KR20100056370A - Manufacturing method of polyolester - Google Patents

Abstract

PURPOSE: A method for manufacturing polyol ester is provided to obtain the polyester of high purity in a short time through ester transesterification of fatty acid and polyol and esterification using an environment-friendly metal catalyst instead of strong acid and strong base. CONSTITUTION: A method for manufacturing polyol ester comprises a step creating a product which includes the polyol ester by chemically reacting a first reactant and polyol of a second reactant under the presence of a solid catalyst. The first reactant comprises pure fatty acid, fatty acid alkyl ester, or a mixture of the pure fatty acid and the fatty acid alkyl ester. The metal catalyst comprises oxides, carbon oxides, and hydroxides of a metal selected from magnesium(Mg), zinc(Zn), titanium(Ti), manganese(Mn), vanadium(V), beryllium(Be), copper(Cu), zirconium(Zr), strontium(Sr), tin(Sn), and barium(Ba).

Description

Method for producing polyol ester {MANUFACTURING METHOD OF POLYOLESTER}

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.

Several theoretical methods of preparing polyol esters have been proposed. A production method in which polyols and fatty acids are synthesized by ester reaction has been proposed, and a production method in which polyols and fatty acid alkyl esters are synthesized by transesterification is also proposed. However, up to now, the only commercially available method for producing a polyol ester is a method of esterifying a polyol and a fatty acid using an acid catalyst to synthesize it.

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. . According to these publications, the polyols used to prepare the polyol esters used pentaerythritol, dipentaerythritol, trimethylolpropane, ethylene glycol As fatty acid, p-toluene sulfonic acid at 150 ~ 250 ℃ using valeric acid, caproic acid, caprylic acid, and capric acid. acid) to give a polyol ester. According to the method disclosed in U.S. Patent No. 6,444,626, 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.

In addition, 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. Oleic acid, isostearic acid, caprylic acid and trimethylolpropane, pentaerythritol, neopentyl, saturated or unsaturated fatty acids having 6 to 20 carbon atoms 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. The time point at which the reaction is completed is determined by acid value measurement, and it is disclosed that the reaction can be obtained in 95% yield when the acid value is 2.4 to 2.8.

In WO 94/10728, 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 is presented. It 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. However, 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. .

In order to solve this problem, 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. Specifically, 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%. At this time, the reaction temperature is very slow and the reaction is not active actively at the synthesis temperature of 180 ° C. or below, but the reaction rate is fast at the temperature above 240 ° C., but the thermal oxidation and the polyol and the acid of low molecular weight evaporate, causing serious evil to the final reactant. Since an influence occurs, it is described that it is suitable to maintain the synthesis temperature at 180 ° C to 240 ° C. Here again, 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.

As a synthesis method without using a catalyst, 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%) and isononanoic acid (isononanoic acid, 50 wt% to 75 wt%) are stirred at 185 ° C. to 190 ° C. under nitrogen and then slowly reacted with increasing temperature to 230 ° C. At this time, 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. Pat. 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 are added dropwise. Sodium hydroxide (NaOH, 0.1wt% to 1.0wt% of reactant) was added as a catalyst and then reduced to 60 Torr during the progress of the reaction. 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.

As such, the synthesis of polyol esters by transesterification of polyols and fatty acid alkyl esters has been studied for a long time, but it does not overcome the fatal problem of low yield as well as long reaction time and complicated purification process. There is a situation.

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 high-purity polyol ester having excellent mass productivity by reacting them under a solid catalyst consisting of at least 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.

In addition, 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. In this case, 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. Here, 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.

(1) 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). , 100 under 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) The product containing the polyol ester was reacted with the second reactant polyol for 0.1 hour to 10 hours at a temperature of 1 torr to 200 torr at a temperature of from 1 ° C. to 350 ° C. according to the chemical reaction scheme shown in FIGS. Create

At this time, 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. In addition, since it is not necessary to separately classify fatty acids and fatty acid alkyl esters as reactants, 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.

At this time, the reaction temperature is maintained in the 100 ~ 350 ℃ 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.

In addition, 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 within the limit of obtaining high conversion.

In addition, 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, and when the reaction time is longer than 10 hours, it is unnecessary because a sufficient conversion is made. 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.

At this time, 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.

In addition, 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, polyglycerin, sorbitol, xylitol, sucrose, or any combination of two or more polyols. .

In addition, 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. At this time, 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 fat and oil. 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 alkyl ester (C17: 1), stearic alkyl ester (C18: 0), oleic alkyl ester (C18: 1), linoleic alkyl ester (C18: 2) , linolenic alkyl ester (C18: 3), ricinoleic alkyl ester (C18: 1-OH), arachidic alkyl ester (C20: 0), gadoleic alkyl ester (C20: 1), elcosadienoic alkyl ester (C20: 2), behenic alkyl Ester (C22: 0), erucic alkyl ester (C22: 1) and lignoceric alkyl ester (C24: 0) can be used.

In addition, as the fatty acid which may be the first reactant, C4 to C24 saturated and unsaturated fatty acids similar to fatty acid alkyl esters are used.

(2) Second step: removing excess fatty acid or excess fatty acid alkyl ester

It is a step of removing excess fatty acid or fatty acid alkyl ester from the product obtained in the first step to increase the reactivity. 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.

However, 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.

(3) removing the solid catalyst from the product after the second step

It is a process of removing a solid catalyst from the product obtained by the 2nd process. Since the catalyst introduced into the first process maintains a solid state, it may be performed by a filtering method such as a simple filter, a pressure reducing filter, or a pressure filter. Here, 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. Similarly, however, this process can also be omitted if the polyol ester is used as a lubricating oil that may contain some catalyst or the like.

As described above, the present invention, 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 ℃ to 350 ℃ 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 polyol ester through a short time reaction through the transesterification reaction or the ester reaction of the first reactant and the second reactant to provide a production method that is easy to commercialize.

In other words, 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 the polyol are magnesium (Mg), zinc (Zn), titanium (Ti), manganese (Mn), vanadium (V), beryllium (Be), copper (Cu), zirconium (Zr), strontium ( Sr), tin (Sn), barium (Ba) can be synthesized by a single solid catalyst composed of any one of oxides, carbonates, hydroxides of any one or more of the above, has the advantage of simplifying the synthesis process of polyol esters .

In addition, 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. By using no strong acid and strong base material it is possible to manufacture the polyol esters environmentally friendly.

Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings.

In the following description, well-known functions or constructions are not described in detail to avoid obscuring the subject matter of the present invention.

Example 1: Standard Reaction Conditions

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. Here, the fatty acid methyl ester as the first reactant was synthesized from soybean oil and methanol. Specifically, 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.

Example


Reaction temperature
(℃)


Reaction pressure
(Torr)

fatty acid
methyl
ester
Volume (g)
Purity (% by weight)


Conversion rate
(%)
Tetra-
ester
(Polyol
ester) tree-
ester D-
ester Mono
ester 1-1 200 10 511.2 98.2 1.4 0.4 0 99.5

As 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. Magnesium (Mg), zinc (Zn), titanium (Ti), manganese (Mn), vanadium (V), beryllium (Be), copper (Cu), zirconium (Zr), strontium while maintaining a reduced pressure range of Torr to 200 Torr Polyol produced by the reaction when the reaction is carried out for 0.1 to 10 hours under a solid catalyst comprising any one of oxides, carbonates, and hydroxides of any one of (Sr), tin (Sn), and barium (Ba) It was confirmed that the purity of the ester is more than 98%, the conversion is also more than 99%.

Comparative Example 1 Preparation of Polyol Ester at Low Temperature

As in 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. To prepare a high purity polyol ester according to the chemical reaction shown in FIG. However, the reaction temperature was set not to 200 ° C but to 80 ° C to react.

That is, after putting MgO 5.1g into the powder catalyst of metal oxide through the flow path 31 inside the 1L reactor 1 shown in FIG. 1, 50 g of pentaerythritol (molecular weight 136.15 g / mol) through the flow path 32. Was introduced into the reactor (1), 511.2 g of fatty acid methyl ester (average molecular weight 290 g / mol) of acid value 1 (containing 0.5% fatty acid) was introduced into the reactor 1 through the reactor 33, and the well was stirred with the stirrer 11. After the mixing, the heater 22 was heated to set the internal temperature at 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 completion of the reaction, the excess fatty acid methyl ester was removed by distillation under reduced pressure, and the powder catalyst was filtered off with 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 2.

compare
Example


Reaction temperature
(℃)


Reaction pressure
(Torr)

fatty acid
methyl
ester
Volume (g)
Purity (% by weight)


Conversion rate
(%)
Tetra-
ester
(Polyol
ester) tree-
ester D-
ester Mono
ester 1-1 80 10 511.2 42.3 26.2 15.8 15.7 73.8

As shown in Table 2, 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.

Comparative Example 2 Preparation of Polyol Ester under High Pressure

As in 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. To prepare a high purity polyol ester according to the chemical reaction shown in FIG. However, the reaction pressure was set to 400 Torr instead of 10 Torr to react.

That is, after putting MgO 5.1g into the powder catalyst as a metal oxide through the flow path 31 inside the 1L reactor 1 shown in FIG. 1, 50 g of pentaerythritol (molecular weight 136.15 g / mol) through the flow path 32. Was introduced into the reactor (1), 511.2 g of fatty acid methyl ester (average molecular weight 290 g / mol) of acid value 1 (containing 0.5% fatty acid) was introduced into the reactor 1 through the reactor 33, and the well was stirred with the stirrer 11. After the mixing, the heater 22 was heated to set the internal temperature at 200 ° C. Then, the dry vacuum pump 21 was connected to the reactor 1, set at 400 Torr, and the reaction was continued for 2 hours under reduced pressure. After completion of the reaction, the excess fatty acid methyl ester was removed by distillation under reduced pressure, and the powder catalyst was filtered off with 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 3.

compare
Example


Reaction temperature
(℃)


Reaction pressure
(Torr)

fatty acid
methyl
ester
Volume (g)
Purity (% by weight)


Conversion rate
(%)
Tetra-
ester
(Polyol
ester) tree-
ester D-
ester Mono
ester 2-1 200 400 511.2 57.3 19.2 10.4 13.1 80.2

As shown in Table 3, 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%.

Example 2 Administration of Various Kinds of Catalysts

In the reactor (1) shown in FIG. 1, 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. . Here, the fatty acid methyl ester as the first reactant was synthesized from soybean oil and methanol. Specifically, after putting various kinds of catalyst into the 1L reactor 1 shown in Figure 1 through the flow path 31, 50g of pentaerythritol (molecular weight 136.15g / mol) through the flow path 32 to the reactor ( 1), 511.2 g of fatty acid methyl ester (average molecular weight 290 g / mol) having an acid value of 50 (including 25% of fatty acids) was added to the jacket reactor (1) and mixed well with the stirrer (11) through the flow path 33. The heater 22 was used to heat the internal temperature at 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 completion of the reaction, the excess fatty acid methyl ester was removed by distillation under reduced pressure, and the powder catalyst was filtered off with 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 4.

Example


Used catalyst
Purity (% by weight)


Conversion rate
(%)
Tetra-
ester
(Polyols
Ter) tree-
ester Di-ester Mono
ester 2-1 Mg (OH) 2
5.1 g 99.2 0.6 0.2 0 99.8 2-2 CaO 5.1g 98.9 1.1 0 0 99.7 2-3 CaCO3 4.5g 97.2 1.7 0.9 0.2 99.0 2-4 TiO2 5.1g 96.3 2.0 1.4 0.3 98.6 2-5 CuO 3.7g 96.7 2.6 0.5 0.2 99.0 2-6 ZrO 3.7g 97.1 2.5 0.3 0.1 99.2

As shown in Table 4, magnesium (Mg), zinc (Zn), titanium (Ti), manganese (Mn), vanadium (V), beryllium (Be), copper (Cu), zirconium (Zr), strontium (Sr ), Tin (Sn), barium (Ba) by applying a solid catalyst consisting of at least one of any one of oxides, carbonates, hydroxides, while maintaining the temperature range and the reduced pressure range of the reactor 1, etc. 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.

Example 3: Reaction with Various Kinds of Polyols

Using a reactor (1) shown in FIG. 1, 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. Here, the fatty acid methyl ester as the first reactant was synthesized from palm oil and methanol.

Specifically, 5.1g of powder catalyst MgO, which is a metal oxide, is introduced into the 1L reactor 1 shown in FIG. 1 through the flow path 31, and then various kinds of polyols are converted into the second reactant through the flow path 32. Into the reactor (1), and through the flow path (33), 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. After mixing well with the stirrer 11, the inside temperature was set to 180 degreeC with the heater 22, and it heated. 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 completion of the reaction, the excess fatty acid methyl ester was removed by distillation under reduced pressure, and the powder catalyst was filtered off with 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 5.

Example

Polyol

fatty acid
Alkyl ester amount

Purity (% by weight)
Conversion rate
Polyol esters 3-1 dipentaerythritol
70 g 560.9 g 98.2 99.1 3-2 trimethylolpropane
60 g 455.6 g 97.3 98.8 3-3 neopentylglycol
100 g 652.1 g 99.1 99.6 3-4 polyethylene glycol
400 200 g 339.6g 98.7 99.4 3-5 glycerin 50g 553.2 g 98.7 98.1 3-6 sorbitol 50g 559.3 g 95.9 97.2

As shown in Table 13, 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.

Example 4: Reaction of Pure Fatty Acid with Polyol

Using a reactor (1) shown in FIG. 1, 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. Here, the pure fatty acid as the first reactant was synthesized from palm oil and water.

Specifically, 5.1 g of powdered catalyst MgO, which is a metal oxide, is placed in the 1L reactor 1 shown in FIG. 1 through the flow path 31, and then pentaerythritol (molecular weight 136.15 g / mol) through the flow path 32. 50 g was introduced into the reactor 1, 472.4 g of fatty acids (average molecular weight 268 g / mol) were introduced into the reactor 1 through the flow passage 33, mixed well with the stirrer 11, and then inside the heater 22. Heated by setting the temperature to 200 ° C. Then, 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. After completion of the reaction, the fatty acid added in excess was distilled off under reduced pressure, and the 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 6.

Example
Purity (% by weight)


Conversion rate
(%)
Tetra-
ester
(Polyol
ester) tree-
ester Di-ester Mono
ester 4-1 97.4 1.8 0.5 0.3 99.1

As shown in Table 6, even when the first reactant is not only fatty acid alkyl ester but also pure fatty acid, 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%.

Although the preferred embodiments of the present invention have been described above by way of example, the scope of the present invention is not limited only to these specific embodiments, and may be appropriately changed within the scope described in the claims.

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

4 is a chemical reaction formula for preparing a polyol ester using a polyol and a fatty acid as a reactant

Claims (10)

A first reactant consisting of at least one of pure fatty acids, fatty acid alkyl esters, and mixtures of pure fatty acids and fatty acid alkyl esters is reacted with a polyol, which is the second reactant, including magnesium (Mg), zinc (Zn), and titanium (Ti). , Oxide of manganese (Mn), vanadium (V), beryllium (Be), copper (Cu), zirconium (Zr), strontium (Sr), tin (Sn), barium (Ba), carbonate, hydroxide A product generation step of chemically reacting under a solid state catalyst consisting of any one or more of the above to produce a product comprising a polyol ester; Method for producing a polyol ester, characterized in that comprising a. The method of claim 1, The product production step is a method for producing a polyol ester, characterized in that the reaction is carried out for 0.1 to 10 hours while maintaining a pressure of 1 Torr to 200 Torr at a temperature of 100 ℃ to 350 ℃. 3. The method of claim 2, The equivalent ratio of the content of the first reactant and the second reactant is 1: 1 to 10: 1 method for producing a polyol ester. The method of claim 3, wherein The solid catalyst is a method for producing a polyol ester, characterized in that administered by 0.01wt% to 10wt% of the first reactant. 3. The method of claim 2, Removing fatty acids or fatty acid alkyl esters from the product; Method for producing a polyol ester, characterized in that it further comprises. 3. The method of claim 2, Removing the solid catalyst from the product; Method for producing a polyol ester, characterized in that it further comprises. The method of claim 6, Removing the solid catalyst from the product; Method for producing a polyol ester, characterized in that it further comprises. The fatty acid alkyl ester according to any one of claims 1 to 7, Soybean oil, rapeseed oil, palm oil, sunflower oil, corn oil, cottonseed oil, castor oil, jatropha oil, coconut oil, palm kernel oil, fish oil, tallow oil, lard, or two or more of these vegetable oils, which are animal or vegetable oils. A process for producing a polyol ester, characterized in that the mixture is C4 to C24 fatty acid alkyl ester obtained by transesterifying any one or more of alcohols having 1 to 4 carbon atoms. The method according to any one of claims 1 to 7, The pure fatty acid is a method for producing a polyol ester, characterized in that the fatty acid of C4 to C24. The method according to any one of claims 1 to 7, The polyol is pentaerythritol, di-pentaerythritol, tri-methylolpropane, trimethylolpropane, neopentyl glycol, polyethylen glycol, polypropylene glycol ), Glycerin (glycerin), polyglycerin (polyglycerin), sorbitol (sorbitol), xylitol (xylitol), sucrose (sucrose) any one or a combination thereof.

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