 반응시간 역시 짧다. 또한, 종래의 방법보다 반응효율이 매우 높다.This method proceeds with a simpler process than the conventional method, and the reaction time is also short. In addition, the reaction efficiency is much higher than that of the conventional method.
상기 설명에서, 과산화수소는 35∼90% 농도 범위의 것을 사용하는 것이 바람직하며, 과산화수소의 양은 대두유 이중결합에 대해 1.0∼2.0mol을 부가하는 것이 바람직하다.In the above description, the hydrogen peroxide is preferably used in the range of 35 to 90% concentration, the amount of hydrogen peroxide is preferably added 1.0 to 2.0 mol to the soybean oil double bond.
그 이유는 상기 과산화수소는 이중결합 하나에 인접한 두개의 탄소원자와 에폭시기를 형성하는 근본적인 원료이기 때문에, 대두유 이중결합 하나에 1몰의 과산화수소가 요구되나, 실제로는 1∼2몰을 사용하는 것이 실제 반응을 좀 더 용이하게 한다.The reason is that since hydrogen peroxide is a fundamental raw material for forming an epoxy group with two carbon atoms adjacent to a double bond, one mole of hydrogen peroxide is required for a single soybean oil double bond, but in practice, 1 to 2 moles are actually used. To make it easier.
상기 대두유 이중결합수는 대두유에 소모되는 과산화수소 및 포름산의 양으로 측정하거나 또는 대두유의 요오드가(iodin value)를 측정하여 얻을 수 있으며, 본 발명에서는 요오드가를 측정하여 대두유의 이중결합수를 결정한다. 본 발명에서는 첨가되는 산 또는 알카리의 양을 몰단위로 표시하였으나, 상업적으로 생산하기 위해서는 이를 ㎏으로 환산하여 적용해도 된다.The soybean oil double bond water can be obtained by measuring the amount of hydrogen peroxide and formic acid consumed in soybean oil or by measuring the iodine value of soybean oil. In the present invention, the double bond water of soybean oil is determined by measuring the iodine value. . In the present invention, the amount of acid or alkali added is expressed in molar units, but for commercial production, this may be converted to kg.
본 발명에 사용된 포름산은 30-90% 농도 범위이고, 대두유 이중결합에 대해 0.1∼1.0mol을 사용하는 것이 바람직하다.Formic acid used in the present invention is in the 30-90% concentration range, it is preferable to use 0.1 to 1.0 mol for soybean oil double bonds.
본 발명에 사용된 촉매로 40∼90% 농도 범위의 인산을 사용하며, 상기 인산의 양은 대두유에 대해 1.0∼5.0중량%를 사용하는 것이 바람직하다. 인산촉매없이도 반응은 진행되나, 이 인산촉매를 사용하므로서 상기 에폭시화를 용이하게 하며, 반응시간을 감소시키며 높은 수율의 에폭시화 대두유를 얻을 수 있다. 상기 인산의 양은 대두유의 양에 따라 변하며, 인산의 양이 1% 이하로 낮을 경우에는 반응이 용이하게 완결되지 않으며 또한 에폭시화 대두유의 옥시란 함량이 낮아 제품의 질이 저하됨을 알 수 있다.As the catalyst used in the present invention, phosphoric acid in a concentration range of 40 to 90% is used, and the amount of phosphoric acid is preferably used in an amount of 1.0 to 5.0% by weight based on soybean oil. The reaction proceeds without the phosphate catalyst, but the phosphate catalyst facilitates the epoxidation, reduces the reaction time and yields a high yield of epoxidized soybean oil. The amount of phosphoric acid varies depending on the amount of soybean oil, and when the amount of phosphoric acid is lower than 1%, the reaction is not easily completed, and the oxirane content of the epoxidized soybean oil is low, and thus the quality of the product may be deteriorated.
본 발명의 제조방법은 40∼120℃의 온도범위에서 실행되며 40℃ 이하의 온도에서는 반응이 진행되지 않으며 120℃ 이상이면 성분의 분해가 일어나 제품을 제조할 수 없었다. 반응시간은 4∼24시간에 내에 실시되는것이 바람직하다.The production method of the present invention is carried out in a temperature range of 40 to 120 ℃ and the reaction does not proceed at a temperature of 40 ℃ or less, if the above 120 ℃ decomposed components could not be produced a product. It is preferable that reaction time is performed in 4 to 24 hours.
본 발명의 제조방법에 의해 제조된 에폭시화 대두유는 그 에폭시화 정도 즉, 옥시란 함량을 측정하기 위하여 반응전 대두유의 요오드가를 측정하고 제조된 에폭시화 대두유의 요오드가 및 산소함량을 측정하였다.The epoxidized soybean oil prepared by the manufacturing method of the present invention was measured the iodine value of the soybean oil before the reaction in order to determine the degree of epoxidation, that is, the oxirane content, and the iodine value and oxygen content of the prepared epoxidized soybean oil.
산소함량 측정은 AOCS(America Oil and Chemistry Society)의 Cd 9-57 방법으로 행하였다.Oxygen content was measured by Cd 9-57 method of the American Oil and Chemistry Society (AOCS).
이하, 본 발명의 에폭시화 대두유의 제조방법 및 산소함유율의 측정시험결과에 대하여 실시예를 들어서 상세히 설명한다.EMBODIMENT OF THE INVENTION Hereinafter, the manufacturing method and the test result of oxygen content rate of the epoxidized soybean oil of this invention are described in detail with an Example.
실시예 1Example 1
온도계, 환류냉각기 및 교반기가 부착된 5L 4구 플라스크에 대두유 2,000g(요오드가 132)을 투입하고 서서히 교반하면서 70℃로 가열한 후 80%의 농도의 포름산 275g(4.78Mol)을 상기 플라스크내에 30분~1시간에 걸쳐 서서히 적하하면서 동시에 50% 농도 과산화수소 1,110g(16.3mol), 85% 농도의 인산 118g의 혼합용액을 플라스크내에 1시간∼5시간에 걸쳐 서서히 적하하면서 온도 70℃를 계속 유지한다.Into a 5L four-necked flask equipped with a thermometer, a reflux condenser and a stirrer, 2,000 g of soybean oil (iodine 132) was heated to 70 ° C. with gentle stirring, and then 275 g (4.78 Mol) of formic acid at a concentration of 80% was added to the flask. Slowly dropwise over 1 minute to 1 hour while maintaining a temperature of 70 ° C while slowly dropping a mixed solution of 1,110 g (16.3 mol) of 50% hydrogen peroxide and 118 g of phosphoric acid at 85% concentration over 1 hour to 5 hours. .
반응중 생성된 과포름산의 분해에 유의하면서 10시간 동안 반응을 시킨다. 반응 종결후 유기층을 분리하여 pH가 중성이 될때까지 수세한 후 감압건조, 여과하여 생성물을 얻고, 이를 AOCS(America oil and chemistry sociate) Cd 9-57 방법으로 산소함량을 측정한 결과 6.78%이고 요오드가는 2.24였다.The reaction is carried out for 10 hours while paying attention to the decomposition of performic acid generated during the reaction. After completion of the reaction, the organic layer was separated, washed with water until neutral, dried under reduced pressure and filtered to obtain a product, and the oxygen content was measured by AOCS (America oil and chemistry sociate) Cd 9-57 method. Going 2.24.
실시예 2Example 2
온도계, 환류냉각기 및 교반기가 부착된 5L, 4구 플라스크에 대두유 2,000g(요오드가 132)을 투입하고 서서히 교반하면서 70℃로 가열한 후 80%의 농도의 포름산 275g(4.78Mol)을 상기 플라스크내에 30분~1시간에 걸쳐 서서히 적하하면서 동시에 50% 농도 과산화수소 832g(12.2mol), 85% 농도의 인산 118g의 혼합용액을 플라스크내에 1시간∼5시간에 걸쳐 서서히 적하하면서 온도 70℃를 계속 유지한다.Into a 5-liter, four-necked flask equipped with a thermometer, a reflux condenser and a stirrer, 2,000 g of soybean oil (iodine 132) was heated to 70 ° C. with gentle stirring, and then 275 g of formic acid at 80% concentration (4.78 Mol) was added to the flask. While slowly dropping over 30 minutes to 1 hour, a mixture of 50% hydrogen peroxide 832 g (12.2 mol) and 85% phosphoric acid 118 g is slowly added dropwise into the flask over 1 hour to 5 hours to maintain the temperature of 70 ° C. .
반응중 생성된 과포름산의 분해에 유의하면서 10시간 동안 반응을 시킨다. 반응 종결후 유기층을 분리하여 pH가 중성이 될때까지 수세한 후 감압건조, 여과하여 생성물을 얻고, 이를 AOCS Cd 9-57 방법으로 산소함량을 측정한 결과 6.75%이고 요오드가는 2.27였다.The reaction is carried out for 10 hours while paying attention to the decomposition of performic acid generated during the reaction. After completion of the reaction, the organic layer was separated, washed with water until the pH became neutral, and dried under reduced pressure and filtered to obtain a product. The oxygen content was measured by AOCS Cd 9-57 method, which was 6.75% and the iodine value was 2.27.
실시예 3Example 3
온도계, 환류냉각기 및 교반기가 부착된 5L 4구 플라스크에 대두유 2,000g(요오드가 132)을 투입하고 서서히 교반하면서 70℃로 가열한 후 80%의 농도의 포름산 275g(4.78Mol)을 상기 플라스크내에 30분∼1시간에 걸쳐 서서히 적하하면서 동시에 50% 농도 과산화수소 925g(16.3mol), 85% 농도의 인산 118g의 혼합용액을 플라스크내 1시간∼5시간에 걸쳐 서서히 적하하면서 온도 70℃를 계속 유지한다.Into a 5L four-necked flask equipped with a thermometer, a reflux condenser and a stirrer, 2,000 g of soybean oil (iodine 132) was heated to 70 ° C. with gentle stirring, and then 275 g (4.78 Mol) of formic acid at a concentration of 80% was added to the flask. The mixture was slowly added dropwise over 1 minute to 1 hour, and the mixture solution of 925 g (16.3 mol) of 50% hydrogen peroxide and 118 g of phosphoric acid at 85% concentration was slowly added dropwise to the flask over 1 hour to 5 hours to maintain the temperature of 70 ° C.
반응중 생성된 과포름산의 분해에 유의하면서 10시간 동안 반응을 시킨다. 반응 종결후 유기층을 분리하여 pH가 중성이 될때까지 수세한 후 감압건조, 여과하여 생성물을 얻고, 이를 AOCS Cd 9-57 방법으로 산소함량을 측정한 결과 6.78%이고 요오드가는 2.26였다.The reaction is carried out for 10 hours while paying attention to the decomposition of performic acid generated during the reaction. After completion of the reaction, the organic layer was separated, washed with water until the pH became neutral, and dried under reduced pressure and filtered to obtain a product. The oxygen content was measured by AOCS Cd 9-57 method, which was 6.78% and the iodine value was 2.26.
실시예 4Example 4
온도계, 환류냉각기 및 교반기가 부착된 5L 4구 플라스크에 대두유 2,000g(요오드가 132)을 투입하고 서서히 교반하면서 70℃로 가열한 후 80%의 농도의 포름산 275g(4.78Mol)을 상기 플라스크내에 30분~1시간에 걸쳐 서서히 적하하면서 동시에 50% 농도 과산화수소 1,586g(1XXX Mol), 85% 농도의 인산 118g의 혼합용액을 플라스크내에 1시간∼5시간에 걸쳐 서서히 적하하면서 온도 70℃를 계속 유지한다.Into a 5L four-necked flask equipped with a thermometer, a reflux condenser and a stirrer, 2,000 g of soybean oil (iodine 132) was heated to 70 ° C. with gentle stirring, and then 275 g (4.78 Mol) of formic acid at a concentration of 80% was added to the flask. Slowly dropwise over 1 minute to 1 hour while maintaining a temperature of 70 ° C while slowly dropping a mixed solution of 1,586 g of 50% hydrogen peroxide (1XXX Mol) and 118 g of phosphoric acid at 85% concentration over 1 hour to 5 hours. .
반응중 생성된 과포름산의 분해에 유의하면서 10시간 동안 반응을 시킨다. 반응 종결후 유기층을 분리하여 pH가 중성이 될때까지 수세한 후 감압건조, 여과하여 생성물을 얻고, 이를 AOCS Cd 9-57 방법으로 산소함량을 측정한 결과 6.78%이고 요오드가는 2.28였다.The reaction is carried out for 10 hours while paying attention to the decomposition of performic acid generated during the reaction. After completion of the reaction, the organic layer was separated, washed with water until the pH became neutral, and dried under reduced pressure and filtered to obtain a product. The oxygen content was measured by AOCS Cd 9-57 method, which was 6.78% and the iodine value was 2.28.
실시예 5Example 5
온도계, 환류냉각기 및 교반기가 부착된 5L 4구 플라스크에 대두유 2,000g(요오드가 132)을 투입하고 서서히 교반하면서 70℃로 가열한 후 80%의 농도의 포름산 469g(8.16Mol)을 상기 플라스크내에 30분∼1시간에 걸쳐 서서히 적하하면서 동시에 50% 농도 과산화수소 1,110g(16.3mol), 85% 농도의 인산 118g의 혼합용액을 플라스크내에 1시간∼5시간에 걸쳐 서서히 적하하면서 온도 70℃를 계속 유지한다.Into a 5L four-necked flask equipped with a thermometer, a reflux condenser and a stirrer, 2,000 g of soybean oil (iodine 132) was heated to 70 ° C. with gentle agitation, and then 469 g (8.16 Mol) of formic acid at a concentration of 80% was added to the flask. Slowly dropwise over 1 minute to 1 hour while maintaining a temperature of 70 ° C while slowly dropping a mixed solution of 1,110 g (16.3 mol) of 50% hydrogen peroxide and 118 g of phosphoric acid at 85% concentration over 1 hour to 5 hours. .
반응중 생성된 과포름산의 분해에 유의하면서 10시간 동안 반응을 시킨다. 반응 종결후 유기층을 분리하여 pH가 중성이 될때까지 수세한 후 감압건조, 여과하여 생성물을 얻고, 이를 AOCS Cd 9-57 방법으로 산소함량을 측정한 결과 6.75%이고 요오드가는 2.30였다.The reaction is carried out for 10 hours while paying attention to the decomposition of performic acid generated during the reaction. After completion of the reaction, the organic layer was separated, washed with water until the pH became neutral, dried under reduced pressure and filtered to obtain a product. The oxygen content was measured by AOCS Cd 9-57 method, which was 6.75% and the iodine value was 2.30.
실시예 6Example 6
온도계, 환류냉각기 및 교반기가 부착된 5L 4구 플라스크에 대두유 2,000g(요오드가 132)을 투입하고 서서히 교반하면서 70℃로 가열한 후 80%의 농도의 포름산 630g(4.79Mol)을 상기 플라스크내에 30분∼1시간에 걸쳐 서서히 적하하면서 동시에 50% 농도 과산화수소 1,110g(16.3mol), 85% 농도의 인산 118g의 혼합용액을 플라스크내에 1시간∼5시간에 걸쳐 서서히 적하하면서 온도 70℃를 계속 유지한다.Into a 5L four-necked flask equipped with a thermometer, a reflux condenser and a stirrer, 2,000 g of soybean oil (iodine 132) was heated to 70 ° C. with gentle stirring, and 630 g (4.79 Mol) of formic acid at a concentration of 80% was added to the flask 30 Slowly dropwise over 1 minute to 1 hour while maintaining a temperature of 70 ° C while slowly dropping a mixed solution of 1,110 g (16.3 mol) of 50% hydrogen peroxide and 118 g of phosphoric acid at 85% concentration over 1 hour to 5 hours. .
반응중 생성된 과포름산의 분해에 유의하면서 10시간 동안 반응을 시킨다. 반응 종결후 유기층을 분리하여 pH가 중성이 될때까지 수세한 후 감압건조, 여과하여 생성물을 얻고, 이를 AOCS Cd 9-57 방법으로 산소함량을 측정한 결과 6.80%이고 요오드가는 2.16였다.The reaction is carried out for 10 hours while paying attention to the decomposition of performic acid generated during the reaction. After completion of the reaction, the organic layer was separated, washed with water until the pH was neutral, dried under reduced pressure and filtered to obtain a product. The oxygen content was measured by AOCS Cd 9-57 method. As a result, the iodine value was 6.16%.
실시예 7Example 7
온도계, 환류냉각기 및 교반기가 부착된 5L 4구 플라스크에 대두유 2,000g(요오드가 132)을 투입하고 서서히 교반하면서 70℃로 가열한 후 80%의 농도의 포름산 469g(4.78Mol)을 상기 플라스크내에 30분~1시간에 걸쳐 서서히 적하하면서 동시에 50% 농도 과산화수소 1,110g(16.3mol), 85% 농도의 인산 48g의 혼합용액을 플라스크내에 1시간∼5시간에 걸쳐 서서히 적하하면서 온도 70℃를 계속 유지한다.Into a 5L four-necked flask equipped with a thermometer, a reflux condenser and a stirrer, 2,000 g of soybean oil (iodine 132) was heated to 70 ° C. with gentle stirring, and then 469 g (4.78 Mol) of formic acid at a concentration of 80% was added to the flask. While slowly dropping over 1 minute to 1 hour, a mixed solution of 1,110 g (16.3 mol) of 50% hydrogen peroxide and 48 g of phosphoric acid at 85% concentration is slowly added dropwise into the flask over 1 hour to 5 hours, and the temperature is maintained at 70 ° C. .
반응중 생성된 과포름산의 분해에 유의하면서 10시간 동안 반응을 시킨다. 반응 종결후 유기층을 분리하여 pH가 중성이 될때까지 수세한 후 감압건조, 여과하여 생성물을 얻고, 이를 AOCS Cd 9-57 방법으로 산소함량을 측정한 결과 6.75%이고 요오드가는 2.36였다.The reaction is carried out for 10 hours while paying attention to the decomposition of performic acid generated during the reaction. After completion of the reaction, the organic layer was separated, washed with water until the pH became neutral, dried under reduced pressure and filtered to obtain a product. The oxygen content was measured by AOCS Cd 9-57 method, which was 6.75% and the iodine value was 2.36.
실시예 8Example 8
온도계, 환류냉각기 및 교반기가 부착된 5L 4구 플라스크에 대두유 2,000g(요오드가 132)을 투입하고 서서히 교반하면서 70℃로 가열한 후 80%의 농도의 포름산 275g(4.78Mol)을 상기 플라스크내에 30분∼1시간에 걸쳐 서서히 적하하면서 동시에 50% 농도 과산화수소 1,110g(16.3mol), 50% 농도의 인산 200g의 혼합 용액을 플라스크내에 1시간∼5시간에 걸쳐 서서히 적하하면서 온도 70℃를 계속 유지한다.Into a 5L four-necked flask equipped with a thermometer, a reflux condenser and a stirrer, 2,000 g of soybean oil (iodine 132) was heated to 70 ° C. with gentle stirring, and then 275 g (4.78 Mol) of formic acid at a concentration of 80% was added to the flask. Slowly dropwise over 1 minute to 1 hour while maintaining a temperature of 70 ° C. while slowly dropping a mixed solution of 1,110 g (16.3 mol) of 50% hydrogen peroxide and 200 g of phosphoric acid at 50% concentration over 1 hour to 5 hours. .
반응중 생성된 과포름산의 분해에 유의하면서 10시간 동안 반응을 시킨다. 반응 종결후 유기층을 분리하여 pH가 중성이 될때까지 수세한 후 감압건조, 여과하여 생성물을 얻고, 이를 AOCS Cd 9-57 방법으로 산소함량을 측정한 결과 6.75%이고 요오드가는 2.32였다.The reaction is carried out for 10 hours while paying attention to the decomposition of performic acid generated during the reaction. After completion of the reaction, the organic layer was separated, washed with water until the pH became neutral, dried under reduced pressure and filtered to obtain a product. The oxygen content was measured by AOCS Cd 9-57, and the result was 6.75% and iodine value was 2.32.
실시예 9Example 9
온도계, 환류냉각기 및 교반기가 부착된 5L 4구 플라스크에 대두유 2,000g(요오드가 132)을 투입하고 서서히 교반하면서 70℃로 가열한 후 80%의 농도의 포름산 275g(4.78Mol)을 상기 플라스크내에 30분∼1시간에 걸쳐 서서히 적하하면서 동시에 50% 농도 과산화수소 1,110g(16.3mol), 85% 농도의 인산 118g의 혼합용액을 플라스크내에 1시간-5시간에 걸쳐 서서히 적하하면서 온도 70℃를 계속 유지한다.Into a 5L four-necked flask equipped with a thermometer, a reflux condenser and a stirrer, 2,000 g of soybean oil (iodine 132) was heated to 70 ° C. with gentle stirring, and then 275 g (4.78 Mol) of formic acid at a concentration of 80% was added to the flask. Slowly dropwise over 1 minute to 1 hour while maintaining a temperature of 70 ° C while slowly dropping a mixed solution of 1,110 g (16.3 mol) of 50% hydrogen peroxide and 118 g of phosphoric acid at 85% concentration over 1 hour-5 hours. .
반응중 생성된 과포름산의 분해에 유의하면서 10시간 동안 반응을 시킨다. 반응 종결후 유기층을 분리하여 pH가 중성이 될때까지 수세한 후 감압건조, 여과하여 생성물을 얻고, 이를 AOCS Cd 9-57 방법으로 산소함량을 측정한 결과 6.80%이고 요오드가는 2.15였다.The reaction is carried out for 10 hours while paying attention to the decomposition of performic acid generated during the reaction. After completion of the reaction, the organic layer was separated, washed with water until the pH became neutral, and dried under reduced pressure and filtered to obtain a product. The oxygen content was measured by AOCS Cd 9-57 method. As a result, the iodine value was 6.15%.
실시예 10Example 10
온도계, 환류냉각기 및 교반기가 부착된 5L 4구 플라스크에 대두유 2,000g(요오드가 132)을 투입하고 서서히 교반하면서 70℃로 가열한 후 80%의 농도의 포름산 275g(4.78Mol)을 상기 플라스크내에 30분∼1시간에 걸쳐 서서히 적하하면서 동시에 50% 농도 과산화수소 1,110g(16.3mol), 85% 농도의 인산 118g의 혼합용액을 플라스크내에 1시간-5시간에 걸쳐 서서히 적하하면서 온도 70℃를 계속 유지한다.Into a 5L four-necked flask equipped with a thermometer, a reflux condenser and a stirrer, 2,000 g of soybean oil (iodine 132) was heated to 70 ° C. with gentle stirring, and then 275 g (4.78 Mol) of formic acid at a concentration of 80% was added to the flask. Slowly dropwise over 1 minute to 1 hour while maintaining a temperature of 70 ° C while slowly dropping a mixed solution of 1,110 g (16.3 mol) of 50% hydrogen peroxide and 118 g of phosphoric acid at 85% concentration over 1 hour-5 hours. .
반응중 생성된 과포름산의 분해에 유의하면서 10시간 동안 반응을 시킨다. 반응 종결후 유기층을 분리하여 pH가 중성이 될때까지 수세한 후 감압건조, 여과하여 생성물을 얻고, 이를 AOCS Cd 9-57 방법으로 산소함량을 측정한 결과 6.78%이고 요오드가는 2.24였다.The reaction is carried out for 10 hours while paying attention to the decomposition of performic acid generated during the reaction. After completion of the reaction, the organic layer was separated, washed with water until the pH became neutral, dried under reduced pressure and filtered to obtain a product. The oxygen content was measured by AOCS Cd 9-57 method, which was 6.78% and the iodine value was 2.24.
실시예 11Example 11
온도계, 환류냉각기 및 교반기가 부착된 5L 4구 플라스크에 대두유 2,000g(요오드가 132)을 투입하고 서서히 교반하면서 70℃로 가열한 후 80%의 농도의 포름산 275g(4.78Mol)을 상기 플라스크내에 30분∼1시간에 걸쳐 서서히 적하하면서 동시에 50% 농도 과산화수소 1,110g(16.3mol), 85% 농도의 인산 118g의 혼합용액을 플라스크내에 1시간∼5시간에 걸쳐 서서히 적하하면서 온도 70℃를 계속 유지한다.Into a 5L four-necked flask equipped with a thermometer, a reflux condenser and a stirrer, 2,000 g of soybean oil (iodine 132) was heated to 70 ° C. with gentle stirring, and then 275 g (4.78 Mol) of formic acid at a concentration of 80% was added to the flask. Slowly dropwise over 1 minute to 1 hour while maintaining a temperature of 70 ° C while slowly dropping a mixed solution of 1,110 g (16.3 mol) of 50% hydrogen peroxide and 118 g of phosphoric acid at 85% concentration over 1 hour to 5 hours. .
반응중 생성된 과포름산의 분해에 유의하면서 10시간 동안 반응을 시킨다. 반응 종결후 유기층을 분리하여 pH가 중성이 될때까지 수세한 후 감압건조, 여과하여 생성물을 얻고, 이를 AOCS Cd 9-57 방법으로 산소함량을 측정한 결과 6.80%이고 요오드가는 2.14였다.The reaction is carried out for 10 hours while paying attention to the decomposition of performic acid generated during the reaction. After completion of the reaction, the organic layer was separated, washed with water until the pH became neutral, dried under reduced pressure and filtered to obtain a product. The oxygen content was measured by AOCS Cd 9-57 method. As a result, the iodine value was 6.14%.
실시예 12Example 12
온도계, 환류냉각기 및 교반기가 부착된 5L 4구 플라스크에 대두유 2,000g(요오드가 132)을 투입하고 서서히 교반하면서 70℃로 가열한 후 80%의 농도의 포름산 275g(4.78Mol)을 상기 플라스크내에 30분∼1시간에 걸쳐 서서히 적하하면서 동시에 50% 농도 과산화수소 1,110g(16.3mol), 85% 농도의 인산 118g의 혼합용액을 플라스크내에 1시간∼5시간에 걸쳐 서서히 적하하면서 온도 70℃를 계속 유지한다.Into a 5L four-necked flask equipped with a thermometer, a reflux condenser and a stirrer, 2,000 g of soybean oil (iodine 132) was heated to 70 ° C. with gentle stirring, and then 275 g (4.78 Mol) of formic acid at a concentration of 80% was added to the flask. Slowly dropwise over 1 minute to 1 hour while maintaining a temperature of 70 ° C while slowly dropping a mixed solution of 1,110 g (16.3 mol) of 50% hydrogen peroxide and 118 g of phosphoric acid at 85% concentration over 1 hour to 5 hours. .
반응중 생성된 과포름산의 분해에 유의하면서 10시간 동안 반응을 시킨다. 반응 종결후 유기층을 분리하여 pH가 중성이 될때까지 수세한 후 감압건조, 여과하여 생성물을 얻고, 이를 AOCS Cd 9-57 방법으로 산소함량을 측정한 결과 6.80고 요오드가는 2.12였다.The reaction is carried out for 10 hours while paying attention to the decomposition of performic acid generated during the reaction. After completion of the reaction, the organic layer was separated, washed with water until the pH became neutral, and dried under reduced pressure and filtered to obtain a product. The oxygen content was measured by AOCS Cd 9-57 method, and the result was 6.80 and iodine value was 2.12.
상기 실시예에서 측정한 본 발명에 의한 에폭시화 대두유의 산소함량은 평균 약 6.75 정도로 나타났으므로 옥시란 콘텐트는 종래의 에폭시화물의 옥시란 콘텐트 보다 높아 반응효율이 월등하고 고순도의 에폭시화 대두유를 얻을 수 있었다.Since the oxygen content of the epoxidized soybean oil according to the present invention measured in the above example was about 6.75 on average, the oxirane content is higher than the oxirane content of the conventional epoxide, resulting in superior reaction efficiency and high purity epoxidized soybean oil. Could.
상기에서 설명한 바과 같이, 본 발명의 에폭시화 대두유의 제조방법에 의하면 플라스크에 대두유를 투입하고 교반 및 가열한 후 포름산을 서서히 적하하면서 과산화수소와 인산의 혼합용액을 상기 플라스크에 적하하면서 반응시킴으로서, 제조공정이 간단하고, 반응시간이 짧으며, 경제적이며 자연 생분해성의 무독한 고순도의 에폭시화 대두유를 제조할 수 있다는 매우 뛰어난 효과가 있다.As described above, according to the manufacturing method of the epoxidized soybean oil of the present invention, by adding soybean oil to the flask, stirring and heating, reacting the mixed solution of hydrogen peroxide and phosphoric acid dropwise to the flask while slowly dropping formic acid. This simple, short reaction time, economical and naturally biodegradable, high purity epoxidized soybean oil can be produced.
Claims (8)
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| KR20160089570A (en) * | 2015-01-19 | 2016-07-28 | 주식회사 사조해표 | Method for purification of an epoxidized soybean oil |
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