KR100192014B1 - Preparation for expoxides of unsaturated fatty acid esters - Google Patents
Preparation for expoxides of unsaturated fatty acid esters Download PDFInfo
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- KR100192014B1 KR100192014B1 KR1019960022459A KR19960022459A KR100192014B1 KR 100192014 B1 KR100192014 B1 KR 100192014B1 KR 1019960022459 A KR1019960022459 A KR 1019960022459A KR 19960022459 A KR19960022459 A KR 19960022459A KR 100192014 B1 KR100192014 B1 KR 100192014B1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/02—Synthesis of the oxirane ring
- C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
- C07D301/12—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with hydrogen peroxide or inorganic peroxides or peracids
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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
본 발명은 불포화 지방사 에스테르 화합물의 에폭시화물의 제조방법에 관한 것으로서, 온도계, 환류냉각기 및 교반기가 부착된 4구 플라스크에 불포화 지방산 에스테르를 투입하고 서서히 교반하면서 70∼80℃로 가열한 후 포름산을 상기 플라스크 내에 30분∼1시간에 걸쳐 서서히 적하하고, 동시에 과산화수소와 인산의 혼합용액을 플라스크 내에 1시간∼5시간에 걸쳐 서서히 적하하면서 상기 온도를 계속 유지하고 10∼12시간 동안 반응시킨 후 유기층을 분리하여 pH가 중성이 될 때까지 수세한 후 감압건조 및 여과하여 불포화 지방산 에스테르 화합물의 에폭시화물을 제조하는 것을 특징으로 한다. 본 발명의 불포화 지방산 에스테르 화합물의 에폭시화물의 제조방법은 종래의 방법에 비해 반응효율이 높고, 제조공정이 간단하므로 반응시간이 크게 단축된 것으로서, 본 발명에 의해 제조된 불포화 지방산 에스테르 화합물의 에폭시화물은 산소함량이 월등히 높을 뿐만 아니라, 고 순도의 자연분해성 에폭시화물이다.The present invention relates to a process for producing an epoxidized unsaturated fatty acid ester compound, which comprises feeding an unsaturated fatty acid ester to a four-necked flask equipped with a thermometer, a reflux condenser and a stirrer, heating the mixture at 70 to 80 ° C with stirring, The mixture was gradually dropped in the flask over a period of 30 minutes to 1 hour, while a mixed solution of hydrogen peroxide and phosphoric acid was gradually dropped in the flask over a period of 1 hour to 5 hours while maintaining the above temperature for 10 to 12 hours, And washed with water until the pH becomes neutral, followed by drying under reduced pressure and filtration to produce an epoxide of an unsaturated fatty acid ester compound. The process for producing an unsaturated fatty acid ester compound of the present invention has a higher reaction efficiency and a simpler production process than the conventional process, and thus the reaction time is greatly shortened. The epoxide of the unsaturated fatty acid ester compound produced by the present invention Is not only significantly higher in oxygen content, but also a high purity, naturally degradable epoxide.
Description
본 발명은 불포화 지방산 에스테르 화합물의 에폭시화물의 제조방법에 관한 것으로,좀 더 상세하게는 불포화 지방산의 에스테르 화합물에 과산화수소와 포름산의 혼합물로부터 생성된 과포름산(HCOOOH)과 촉매를 첨가하여 불포화 지방산의 이중결합을 에폭시화한 불포화 지방산 에스테르 화합물의 에폭시화물의 제조방법에 관한 것이다.More particularly, the present invention relates to a method for producing epoxides of unsaturated fatty acid esters by adding peroxy formic acid (HCOOOH) and a catalyst formed from a mixture of hydrogen peroxide and formic acid to an ester compound of an unsaturated fatty acid, Linking an epoxidized unsaturated fatty acid ester compound.
종래에는, 미국 툭허 제2, 801, 253호의 공보에 기재된 바와 같은 아세트산, 황산 및 과산화수소를 사용하는 에폭시화물의 제조방법에 의하면, 촉매로서 황산을 사용하나 높은 산도로 인해 반응이 불균일하게 일어나고, 또한 반응후의 에폭시화물이 황산 등의 촉매로 인한 분해반응, 즉 글리콜이 쉽게 생성되는 등 새로운 부반응이 일어나서 결국 반응율이 낮아지게 된다.Conventionally, according to the process for producing epoxides using acetic acid, sulfuric acid and hydrogen peroxide as described in USP No. 2, 801, 253, sulfuric acid is used as a catalyst, but the reaction occurs unevenly due to high acidity, A new side reaction occurs such that the decomposition reaction of the epoxide after the reaction with the catalyst such as sulfuric acid, that is, the glycol is easily generated, and the reaction rate becomes low.
따라서, 본 발명은 상기 종래의 문제점을 해소하기 위하여 이루어진 것으로, 본 발명의 목적은 제조비용이 저렴하고 제조공정이 간단하며, 동시에 반응시간이 짧고, 반응효율이 높은 자연생분해성의 무독한 불포화 지방산 에스테르 화합물의 에폭시화물의 제조방법을 제공하는데 있다.Accordingly, an object of the present invention is to provide a non-toxic, unsaturated fatty acid ester which is low in production cost, simple in production process, short in reaction time and high in reaction efficiency, And to provide a process for preparing an epoxide of a compound.
상기 목적을 달성하기 위하여, 본 발명에 의한 불포화 지방산 에스테르 화합물의 에폭시화물의 제조방법은 온도계, 환류냉각기 및 교반기가 부착된 4구 플라스크에 불포화 지방산 에스테르를 투입하고 서서히 교반하면서 70∼80℃로 가열한 후 포름산을 상기 플라스크 내에 30분∼1시간에 걸쳐 서서히 적하하고, 동시에 과산화수소와 인산의 혼합용액을 플라스크 내에 1시간∼5시간에 걸쳐 서서히 적하하면서 상기 온도를 계속 유지하고 10∼12시간 동안 반응시킨 후 유기층을 분리하여 pH가 중성이 될 때까지 수세한 후 감압건조 및 여과하여 불포화 지방산 에스테르 화합물의 에폭시화물을 제조하는 것을 특징으로 한다.In order to achieve the above object, an unsaturated fatty acid ester compound according to the present invention is prepared by introducing an unsaturated fatty acid ester into a four-necked flask equipped with a thermometer, a reflux condenser and a stirrer, Then, formic acid is slowly dropped in the flask over a period of 30 minutes to 1 hour, and at the same time, a mixed solution of hydrogen peroxide and phosphoric acid is slowly dropped in the flask over a period of 1 hour to 5 hours, The organic layer is separated, washed with water until the pH becomes neutral, dried under reduced pressure, and filtered to produce an epoxide of an unsaturated fatty acid ester compound.
본 발명에 있어서, 올레산, 리놀레산, 리놀렌산 등의 탄소수 18의 불포화 지방산이 많이 사용되지만, 팔미톨레산(탄소수 16), 미리스톨레산(Myristoleic acid : 탄소수 14) 등의 불포화 지방산도 사용할 수 있다. 또한, 올레산, 리놀레산 등은 천연지방산으로, 무독성이고 생분해성이 우수하며, 열안정성 및 광안정성이 뛰어나기 때문에 음식물 포장용 푸드랩(Food Wrap) 등 식품포장용기의 제조에 첨가제로 사용된다.In the present invention, unsaturated fatty acids having 18 carbon atoms such as oleic acid, linoleic acid and linolenic acid are frequently used, but unsaturated fatty acids such as palmitoleic acid (having 16 carbon atoms) and myristoleic acid (having 14 carbon atoms) can also be used. In addition, oleic acid, linoleic acid, and the like are natural fatty acids, which are non-toxic, excellent in biodegradability, excellent in thermal stability and light stability, and thus used as additives in the manufacture of food packaging such as food wrap for food packaging.
또한, 본 발명에 있어서, 상기 불포화 지방산을 메틸알콜, 에틸알콜, 부틸알콜, 옥틸알콜 등의 알콜 화합물과 반응시켜 보다 안정화된 불포화 지방산 메틸 에스테르 화합물, 불포화 지방산 에틸 에스테르 화합물, 불포화 지방산 부틸 에스테르 화합물 등의 불포화 지방산 에스테르 화합물을 제조하여 이들을 에폭시화한다.In the present invention, the unsaturated fatty acid is reacted with an alcohol compound such as methyl alcohol, ethyl alcohol, butyl alcohol or octyl alcohol to obtain a more stabilized unsaturated fatty acid methyl ester compound, unsaturated fatty acid ethyl ester compound, unsaturated fatty acid butyl ester compound Unsaturated fatty acid ester compounds are prepared and epoxidized.
상기 불포화 지방산 에스테르 화합물은 무기한 촉매하에 포름산과 과산화수소와 반응시켜 산소함량이 높은 경제적인 에폭시화물을 얻을 수 있다.The unsaturated fatty acid ester compound can be reacted with formic acid and hydrogen peroxide under an indefinite catalyst to obtain an economical epoxide having a high oxygen content.
상기 올레산, 리놀레산 등의 에스테르 화합물의 에폭시화물은 폴리염화비닐(PVC) 가공시에 첨가제로 사용되는데, 이를 첨가함으로써 열안정성 및 가공성이 우수한 폴리염화비닐을 제조할 수 있다. 따라서, 바닥장식재, 벽지, 레자, 시트 등의 PVC 가공시에 널리 사용되며, 또한 농약 제조시의 안정제, 기타 도료, 접착제 및 유기 화합물의 제조시에 첨가제로서 사용될 수 있다.The epoxide of the ester compound such as oleic acid and linoleic acid is used as an additive in the processing of polyvinyl chloride (PVC). By adding it, it is possible to produce polyvinyl chloride excellent in heat stability and processability. Therefore, it is widely used in the processing of PVC such as floor coverings, wallpaper, leathers, sheets, etc., and can also be used as an additive in the production of stabilizers, other paints, adhesives and organic compounds in the production of agricultural chemicals.
불포화 지방산 에스테르의 에폭시화물은 옥시란 산소의 함량이 높아서 종래의 다른 에폭시화물에 대하여 그 성능이 우수하여 폴리염화비닐 가공시에 첨가제로 사용하면 가공시에 발생하거나 또는 사용중에 발생하여 그 물질을 열화시키는 원인이 되는 염산과 같은 물질로 된 산을 매우 효과적으로 제거할 수 있다. 또한, 불포화 지방산 에스테르의 에폭시화물은 종래의 에폭시화물에 비하여 옥시란 산소의 함량이 높기 때문에, 적은 양으로도 그 효과가 클 뿐만 아니라, PVC 수지 등과의 상용성이 우수하다. 그리하여, PVC 캘린더 가공시에 회전롤 표면에 에폭시화물이 유출되는 현상(bleeding out)을 크게 개선할 수 있다.The epoxidation of unsaturated fatty acid esters has a high content of oxiranium oxide, which is superior in performance to other conventional epoxides. When used as an additive in polyvinyl chloride processing, it occurs during processing or during use, It is possible to very effectively remove an acid composed of a substance such as hydrochloric acid, which is a cause. In addition, since the content of oxirane oxygen is higher than that of the conventional epoxide, unsaturated fatty acid ester epoxides are not only effective in small amounts but also excellent in compatibility with PVC resins and the like. Thus, the bleeding out of the epoxides on the surface of the rotating roll during the processing of the PVC calender can be greatly improved.
본 발명은 상술한 종래의 에폭시화 방법에서보다 생성물의 요오드값이 훨씬 낮다. 예를 들면 올레산부틸 에스테르의 경우, 상술한 미국 특허 발명에 있어서는 요오드값이 5.4이상인데 반해, 후술되는 바와 같이 본 발명에서는 4.0이하의 낮은 요오드값을 얻을 수 있다. 즉, 본 발명의 에폭시화 반응에 의해 불포화 지방산의 이중결합위치에 옥시란 그룹이 형성되는, 즉 에폭시를 함유하는 에폭시화물을 생성하므로 불포화 지방산내의 이중결합수가 상당히 감소되어 생성물의 요오드값은 낮아지고 불포화 지방산 에스테르의 산소함량은 증가된다.The present invention is much lower in iodine value of the product than in the above-described conventional epoxidation process. For example, in the case of oleic acid butyl ester, the iodine value is at least 5.4 in the above-mentioned US patent invention, but as described later, a low iodine value of 4.0 or less can be obtained in the present invention. That is, since the oxirane group is formed at the double bond position of the unsaturated fatty acid by the epoxidation reaction of the present invention, that is, the epoxide compound containing epoxy is produced, the number of double bond in the unsaturated fatty acid is considerably decreased to lower the iodine value of the product The oxygen content of the unsaturated fatty acid ester is increased.
본 발명에 사용되는 과산화수소는 농도가 35∼90%인 것이 바람직하며, 사용되는 불포화 지방산에서 하나의 이중결합에 대해 1.0∼2.0몰을 부가하는 것이 바람직하다. 왜냐하면, 상기 과산화수소가 이중결합 하나에 인접하는 2개의 탄소원자와 함께 에폭시기를 형성하기 때문이며, 이론적으로는 이중결합 하나에 1몰의 과산화수소가 요구되나, 실제로는 1∼2몰을 사용하는 것이 실제반응을 더욱 더 용이하게 한다.The concentration of hydrogen peroxide used in the present invention is preferably 35 to 90%, and it is preferable to add 1.0 to 2.0 mol per one double bond in the used unsaturated fatty acid. This is because the hydrogen peroxide forms an epoxy group together with two carbon atoms adjacent to one double bond. Theoretically, one mole of hydrogen peroxide is required for one double bond, but actually 1 to 2 moles is used in practice. . ≪ / RTI >
상기 불포화 지방산의 이중결합수는 반응에 사용되는 과산화수소 및 포름산의 양으로 측정되거나, 또는 불포화 지방산의 요오드값을 측정하여 얻을 수 있는데, 본 발명에서는 요오드값을 측정하여 불포화 지방산의 이중결합수를 결정한다.The number of double bonds of the unsaturated fatty acid can be measured by measuring the amount of hydrogen peroxide and formic acid used in the reaction or by measuring the iodine value of the unsaturated fatty acid. In the present invention, the number of double bonds of the unsaturated fatty acid is determined do.
본 발명에 사용되는 포름산은 그 농도가 30∼90%이고, 불포화 지방산 에스테르에서 하나의 이중결합에 대해 0.1∼1.0몰을 사용하는 것이 바람직하다.The concentration of formic acid used in the present invention is preferably 30 to 90%, and it is preferable to use 0.1 to 1.0 mol per one double bond in the unsaturated fatty acid ester.
또한, 본 발명에 사용되는 촉매로는 농도가 40∼90%인 인산을 불포화 지방산 에스테르의 중량에 대해 1.0∼5.0%를 사용하는 것이 바람직하다. 인산촉매 없이도 반응은 진해되나, 인산에 의해 에폭시화 반응이 용이하게 일어나므로, 반응시간을 감소시키고 에폭시화물을 고수율로 얻을 수 있다. 상기 인산의 양은 불포화 지방산 에스테르의 양에 의존하며, 인산의 양이 1% 이하로 낮은 경우에는 반응이 용이하게 완결되지 않고 불포화 지방산 에스테르 화합물의 옥시란 함량이 낮으므로 제품의 질이 저하될 수 있다.As the catalyst used in the present invention, it is preferable to use 1.0 to 5.0% of phosphoric acid having a concentration of 40 to 90% with respect to the weight of the unsaturated fatty acid ester. The reaction is accelerated without the phosphoric acid catalyst, but since the epoxidation reaction is easily caused by phosphoric acid, the reaction time can be reduced and the epoxide can be obtained in high yield. The amount of phosphoric acid depends on the amount of the unsaturated fatty acid ester. When the amount of the phosphoric acid is as low as 1% or less, the reaction is not easily completed and the oxirane content of the unsaturated fatty acid ester compound is low, .
본 발명은 50∼130℃의 온도에서 수행되며, 50℃이하의 온도에서는 반응이 진행되지 않고, 반면에 130℃이상이면 성분의 분해가 일어나 제품을 제조할 수 없다.The present invention is carried out at a temperature of 50 to 130 캜, and the reaction does not proceed at a temperature of 50 캜 or lower. On the other hand, when the temperature is higher than 130 캜, decomposition of the component occurs and a product can not be produced.
본 발명의 전체 반응시간은 7∼15시간내에 실시하는 것이 바람직하다.The total reaction time of the present invention is preferably within 7 to 15 hours.
본 발명의 의해 제조된 에폭시화물은 에폭시화도, 즉 옥시란 함량을 측정하기 위하여, 반응전의 불포화 지방산 에스테르 화합물의 요오드값을 측정하고, 제조된 에폭시화물의 요오드값 및 산소함량을 측정한다.In order to measure the degree of epoxidation, that is, the content of oxirane, the iodine value of the unsaturated fatty acid ester compound before the reaction is measured, and the iodine value and the oxygen content of the produced epoxide are measured.
이하, 본 발명은 하기의 실시예에 의해 구체적으로 설명한다.Hereinafter, the present invention will be described in detail with reference to the following examples.
[실시예 1][Example 1]
온도계, 환류냉각기 및 교반기가 부착된 5L 4구 플라스크에 올레산메틸 에스테르 2,000g을 투입하고 서서히 교반하면서 80℃로 가열한 후 80% 포름산 184g(3.2몰)을 상기 플라스크에 30분간에 걸쳐 서서히 적하하고, 동시에 50% 과산화수소 555g(8.2몰)과 85% 인산 118g의 혼합용액을 플라스크내에 1시간에 걸쳐 서서히 적가하면서 80℃를 계속 유지한다. 반응중에 생성된 과포름산의 분해에 유의하면서 10시간동안 반응시킨다. 반응 종결 후 유기층을 분리하여 pH가 중성이 될 때까지 수세한 후 감압건조 및 여과하여 생성물을 얻고,이를 AOCS(American Oil and Chemistry Society) cd 9-57방법으로 산소함량을 측정한 결과 4.9%(이론치 : 5.4%), 요오드값은 3.4였다.Neck flask equipped with a stirrer, a thermometer, a reflux condenser, and a stirrer was charged with 2,000 g of oleic acid methyl ester and heated to 80 DEG C with gentle stirring. 184 g (3.2 moles) of 80% formic acid was slowly added dropwise to the flask over 30 minutes , And at the same time, a mixed solution of 555 g (8.2 moles) of 50% hydrogen peroxide and 118 g of 85% phosphoric acid was gradually dropped in the flask over 1 hour while maintaining 80 ° C. The reaction is carried out for 10 hours while paying attention to the decomposition of formic acid formed during the reaction. After completion of the reaction, the organic layer was separated, washed with water until the pH became neutral, and then dried under reduced pressure and filtered to obtain a product. The oxygen content was measured by AOCS (American Oil and Chemistry Society) cd 9-57, Theoretical value: 5.4%) and the iodine value was 3.4.
[실시예 2][Example 2]
온도계, 환류냉각기 및 교반기가 부착된 5L 4구 플라스크에 리놀레산메틸 에스테르 2,000g을 투입하고 서서히 교반하면서 80℃로 가열한 후 80% 포름산 368g(6.4몰)을 상기 플라스크에 1시간에 걸쳐 서서히 적하하고, 동시에 50% 과산화수소 1,110g(16.3몰)과 85% 인산 118g의 혼합용액을 플라스크내에 2시간에 걸쳐 서서히 적가하면서 80℃를 계속 유지한다. 반응중에 생성된 과포름산의 분해에 유의하면서 10시간동안 반응시킨다. 반응 종결 후 유기층을 분리하여 pH가 중성이 될 때까지 수세한 후 감압건조 및 여과하여 생성물을 얻고, 이를 AOCS cd 9-57방법으로 산소함량을 측정한 결과 9.8%(이론치 : 10.8%), 요오드값은 1.7였다.2,000 g of linoleic acid methyl ester was added to a 5-liter four-necked flask equipped with a thermometer, a reflux condenser and a stirrer, and heated to 80 DEG C with gentle stirring. 368 g (6.4 mol) of 80% formic acid was slowly added dropwise to the flask over 1 hour , And at the same time, a mixed solution of 1,110 g (16.3 mol) of 50% hydrogen peroxide and 118 g of 85% phosphoric acid was gradually dropped in the flask over 2 hours while maintaining 80 ° C. The reaction is carried out for 10 hours while paying attention to the decomposition of formic acid formed during the reaction. After completion of the reaction, the organic layer was separated, washed with water until the pH became neutral, and then dried under reduced pressure and filtered to obtain a product. The oxygen content of the product was measured by AOCS cd 9-57. The result was 9.8% (theoretical value: 10.8% The value was 1.7.
[실시예 3][Example 3]
온도계, 환류냉각기 및 교반기가 부착된 5L 4구 플라스크에 올레산메틸 에스테르 2,000g을 투입하고 서서히 교반하면서 80℃로 가열한 후 80% 포름산 156g(2.7몰)을 상기 플라스크에 30분간에 걸쳐 서서히 적하하고, 동시에 50% 과산화수소 472g(6.9몰)과 85% 인산 118g의 혼합용액을 플라스크내에 1시간에 걸쳐 서서히 적가하면서 80℃를 계속 유지한다. 반응중에 생성된 과포름산의 분해에 유의하면서 10시간동안 반응시킨다. 반응 종결 후 유기층을 분리하여 pH가 중성이 될 때까지 수세한 후 감압건조 및 여과하여 생성물을 얻고, 이를 AOCS cd 9-57방법으로 산소함량을 측정한 결과 3.2%(이론치 : 3.4%), 요오드값은 5.3였다.Neck flask equipped with a stirrer, a thermometer, a reflux condenser and a stirrer was charged with 2,000 g of oleic acid methyl ester and heated to 80 DEG C with gentle stirring, and 156 g (2.7 mol) of 80% formic acid was slowly added dropwise to the flask over 30 minutes , And at the same time, a mixed solution of 472 g (6.9 mol) of 50% hydrogen peroxide and 118 g of 85% phosphoric acid was gradually dropped in the flask over one hour while maintaining 80 ° C. The reaction is carried out for 10 hours while paying attention to the decomposition of formic acid formed during the reaction. After completion of the reaction, the organic layer was separated, washed with water until the pH became neutral, and then dried under reduced pressure and filtered to obtain a product. The oxygen content was measured by AOCS cd 9-57, and 3.2% (calculated value: 3.4% The value was 5.3.
[실시예 4][Example 4]
온도계, 환류냉각기 및 교반기가 부착된 5L 4구 플라스크에 올레산메틸 에스테르 2,000g을 투입하고 서서히 교반하면서 80℃로 가열한 후 80% 포름산 184g(3.2몰)을 상기 플라스크에 1시간에 걸쳐 서서히 적하하고, 동시에 50% 과산화수소 694g(10.2몰)과 85% 인산 118g의 혼합용액을 플라스크내에 2시간에 걸쳐 서서히 적가하면서 80℃를 계속 유지한다. 반응중에 생성된 과포름산의 분해에 유의하면서 10시간동안 반응시킨다. 반응 종결 후 유기층을 분리하여 pH가 중성이 될 때까지 수세한 후 감압건조 및 여과하여 생성물을 얻고, 이를 AOCS cd 9-57방법으로 산소함량을 측정한 결과 5.0%(이론치 : 5.4%), 요오드값은 3.4였다.Neck flask equipped with a stirrer, a thermometer, a reflux condenser, and a stirrer was charged with 2,000 g of oleic acid methyl ester, and the mixture was heated to 80 DEG C with gentle stirring. 184 g (3.2 mol) of 80% formic acid was slowly added dropwise to the flask over one hour , And at the same time, a mixed solution of 694 g (10.2 mol) of 50% hydrogen peroxide and 118 g of 85% phosphoric acid was slowly dropped in the flask over 2 hours while maintaining 80 ° C. The reaction is carried out for 10 hours while paying attention to the decomposition of formic acid formed during the reaction. After completion of the reaction, the organic layer was separated, washed with water until the pH became neutral, and then dried under reduced pressure and filtered to obtain a product. The oxygen content was 5.0% (calculated by AOCS cd 9-57) The value was 3.4.
[실시예 5][Example 5]
온도계, 환류냉각기 및 교반기가 부착된 5L 4구 플라스크에 올레산메틸 에스테르 2,000g을 투입하고 서서히 교반하면서 80℃로 가열한 후 80% 포름산 184g(3.2몰)을 상기 플라스크에 30분간에 걸쳐 서서히 적하하고, 동시에 50% 과산화수소 694g(10.2몰)과 85% 인산 118g의 혼합용액을 플라스크내에 1시간에 걸쳐 서서히 적가하면서 80℃를 계속 유지한다. 반응중에 생성된 과포름산의 분해에 유의하면서 12시간동안 반응시킨다. 반응 종결 후 유기층을 분리하여 pH가 중성이 될 때까지 수세한 후 감압건조 및 여과하여 생성물을 얻고, 이를 AOCS cd 9-57방법으로 산소함량을 측정한 결과 5.1%(이론치 : 5.4%), 요오드값은 3.3였다.Neck flask equipped with a stirrer, a thermometer, a reflux condenser, and a stirrer was charged with 2,000 g of oleic acid methyl ester and heated to 80 DEG C with gentle stirring. 184 g (3.2 moles) of 80% formic acid was slowly added dropwise to the flask over 30 minutes , And at the same time, a mixed solution of 694 g (10.2 mol) of 50% hydrogen peroxide and 118 g of 85% phosphoric acid was gradually dropped in the flask over one hour while maintaining 80 ° C. The reaction is carried out for 12 hours while paying attention to decomposition of per formic acid produced during the reaction. After completion of the reaction, the organic layer was separated, washed with water until the pH became neutral, and then dried under reduced pressure and filtered to obtain the product. The oxygen content was measured by AOCS cd 9-57, and 5.1% (calculated value: 5.4% The value was 3.3.
[실시예 6][Example 6]
온도계, 환류냉각기 및 교반기가 부착된 5L 4구 플라스크에 올레산메틸 에스테르 2,000g을 투입하고 서서히 교반하면서 80℃로 가열한 후 80% 포름산 184g(3.2몰)을 상기 플라스크에 1시간에 걸쳐 서서히 적하하고, 동시에 50% 과산화수소 694g(10.2몰)과 85% 인산 118g의 혼합용액을 플라스크내에 2시간에 걸쳐 서서히 적가하면서 80℃를 계속 유지한다. 반응중에 생성된 과포름산의 분해에 유의하면서 12시간동안 반응시킨다. 반응 종결 후 유기층을 분리하여 pH가 중성이 될 때까지 수세한 후 감압건조 및 여과하여 생성물을 얻고, 이를 AOCS cd 9-57방법으로 산소함량을 측정한 결과 5.2%(이론치 : 5.4%), 요오드값은 3.2였다.Neck flask equipped with a stirrer, a thermometer, a reflux condenser, and a stirrer was charged with 2,000 g of oleic acid methyl ester, and the mixture was heated to 80 DEG C with gentle stirring. 184 g (3.2 mol) of 80% formic acid was slowly added dropwise to the flask over one hour , And at the same time, a mixed solution of 694 g (10.2 mol) of 50% hydrogen peroxide and 118 g of 85% phosphoric acid was slowly dropped in the flask over 2 hours while maintaining 80 ° C. The reaction is carried out for 12 hours while paying attention to decomposition of per formic acid produced during the reaction. After completion of the reaction, the organic layer was separated, washed with water until the pH became neutral, and then dried under reduced pressure and filtered to obtain a product. The oxygen content of the product was measured by AOCS cd 9-57 and found to be 5.2% (theoretical value: 5.4% The value was 3.2.
[실시예 7][Example 7]
온도계, 환류냉각기 및 교반기가 부착된 5L 4구 플라스크에 올레산메틸 에스테르 2,000g을 투입하고 서서히 교반하면서 70℃로 가열한 후 80% 포름산 184g(3.2몰)을 상기 플라스크에 30분간에 걸쳐 서서히 적하하고, 동시에 50% 과산화수소 555g(8.20몰)과 85% 인산 118g의 혼합용액을 플라스크내에 1시간에 걸쳐 서서히 적가하면서 70℃를 계속 유지한다. 반응중에 생성된 과포름산의 분해에 유의하면서 10시간동안 반응시킨다. 반응 종결 후 유기층을 분리하여 pH가 중성이 될 때까지 수세한 후 감압건조 및 여과하여 생성물을 얻고, 이를 AOCS cd 9-57방법으로 산소함량을 측정한 결과 4.8%(이론치 : 5.4%), 요오드값은 3.5였다.Neck flask equipped with a stirrer, a thermometer, a reflux condenser, and a stirrer was charged with 2,000 g of oleic acid methyl ester and heated to 70 DEG C with gentle stirring. 184 g (3.2 mol) of 80% formic acid was slowly added dropwise to the flask over 30 minutes , And at the same time, a mixed solution of 555 g (8.20 mol) of 50% hydrogen peroxide and 118 g of 85% phosphoric acid was gradually dropped in the flask over 1 hour while maintaining 70 ° C. The reaction is carried out for 10 hours while paying attention to the decomposition of formic acid formed during the reaction. After completion of the reaction, the organic layer was separated, washed with water until the pH became neutral, and then dried under reduced pressure and filtered to obtain a product. The oxygen content of the product was measured by AOCS cd 9-57. The result was 4.8% (theoretical value: 5.4% The value was 3.5.
[실시예 8][Example 8]
대두유로부터 제조한 혼합 지방산(이는 대두유를 가수분해하여 글리세린 등을 분리해내고 정제한 지방산으로 시중에서 판매하고 있음)을 40℃에서 10시간동안 방치(winterizing)하여 저비점 물질인 스테아르산 등 포화지방산을 제지한 혼합 불포화 지방산을 만들고 이것에 메틸알콜을 가하여 대두혼합 지방산 메틸 에스테르 화합물을 제조한다.Mixed fatty acids made from soybean oil (which is hydrolyzed with soybean oil to isolate glycerin and then purified and sold on the market) are left at 40 ° C for 10 hours to make saturated fatty acids such as stearic acid Mixed unsaturated fatty acids are prepared and methyl alcohol is added to them to prepare soybean mixed fatty acid methyl ester compounds.
온도계, 환류냉각기 및 교반기가 부착된 5L 4구 플라스크에 혼합 지방산 메틸 에스테르 2,000g을 투입하고 서서히 교반하면서 80℃로 가열한 후 80% 포름산 331g(5.7몰)을 상기 플라스크에 1시간에 걸쳐 서서히 적하하고, 동시에 50% 과산화수소 998g(14.6몰)과 85% 인산 118g의 혼합용액을 플라스크내에 2시간에 걸쳐 서서히 적가하면서 80℃를 계속 유지한다. 반응중에 생성된 과포름산의 분해에 유의하면서 10시간동안 반응시킨다. 반응 종결 후 유기층을 분리하여 pH가 중성이 될 때까지 수세한 후 감압건조 및 여과하여 생성물을 얻고, 이를 AOCS cd 9-57방법으로 산소함량을 측정한 결과 8.8%(이론치 : 9.7%), 요오드값은 1.9였다.2,000 g of mixed fatty acid methyl ester was added to a 5 L four-necked flask equipped with a thermometer, a reflux condenser and a stirrer, and heated to 80 ° C while stirring slowly. 331 g (5.7 mol) of 80% formic acid was slowly added dropwise to the flask And at the same time, a mixed solution of 998 g (14.6 mol) of 50% hydrogen peroxide and 118 g of 85% phosphoric acid was gradually dropped in the flask over 2 hours while maintaining 80 ° C. The reaction is carried out for 10 hours while paying attention to the decomposition of formic acid formed during the reaction. After completion of the reaction, the organic layer was separated, washed with water until the pH became neutral, and then dried under reduced pressure and filtered to obtain a product. The oxygen content of the product was measured by AOCS cd 9-57 and found to be 8.8% (theoretical value: 9.7% The value was 1.9.
상기 실시예로부터 알 수 있는 바와 같이, 본 발명에 의한 불포화 지방산 에스테르 화합물에서 약 90% 이상의 이중결합이 에폭시화된 것으로서, 반응율이 월등하고 고 순도의 불포화 지방산 에스테르의 에폭시화물을 얻을 수 있다.As can be seen from the above examples, the unsaturated fatty acid ester compound according to the present invention has about 90% or more of double bonds epoxidized. Thus, it is possible to obtain epoxides of unsaturated fatty acid esters having a high reaction rate and high purity.
상술한 바와 같이, 본 발명의 불포화 지방산 에스테르 화합물의 에폭시화 제조방법에 의하면 플라스크내의 대두유에 불포화 지방산 에스테르 화합물을 투입하고 교반 및 가열한 후 경제적이고, 자연생분해성을 지닌 무독한 고 순도의 불포화 지방산 에스테르의 에폭시화물을 제조할 수 있으며 반응효율이 매우 높다.As described above, according to the method for producing an epoxidation of an unsaturated fatty acid ester compound of the present invention, an unsaturated fatty acid ester compound is added to soybean oil in a flask, followed by stirring and heating, and then an economical and naturally degradable unsaturated fatty acid ester Can be prepared and the reaction efficiency is very high.
Claims (6)
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