WO2010058918A2 - Procédé de préparation d'ester de polyol - Google Patents

Procédé de préparation d'ester de polyol Download PDF

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WO2010058918A2
WO2010058918A2 PCT/KR2009/006390 KR2009006390W WO2010058918A2 WO 2010058918 A2 WO2010058918 A2 WO 2010058918A2 KR 2009006390 W KR2009006390 W KR 2009006390W WO 2010058918 A2 WO2010058918 A2 WO 2010058918A2
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fatty acid
polyol
ester
reactant
polyol ester
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PCT/KR2009/006390
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English (en)
Korean (ko)
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WO2010058918A3 (fr
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유정우
장혜련
형희준
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(주)에스엠피오티
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/78—Preparation processes
    • C08G63/82—Preparation processes characterised by the catalyst used
    • C08G63/83—Alkali metals, alkaline earth metals, beryllium, magnesium, copper, silver, gold, zinc, cadmium, mercury, manganese, or compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
    • C11C3/00—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom
    • C11C3/04—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by esterification of fats or fatty oils
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/03—Preparation of carboxylic acid esters by reacting an ester group with a hydroxy group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/78—Preparation processes
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
    • C11C3/00—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom
    • C11C3/003—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by esterification of fatty acids with alcohols

Definitions

  • the present invention relates to a catalyst used to prepare a polyol ester and a method for producing a high purity polyol ester using the same, comprising a pure fatty acid and a fatty acid alkyl ester or a mixture containing the same and a polyol having two or more hydroxyl groups (-OH). It relates to a process for producing high purity polyol esters by reacting under a solid catalyst and removing fatty acids and fatty acid alkyl esters in the reaction mixture.
  • the method for synthesizing polyol esters using acid catalysts can be found in patent publications or patent publications filed by world-renowned companies such as IFP, Inventor AG, Ethyl Corp, Ruhrchemie, Esso, Bp Chemical, Sell, Geigy, etc. .
  • the polyols used to prepare the polyol esters used pentaerythritol, di-pentaerythritol, trimethylolpropane, ethylene glycol, As fatty acid, p-toluene sulfonic acid at 150 ⁇ 250 °C using valeric acid, caproic acid, caprylic acid, and capric acid. ) Under a catalyst to obtain a polyol ester.
  • an excess of pentaerythritol, heptanoic acid, and caprylic-capric acid are first reacted at 150 to 200 ° C under sulfuric acid catalyst.
  • Poly-diols other than pentaerythritol, di-pentaerythritol, tri-pentaerythritol, and tetra-pentaerythritol were synthesized first, and then 10% to 25% excess heptanoic acid and capryl-capric acid (caprylic-capric acid). ) was added to obtain a poly (neopentylpolyol) ester.
  • Korean Unexamined Patent Publication No. 194-561 discloses a method for producing a polyol ester by an ester reaction which is reacted under an acid catalyst.
  • a polyhydric alcohol such as glycol (neopentylglycol) is used under a nitrogen atmosphere at a temperature of 180 to 240 ° C. for 5 to 24 hours under a p-toluene sulfuric acid catalyst. It is disclosed that the time point at which the reaction is completed is determined by acid value measurement and can be obtained in 95% yield by terminating the reaction when the acid value is 2.4 to 2.8.
  • an acid or anhydride and a mono-alcohol or poly hydroxyl are synthesized using an acid catalyst such as titanium, zirconium, and tin-based catalysts to synthesize 95% of a polyol ester.
  • the method includes internally recycling at least about 2.5 volumes of reaction mixture per minute to improve the rate of conversion, thereby removing water with steam while continuously mixing the reaction mixture in the reaction vessel.
  • the polyol ester synthesized as described above has a problem in that the catalyst remains in the reactant as it is prepared using an acid catalyst, thereby causing problems such as reverse reaction, discoloration and oxidation, and it is difficult to remove the catalyst. .
  • Korean Patent Publication No. 10-169565 proposes a method for synthesizing a polyol ester by a reaction without using a catalyst at a high temperature.
  • polyhydric alcohols such as oleic acid, isostearic acid, caprylic acid and trimethylolpropane, pentaerythritol, and neopentylglycol which are saturated or unsaturated fatty acids having 6 to 20 carbon atoms are used.
  • the reaction can be carried out at a temperature of 120 to 260 ° C. for 5 to 40 hours under a nitrogen atmosphere to obtain a yield of 95%.
  • the reaction temperature is very slow and the reaction is not active actively at the synthesis temperature of 180 ° C. or lower, but the reaction rate is fast at 240 ° C. or higher, but serious adverse effects on the final reactant are caused by thermal oxidation and evaporation of polyol and low molecular weight acid. Since this occurs, it is described that it is suitable to maintain the synthesis temperature at 180 ° C to 240 ° C.
  • a technique is disclosed in which the end point of the reaction can be obtained in 95% yield by measuring the acid value to terminate the reaction when the acid value is 2.0 to 2.5.
  • US Patent No. 6,436,881 discloses a process for preparing polyol esters by esterification of fatty acids and polyols under a catalyst.
  • Industrial di-pentaerythritol a substance containing from about 80 wt% to 85 wt% of di-pentaerythritol, about 10 wt% of mono-pentaerythritol, and about 10 wt% of tri-tetra pentaerythritol
  • heptanoic acid and capryl -Caproic acid 25 wt% to 50 wt%)
  • isononanoic acid isononanoic acid, 50 wt% to 75 wt%) are stirred at 185 ° C.
  • the amount of fatty acid is required in excess of about 5wt% to 10wt% of the polyol amount. Fatty acids in excess are used for a complete reaction. Di-pentaerythritol has also been used for industrial purposes, and the reaction conditions persist until the hydroxyl number in the reaction mixture is less than 3.0. After completion of the reaction, the excess fatty acid is removed by vacuum distillation and the remaining acid is removed by alkali.
  • the method for producing a polyol ester by reacting under a catalyst has the advantage of avoiding the problem of discoloration or oxidation without the use of an acid catalyst, which leads to the elimination of acid catalysts, thereby eliminating the need for catalyst removal. It is not suitable for commercialization because it requires high and long reaction time.
  • Synthesis method by transesterification of polyol and fatty acid alkyl ester another method of preparing polyol ester, has not been commercialized, but has been studied as a method to solve the difficulty of the synthesis method by ester reaction of polyol and fatty acid. come.
  • EP 0,646,638 discloses a process for the synthesis of carboxylic esters. According to this, 5 g of tetraisopropyl orthotitanate was added dropwise as a catalyst to 408 g (3 moles) of pentaerythritol and 660 g (3 moles) of CE1270 methyl ester (C12 75% + C14 25%), and the reaction was carried out in nitrogen. Heated to 220 ° C. In this state, no reaction occurs. Lower the reaction to 130 ° C. and add 250 g of acetic acid. A small amount of p-toluene sulfuric acid was added to the reaction and reacted at 200 ° C. for 48 hours to remove 60 g of methanol. Add 450 g of acetic anhydride and stir at 150 ° C. until acetic acid / water no longer release. The remaining residue can be filtered to give the final product penaerythitol ester.
  • U.S. Patent No. 5,885,946 describes the preparation of polyol esters by reacting vegetable oils, such as rapeseed oil, soybean oil, and tallow, under an alkali catalyst to produce fatty acid methyl esters, and then reacting fatty acid methyl esters with neopentylpolyol.
  • a method is disclosed. Specifically, 0.65 mole of fatty acid methyl ester is added dropwise to a three neck flask equipped with a thermometer, a cooler, a stirrer, and a pressure reducing device, and then heated to 50 ° C to 110 ° C. And 0.19 mol of tri-methylol propanes is added dropwise.
  • Sodium hydroxide NaOH, 0.1wt% to 1.0wt% of reactant
  • the reaction temperature is reacted at 50 ° C to 110 ° C for 1 hour to 7 hours and then at 110 ° C to 160 ° C for 1 hour to 10 hours. While the reaction is in progress, it is checked by thin layer chromatography and infrared spectrum to determine the end of the reaction. After completion of the reaction, the mixture was washed with aqueous acid and filtered, washed with water and dried over anhydrous sodium sulfate to purify the reaction. It is disclosed that the final reaction can be confirmed by liquid chromatography and infrared spectrum to yield 90.5% yield.
  • the present invention has been made to solve the above problems, and any one or more of pure fatty acids, fatty acid alkyl esters, mixtures of pure fatty acids and fatty acid alkyl esters as the first reaction material and polyol as the second reaction material magnesium ( Mg), zinc (Zn), titanium (Ti), manganese (Mn), vanadium (V), beryllium (Be), copper (Cu), zirconium (Zr), strontium (Sr), tin (Sn), barium ( It is an object of the present invention to provide a method for synthesizing a polyol ester of high purity and high purity by reacting them under a solid catalyst consisting of any one of oxides, carbonates, and hydroxides of any one of Ba).
  • Another object of the present invention is not only to prepare a polyol ester by esterifying a fatty acid and a polyol, but also to react a polyol and an ester using the same catalyst for not only pure fatty acids or fatty acid alkyl esters but also mixtures of fatty acid alkyl esters and pure fatty acids It is to provide a method for producing a polyol ester through the transesterification reaction.
  • the present invention excludes the use of strong acids and strong bases that cause air pollution and water pollution as catalysts, and includes magnesium (Mg), zinc (Zn), titanium (Ti), manganese (Mn), and vanadium (V). ),
  • An environmentally friendly metal made of at least one of oxides, carbonates, and hydroxides of any one of beryllium (Be), copper (Cu), zirconium (Zr), strontium (Sr), tin (Sn), and barium (Ba) It is another object to produce high purity polyol esters having a purity of at least 95% by replacement with a catalyst.
  • the present invention in order to achieve the object as described above, the present invention, magnesium (Mg), zinc (Zn), titanium (Ti), manganese (Mn), vanadium (V), beryllium (Be), copper (Cu ), Pure fatty acids and fatty acid alkyl esters under a solid catalyst consisting of at least one of oxides, carbonates, and hydroxides of any one of zirconium (Zr), strontium (Sr), tin (Sn), and barium (Ba); Is a process for producing a high purity polyol ester through the chemical reaction shown in Figures 2 to 4 of the mixture and polyol.
  • the catalyst used is a solid catalyst composed of any one or more of metal carbonate, hydroxide, and oxide, which is environmentally friendly because it does not use strong acids and strong bases, which cause air pollution or water pollution, as catalysts. It has the advantage of not causing pollution.
  • the solid catalyst may be formed in the form of a powder, but may also be formed in the form of agglomerates such as beads or pellets.
  • the process is as follows.
  • first step a reaction step for producing a polyol ester
  • the first reactant consisting of at least one of pure fatty acid, fatty acid alkyl ester and mixture of pure fatty acid and fatty acid alkyl ester is magnesium (Mg), zinc (Zn), titanium (Ti), manganese (Mn), vanadium (V).
  • Mg magnesium
  • Zn zinc
  • Ti titanium
  • Mn manganese
  • V vanadium
  • a solid catalyst consisting of at least one of oxides, carbonates, and hydroxides of any one of beryllium (Be), copper (Cu), zirconium (Zr), strontium (Sr), tin (Sn), and barium (Ba)
  • Be beryllium
  • Cu copper
  • Zr zirconium
  • Sr strontium
  • Sn tin
  • barium barium
  • the catalyst is capable of synthesizing fatty acid alkyl esters and polyols without the use of strong acids and strong base materials that cause air pollution or water pollution as a catalyst, it is also environmentally friendly and does not cause pollution.
  • polyol esters can be prepared at the same time even when these components are mixed, so that the process for producing polyol esters is also very simple.
  • the reaction temperature is maintained in the 100 ⁇ 350 °C range. If the reaction temperature does not reach 100 ° C, the reaction conversion rate of the polyol ester is lowered, and if the reaction temperature exceeds 350 ° C, energy consumption increases due to unnecessary high temperature, which is not preferable.
  • the reduced pressure of the reactor is reacted while maintaining 1 Torr to 200 Torr to increase the reaction rate through the rapid removal of water or alcohol generated during the reaction.
  • the alcohol produced during the reaction produces methanol, ethanol, propanol, butanol, etc., depending on the type of fatty acid alkyl ester.
  • As the pressure decreases a higher conversion can be achieved, but too low pressure increases the process cost, so it is better to set the pressure to the minimum required to obtain a high conversion.
  • the reaction time of the first reactant and the second reactant takes 0.1 hours to 10 hours. As the reaction time increases, a higher conversion can be obtained, but when the reaction time is shorter than 0.1 hour, sufficient reaction does not occur. That is, the present invention, since it is possible to prepare a polyol ester having a high purity of 95% or more by synthesizing the first reactant and the polyol in a relatively short time compared to the prior art, it has the advantage of being very suitable for commercialization.
  • the solid catalyst used in the above reaction is used in the range of 0.01wt% to 10wt% of the first reactant. This is because when the amount of the solid catalyst is less than 0.01wt%, the reaction conversion rate of the polyol ester is lowered, and when it exceeds 10wt%, energy consumption for the catalyst removal after the reaction is excessive.
  • the amount of fatty acid and fatty acid alkyl ester used in the above reaction is one of the regulatory elements to increase the reactivity.
  • the equivalent ratio of pure fatty acids and fatty acid alkyl esters or mixtures containing both and polyol content is preferably used in the range of 1: 1 to 10: 1. If the amount of the fatty acid and fatty acid alkyl ester used is less than 1 equivalent, the reaction conversion rate of the polyol ester is lowered. If it exceeds 10 equivalents, the energy consumption for the separation of the fatty acid and fatty acid alkyl ester is increased after the reaction. Not desirable
  • the polyol is neopentyl polyol (neopentylpolyol) -based pentaerythritol (pentaerythritol), di-pentaerythritol (dipentaerythritol), tri-methylol propane (trimethylolpropane), neopentyl glycol (neopentylglycol), polyethylene glycol (polyethylene glycol ), Polypropylene glycol, glycerin (glycerin), polyglycerin (polyglycerin), sorbitol (sorbitol), xylitol (xylitol), sucrose (sucrose) or a polyol having a combination of two or more.
  • neopentyl polyol neopentylpolyol
  • pentaerythritol pentaerythritol
  • di-pentaerythritol di
  • the fatty acid alkyl ester which is one of the first reactants, is used as a saturated and unsaturated fatty acid alkyl ester of C4 to C24 produced by transesterification of copper, vegetable oil and alcohol containing fatty acids.
  • the copper and vegetable oils are soybean oil, rapeseed oil, palm oil, sunflower oil, corn oil, cottonseed oil, castor oil, jatropha oil, coconut oil, palm kernel oil, fish oil, tallow, lard and waste oil and two of them. The above is applied to the combined fats and oils.
  • the alcohol is any one of methanol, ethanol, propanol, butanol, and the like, which is a lower alcohol having 1 to 4 carbon atoms, or an alcohol of a combination of two or more thereof.
  • One of the first reactants C4 to C24 fatty acid alkyl esters, butyric alkyl ester (C4: 0), caproic alkyl ester (C6: 0), caprylic alkyl ester (C8: 0), capric alkyl ester (C10: 0 ), lauric alkyl ester (C12: 0), myristic alkyl ester (C14: 0), myristoleic alkyl ester (C14: 1), pentadecanoic alkyl ester (C15: 0), palmitic alkyl ester (C16: 0), palmitoleic alkyl ester (C16: 1), margaric alkyl ester (C17: 0), margaroleic alky
  • fatty acid which may be the first reactant
  • C4 to C24 saturated and unsaturated fatty acids similar to fatty acid alkyl esters are used.
  • the removal method may be in various forms, and conventional distillation methods performed in the art, for example, distillation using a single distillation, vacuum distillation, fractional distillation, thin film distillation, and the like may be used.
  • this process can be omitted when the polyol ester is used as a lubricating oil that may contain some fatty acid or fatty acid alkyl ester.
  • the catalyst introduced into the first process may be performed by a filtering method such as a simple filter, a pressure reducing filter, or a pressure filter.
  • the solid catalyst may be formed in the form of agglomerates such as beads or pellets, but may be formed in powder form. Even if it is formed in powder form, the solid powder catalyst remains in a heterogeneous state in the product which has passed through the second process, and can be easily separated by a filtering method.
  • this process can also be omitted if the polyol ester is used as a lubricating oil that may contain some catalyst or the like.
  • the first reaction material consisting of at least one of pure fatty acid, fatty acid alkyl ester, a mixture of pure fatty acid and fatty acid alkyl ester, magnesium (Mg), zinc (Zn), titanium (Ti) , Oxide of manganese (Mn), vanadium (V), beryllium (Be), copper (Cu), zirconium (Zr), strontium (Sr), tin (Sn), barium (Ba), carbonate, hydroxide Under a solid catalyst consisting of any one or more of which is maintained at a pressure of 1 Torr to 200 Torr at a temperature of 100 °C to 350 °C for 0.1 hour to 10 hours to react with the polyol which is a second reactant to produce a product comprising a polyol ester Steps; Removing fatty acids or fatty acid alkyl esters from the product; Removing the solid catalyst from the product; It is configured to include, it is possible to obtain a high-purity
  • the present invention not only enables the synthesis of fatty acids and polyols to produce polyol esters with high purity, but also the synthesis of fatty acid alkyl esters and polyols to produce polyol esters with high purity.
  • the mixed material and polyol are magnesium (Mg), zinc (Zn), titanium (Ti), manganese (Mn), vanadium (V), beryllium (Be), copper (Cu), zirconium (Zr), and strontium (Sr).
  • Tin (Sn), barium (Ba) can be synthesized by a single solid catalyst consisting of any one or more of oxides, carbonates, hydroxides of any one of the above, has the advantage of simplifying the synthesis process of polyol esters.
  • the present invention not only can be utilized as a homogeneous catalyst that is not dissolved in the product but also as a homogeneous catalyst that is dissolved in a conventionally presented product, and the solid catalyst used in the present invention is unlikely to cause air pollution or water pollution.
  • the solid catalyst used in the present invention is unlikely to cause air pollution or water pollution.
  • FIG. 1 is a schematic diagram of a configuration of a reactor for producing a polyol ester according to the present invention
  • 2 is a chemical reaction formula for preparing a polyol ester using a polyol and a fatty acid methyl ester as a reactant.
  • Figure 3 is a chemical reaction for preparing a polyol ester using a polyol and fatty acid ethyl ester as a reaction material
  • a high-purity polyol ester was prepared according to the chemical reaction shown in FIG. 2 using fatty acid methyl ester as a first reactant and polyol pentaerythritol as a second reactant using the reactor 1 shown in FIG. Prepared.
  • the fatty acid methyl ester as the first reactant was synthesized from soybean oil and methanol.
  • 5.1 g of MgO is introduced into the 1L reactor 1 shown in FIG. 1 through a flow path 31 as a solid powder catalyst, which is a metal oxide, and then pentaerythritol (molecular weight 136.15 g /) through the flow path 32.
  • mol) 50 g was introduced into the reactor 1, 511.2 g of a fatty acid methyl ester (average molecular weight 290 g / mol) having an acid value 1 (including 0.5% fatty acid) was introduced through a flow passage 33 into a jacket reactor 1, followed by an agitator (11). After mixing well), the heater 22 was heated to an internal temperature of 200 ° C. Then, the dry vacuum pump 21 was connected to the reactor 1, set at 10 Torr, and the reaction was continued for 2 hours under reduced pressure. After the completion of the reaction, the excess fatty acid methyl ester was removed by distillation under reduced pressure, and the non-homogeneous powder catalyst was filtered off using a reduced pressure filter to obtain a polyol ester. The polyol ester product was analyzed by liquid chromatography IATROSCAN and indicated purity and conversion. The analysis results are shown in Table 1.
  • the equivalent ratio of the content of the first reactant (fatty acid alkyl ester) and the second reactant (polyol) is 1: 1 to 10: 1, and the temperature range is 100 ° C to 350 ° C.
  • Example 1 a fatty acid methyl ester prepared by synthesizing soybean oil and methanol using the reactor 1 shown in FIG. 1 is used as a first reactant, and pentaerythritol, a polyol, is used as a second reactant.
  • the reaction temperature was set not to 200 ° C but to 80 ° C to react.
  • the pentaerythritol and fatty acid methyl ester when the reaction temperature is set to 80 ° C. lower than 100 ° C. even if the equivalence ratio and the reduced pressure range of the contents of the first and second reactants are properly maintained.
  • the purity of the polyol ester prepared by the reaction was only 42.3% and the conversion was 73.8%, and it was confirmed that the reactivity was not good.
  • Example 1 a fatty acid methyl ester prepared by synthesizing soybean oil and methanol using the reactor 1 shown in FIG. 1 is used as a first reactant, and pentaerythritol, a polyol, is used as a second reactant.
  • the reaction pressure was set to 400 Torr instead of 10 Torr to react.
  • pentaerythritol and fatty acid may be reduced when the reaction pressure is set to 400 Torr lower than 200 Torr even if the equivalence ratio and temperature range of the content of the first reactant and the second reactant are properly maintained.
  • the purity of the polyol ester prepared by the reaction of the methyl ester is only 57.3% and the conversion was also confirmed that the reactivity was not good at 80.2%.
  • polyol esters of high purity were prepared according to the chemical reaction shown in FIG. 2 using fatty acid methyl ester as a first reactant and polyol as a second reactant using various kinds of catalysts.
  • the fatty acid methyl ester as the first reactant was synthesized from soybean oil and methanol.
  • the polyol ester prepared by reacting a fatty acid methyl ester as a reactant with a polyol as a second reactant has a high purity of 96% or more, and a conversion rate of 98% or more.
  • a high purity polyol ester was prepared according to the chemical reaction formula shown in FIG. 2 using a fatty acid methyl ester as a first reactant and various kinds of polyols as a second reactant.
  • the fatty acid methyl ester as the first reactant was synthesized from palm oil and methanol.
  • powder catalyst MgO which is a metal oxide
  • various kinds of polyols are converted into the second reactant through the flow path 32.
  • the fatty acid methyl ester (average molecular weight 290 g / mol) having an acid value of 100 (including 50% of fatty acids) was added to the jacket reactor (1) corresponding to 1.2 equivalents of the polyol.
  • the inside temperature was set to 180 degreeC with the heater 22, and it heated.
  • the dry vacuum pump 21 was connected to the reactor 1, set at 10 Torr, and the reaction was continued for 2 hours under reduced pressure.
  • a polyol ester prepared by reacting a fatty acid methyl ester as a first reactant with a polyol of various kinds as a second reactant and a chemical reaction shown in FIG. 2 has a high purity of 95% or more. It was found that the conversion rate was also high as 97% or more.
  • a high purity polyol ester was prepared according to the chemical reaction shown in FIG. 4 using pure fatty acid as a first reactant and polyol as a second reactant.
  • the pure fatty acid as the first reactant was synthesized from palm oil and water.
  • powdered catalyst MgO which is a metal oxide
  • pentaerythritol molecular weight 136.15 g / mol
  • 50 g was introduced into the reactor 1
  • 472.4 g of fatty acids average molecular weight 268 g / mol
  • the dry vacuum pump 21 was connected to the reactor 1, set at 20 Torr, and the reaction was continued for 2 hours under reduced pressure.
  • the polyol ester prepared by reacting the polyol with the chemical reaction shown in FIG. 4 has a high purity of 97% or more. In addition, the conversion rate was found to be higher than 99%.

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Abstract

La présente invention concerne un procédé de préparation d'ester de polyol. Le procédé comprend les étapes consistant à: faire réagir un premier réactif avec un second réactif suivant un rapport équivalent compris entre 1:1 et 10:1 à une température comprise entre 100 et 350℃ dans des conditions de pression comprises entre 1 et 200 Torr pendant une durée comprise entre 0,1 et 10 heures en présence d'un catalyseur solide afin d'obtenir un produit contenant de l'ester de polyol; à éliminer du produit, les acides gras ou les esters alkyliques d'acides gras; et à éliminer du produit, le catalyseur solide. Le premier réactif comprend au moins un acide gras pur et/ou un ester alkylique d'acide gras et/ou un mélange d'acides gras purs et d'esters akyliques d'acides gras et le second réactif est le polyol. Le catalyseur solide comprend au moins un oxyde et/ou un carbonate et/ou hydroxyde de tout type sélectionné parmi le magnésium (Mg), le zinc (Zn), le titane (Ti), le manganèse (Mn), le vanadium (V), le béryllium (Be), le cuivre (Cu), le zirconium (Zr), le strontium (Sr), l'étain (Sn) et le barium (Ba). Cette invention porte sur un procédé de préparation d'ester de polyol de grande pureté d'un degré de pureté supérieur ou égal à 95% par une synthèse simultanée d'esters alkyliques d'acides gras et d'acides gras avec du polyol au moyen du catalyseur solide pendant un temps de réaction court ne dépassant pas 10 heures.
PCT/KR2009/006390 2008-11-19 2009-11-02 Procédé de préparation d'ester de polyol WO2010058918A2 (fr)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013050854A1 (fr) * 2011-10-03 2013-04-11 Industrial Agraria La Palma Limitada, Indupalma Ltda. Procédés permettant d'obtenir un polyol à partir d'huile de palme, polyols obtenus selon ces procédés, produits dérivés de ce polyol et procédé de préparation
CN112574029A (zh) * 2019-09-27 2021-03-30 中国石油天然气股份有限公司 一种多元醇酯的制备方法

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US5885946A (en) * 1994-09-07 1999-03-23 Raision Tehtaat Oy Ab Process for preparing a synthetic ester from a vegetable oil

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Publication number Priority date Publication date Assignee Title
WO2013050854A1 (fr) * 2011-10-03 2013-04-11 Industrial Agraria La Palma Limitada, Indupalma Ltda. Procédés permettant d'obtenir un polyol à partir d'huile de palme, polyols obtenus selon ces procédés, produits dérivés de ce polyol et procédé de préparation
CN112574029A (zh) * 2019-09-27 2021-03-30 中国石油天然气股份有限公司 一种多元醇酯的制备方法
CN112574029B (zh) * 2019-09-27 2023-01-10 中国石油天然气股份有限公司 一种多元醇酯的制备方法

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