JP2010148456A - Method for producing polyol partial ester - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for selectively producing a polyol partial ester. <P>SOLUTION: The method includes the following steps: a hindered polyol and a fatty acid methyl ester are reacted with each other under a solventless condition, under a reduced pressure condition of 1-90 kPa of reduced-pressure degree, and at 20-100°C, in the presence of a lipase. In this step, Preferable embodiments are such that the fatty acid methyl ester is a 6-18C saturated or unsaturated methyl ester, and the hindered polyol is either trimethylolpropane or neopentyl glycol. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a method for producing a polyol partial ester, and more particularly to a method for producing a polyol partial ester in which a hindered polyol and a fatty acid methyl ester are reacted with lipase under mild conditions.

Conventionally, alkali catalysts and acid catalysts are well known as catalysts for the broad esterification reaction of polyols. For example, when baking soda is used as the catalyst, there are problems that the reaction temperature is high (150 to 220 ° C.) and it is difficult to control the formation of the partially esterified product.
In order to advance the esterification of the polyol under mild conditions and to facilitate the treatment of the catalyst in the purification process, the esterification of the polyol using lipase as a catalyst has been studied.
As a method of esterifying a polyol using lipase as a catalyst, a method is known in which a divalent carboxylic acid ester and an alcohol containing three or more hydroxyl groups are transesterified using lipase in the presence of a water-insoluble organic solvent. (For example, refer to Patent Document 1). However, in this method, since the reaction is carried out in the presence of a water-insoluble organic solvent, there is a problem in mixing and purification.
In addition, as a method of esterifying a polyol using lipase as a catalyst, a method is known in which a polyol having no hydrogen atom on the β-position carbon and a fatty acid are reacted in a water / organic solvent two-phase system in the presence of lipase. (For example, refer to Patent Document 2). However, in this method, since the reaction is carried out in a two-phase system of water / organic solvent, there is a problem in mixing and purification.
In addition, as an esterification of a polyol using lipase as a catalyst, a lipase obtained from a microorganism belonging to the genus Alkaligenes at a temperature of 81 to 130 ° C. is obtained on a molten organic material for transesterification under substantially solvent-free and anhydrous conditions. There is known a method of making it act (for example, see Patent Document 3). However, this method has a problem that the esterification reaction cannot be controlled to selectively produce a partially esterified product.
In addition, as esterification of a polyol using lipase as a catalyst, alcohol and a hydroxy fatty acid and / or a hydroxy fatty acid alkyl ester may be used in the presence of an enzyme, optionally in a solvent, and if necessary, at a pressure lower than atmospheric pressure. And the method of making it react, removing the water or alcohol produced | generated by reaction at the temperature of 20 to 110 degreeC (for example, refer patent document 4). However, this method has a problem that the esterification reaction cannot be controlled to selectively produce a partially esterified product.
In addition, as a method of esterifying a polyol using lipase as a catalyst, a method of esterifying a hydroxyl group-containing compound selected from the group consisting of a monoalcohol and a polyhydric alcohol partial ester in the presence of lipase and a fatty acid is known ( For example, see Patent Document 5). However, this method has a problem that the esterification reaction cannot be controlled to selectively produce a partially esterified product.
In addition, as a method of esterifying a polyol using lipase as a catalyst, a method of selectively esterifying hydroxyl groups at 1-position and 3-position in glycerin is already known, but an equivalent hydroxyl group in a hindered polyol having a large steric hindrance is used. The method of selectively esterifying has not been established yet.

JP 2008-214417 A Japanese Patent Laid-Open No. 62-29684 JP-A-7-79786 JP 2002-191389 A JP 2006-325465 A

  An object of the present invention is to solve the above-described problems and achieve the following objects. That is, this invention aims at providing the manufacturing method of the polyol partial ester which can selectively manufacture a polyol partial ester.

Means for solving the above problems are as follows. That is,
<1> including reacting a hindered polyol with a fatty acid methyl ester using a lipase under a solvent-free condition, under a reduced pressure condition of 1 kPa to 90 kPa in a reduced pressure, and under a temperature condition of 20 ° C. to 100 ° C. This is a process for producing a polyol partial ester.
In the method for producing a partial polyol ester according to <1>, the hindered polyol and the fatty acid methyl ester are solvent-free, under reduced pressure at a degree of vacuum of 1 kPa to 90 kPa, and at 20 ° C. to 100 ° C. Below, lipase is used to react. As a result, a polyol partial ester is selectively produced.
<2> The method for producing a partial polyol ester according to <1>, wherein the fatty acid methyl ester is a saturated or unsaturated methyl ester having 6 to 18 carbon atoms.
<3> The method for producing a polyol partial ester according to any one of <1> to <2>, wherein the hindered polyol is any one of trimethylolpropane and neopentyl glycol.

  ADVANTAGE OF THE INVENTION According to this invention, the said conventional problems can be solved, the said objective can be achieved, and the manufacturing method of the polyol partial ester which can selectively manufacture a polyol partial ester can be provided.

(Method for producing polyol partial ester)
The method for producing a polyol partial ester of the present invention includes at least a reaction step, and further includes other steps appropriately selected as necessary.

<Polyol partial ester>
The polyol partial ester is not particularly limited as long as it is an ester compound of a hindered polyol and has at least one unreacted hydroxyl group of the hindered polyol, and can be appropriately selected according to the purpose. For example, when the hindered polyester is neopentyl glycol, examples include monoesters, and when trimethylolpropane is used, examples include monoesters or diesters, and in the case of pentaerythritol, monoesters. , Diesteri or triester.

<Reaction process>
The reaction step is a step of reacting a hindered polyol and a fatty acid methyl ester with lipase under a solvent-free condition, under a reduced pressure condition of 1 kPa to 90 kPa under reduced pressure, and under a temperature condition of 20 ° C. to 100 ° C. It is.

<< Hindered Polyol >>
The hindered polyol is not particularly limited as long as it is a polyol containing hindered carbon and having two or more hydroxyl groups, and can be appropriately selected according to the purpose. For example, neopentyl glycol, trimethylolethane , Trimethylolpropane, trimethylolbutane, pentaerythritol, dipentaerythritol, and the like.
Among these, neopentyl glycol and trimethylolpropane are preferable because they have an advantage that the reaction proceeds even under a low reaction temperature (under mild conditions).

<< Fatty acid methyl ester >>
The fatty acid methyl ester is not particularly limited as long as it is a methyl ester of a fatty acid having 6 to 18 carbon atoms, and can be appropriately selected according to the purpose. For example, methyl caproate, methyl caprylate, methyl caprate , Methyl laurate, methyl myristate, methyl palmitate, methyl stearate, methyl oleate, methyl palm oleate, and the like.
Among them, methyl caprylate, methyl caprate, and methyl laurate are preferable in that they have a low melting point and can be reacted at low temperatures.

<< Quantitative ratio of fatty acid methyl ester to hindered polyol >>
The quantitative ratio of fatty acid methyl ester to the hindered polyol (fatty acid methyl ester / hindered polyol) is not particularly limited and can be appropriately selected according to the type of raw material and the polyol partial ester to be synthesized. Is preferably 1 to 3 moles when the hindered polyol has 3 hydroxyl groups, 1 to 5 moles are preferred and the hindered polyol has 4 hydroxyl groups. In this case, 1 to 8 times mole is preferable.

<< Decompression degree >>
The degree of decompression is not particularly limited as long as it is 1 kPa to 90 kPa, and can be appropriately selected according to the purpose, but is preferably 3.5 kPa to 90 kPa. If the degree of vacuum is less than 1 kPa, the raw material will azeotrope with the distilled methanol when a low boiling point raw material is used, which is not preferable. If the degree of vacuum exceeds 90 kPa, it is generated in the reaction system. Methanol becomes difficult to distill.

<< Temperature >>
The temperature is not particularly limited as long as it is 20 ° C. to 100 ° C., and can be appropriately selected according to the purpose, but is preferably 45 ° C. to 80 ° C. If the temperature is lower than 45 ° C or higher than 80 ° C, the catalytic activity of the enzyme may decrease and the reaction may not proceed easily.

<< Lipase >>
The lipase is a kind of hydrolase, and can be used as an immobilized enzyme supported on a carrier such as a resin, or can be used as a powder.
The lipase is not particularly limited and may be appropriately selected depending on the intended purpose. Examples include various sources obtained from microorganisms such as the genus Rhizopus, the genus Aspergillus, the genus Rhizopus and the genus Mucor.
The commercial product of the lipase is not particularly limited and may be appropriately selected depending on the intended purpose. And Pro Leather (Amano Enzyme).
Among them, an immobilized lipase commercially available as Novozym (registered trademark) 435 is preferable in that it is difficult to deactivate as a catalyst.
The addition amount of the lipase is not particularly limited and may be appropriately selected depending on the purpose. It is preferably 1% by mass to 10% by mass with respect to the total mass of the hindered polyol and the fatty acid methyl ester, 5 mass% is more preferable. If the amount of the lipase added is less than 1% by mass, the reaction rate may be slow, and if it exceeds 10% by mass, further improvement in selectivity may not be expected. May be undesirable.

<Other processes>
There is no restriction | limiting in particular as said other process, According to the objective, it can select suitably, For example, a refinement | purification process etc. are mentioned.

<< Purification process >>
The purification step is not particularly limited and may be appropriately selected depending on the intended purpose. For example, a catalyst filtration step for separating lipase as a catalyst, a fatty acid for removing residual fatty acid methyl ester by simple distillation And a methyl ester removing step.

  Examples of the present invention will be described below, but the present invention is not limited to these examples.

Example 1
In a flask equipped with a condenser tube, 59.34 g of methyl caprylate (Pastel M-08, manufactured by Lion Corporation, molecular weight 158.24), 10 g of trimethylolpropane (manufactured by Mitsubishi Gas Chemical Co., Ltd., molecular weight 134.18), and 2.28 g of Novozym (registered trademark) 435 (Candida genus, manufactured by Novozyme Japan) as a catalyst is added, under no-solvent conditions, under a reduced pressure condition of 3.5 kPa, and under a temperature condition of 65 ° C. The reaction was carried out for 10 hours while removing the produced methanol. The catalyst (Novozym® 435) was filtered off and the remaining methyl caprylate was removed by simple distillation. As a result of measuring the reaction solution by gas chromatography (HP-5890, manufactured by Hewlett Packard), it was found that trimethylolpropane dicaprylate was obtained with a selectivity of 82%.
In addition, the measurement conditions of gas chromatography are as shown below.
Column: HP ULTRA2
Oven temperature: 80-330 ° C, 10 ° C / min
Vaporization chamber temperature: 330 ° C
Detector temperature: 330 ° C. (FID)
Carrier gas: He

The selectivity (%) is calculated by the following formula (1).
Selectivity (%) = peak area of partially esterified product in reaction solution / peak area of all reaction products in reaction solution × 100 (1)
The total reaction product is a compound other than the raw material, which is generated after the start of the reaction.

(Example 2)
In Example 1, except that the reaction time was changed from 10 hours to 3 hours, the reaction was performed in the same manner as in Example 1, the catalyst was filtered off, and the remaining methyl caprylate was removed by simple distillation, and the reaction was performed. The liquid was measured. As a result, it was found that trimethylolpropane monocaprylate was obtained with a selectivity of 81%.

Example 3
In a flask equipped with a condenser tube, 23.7 g of methyl caprylate (Pastel M-08, manufactured by Lion Corporation, molecular weight 158.24), 10 g of trimethylolpropane (manufactured by Mitsubishi Gas Chemical Co., Inc., molecular weight 134.18), and 2.28 g of Novozym (registered trademark) 435 (Candida genus, manufactured by Novozyme Japan) as a catalyst is added, under no-solvent conditions, under a reduced pressure condition of 3.5 kPa, and under a temperature condition of 65 ° C. The reaction was carried out for 5 hours while removing the produced methanol. The catalyst (Novozym® 435) was filtered off and the remaining methyl caprylate was removed by simple distillation. As a result of measuring the reaction solution by gas chromatography (HP-5890, manufactured by Hewlett Packard), it was found that trimethylolpropane dicaprylate was obtained with a selectivity of 68%.

(Example 4)
In Example 1, except that the reaction temperature was changed from 65 ° C. to 95 ° C., the reaction was carried out in the same manner as in Example 1, the catalyst was filtered off, and the remaining methyl caprylate was removed by simple distillation. The liquid was measured. As a result, it was found that trimethylolpropane dicaprylate was obtained with a selectivity of 71%.

(Example 5)
In a flask equipped with a condenser tube, 80.4 g of methyl laurate (Pastel M-12, Lion Corporation, molecular weight 214.34), 10 g of trimethylolpropane (Mitsubishi Gas Chemical Co., Ltd., molecular weight 134.18), and 2.9 g of Novozym (registered trademark) 435 (Candida sp., Novozyme Japan) is added, and methanol is produced under solvent-free conditions, under reduced pressure at a reduced pressure of 3.5 kPa, and at 65 ° C. The reaction was allowed to proceed for 1 hour. The catalyst (Novozym® 435) was filtered off and the remaining methyl laurate was removed by simple distillation. As a result of measuring the reaction solution by gas chromatography (HP-5890, manufactured by Hewlett Packard), it was found that trimethylolpropane monolaurate was obtained with a selectivity of 89%.

(Example 6)
In a flask equipped with a condenser, methyl caprylate (Pastel M-08, manufactured by Lion Corporation, molecular weight 158.24) 11.86 g, neopentyl glycol (Mitsubishi Gas Chemical Co., Ltd., molecular weight 104.15) 7.8 g And Novozym (Registered Trademark) 435 (Candida sp., Novozyme Japan) 0.98 g is added, and it is produced under a solvent-free condition, a reduced pressure condition of 3.5 kPa, and a temperature condition of 65 ° C. The reaction was allowed to proceed for 1 hour while removing methanol. The catalyst (Novozym® 435) was filtered off and the remaining methyl caprylate was removed by simple distillation. As a result of measuring the reaction solution by gas chromatography (HP-5890, manufactured by Hewlett Packard), it was found that neopentyl glycol monocaprylate was obtained with a selectivity of 71%.

(Example 7)
In Example 1, except that the degree of vacuum was changed from 3.5 kPa to 80 kPa, the reaction was performed in the same manner as in Example 1, the catalyst was filtered off, and the remaining methyl caprylate was removed by simple distillation, and the reaction was performed. The liquid was measured. As a result, it was found that trimethylolpropane dicaprylate was obtained with a selectivity of 79%.

(Comparative Example 1)
In a flask equipped with a condenser tube, 59.34 g of methyl caprylate (Pastel M-08, manufactured by Lion Corporation, molecular weight 158.24), 10 g of trimethylolpropane (manufactured by Mitsubishi Gas Chemical Co., Ltd., molecular weight 134.18), and 2.28 g of sodium bicarbonate (sodium hydrogen carbonate (Cat. No. 37116-00), manufactured by Kanto Chemical Co., Inc.) was added, and under solvent-free conditions, reduced pressure conditions of 3.5 kPa, and 170 ° C. The reaction was carried out for 10 hours while removing the produced methanol. The catalyst (sodium bicarbonate) was filtered off and the remaining methyl caprylate was removed by simple distillation. As a result of measuring the reaction solution by gas chromatography (HP-5890, manufactured by Hewlett Packard), trimethylolpropane monocaprylate was obtained with a selectivity of 1%, and trimethylolpropane dicaprylate was obtained with a selectivity of 19%. I understood that.

(Comparative Example 2)
In Example 1, caprylic acid (n-octanoic acid, manufactured by Tokyo Chemical Industry Co., Ltd., molecular weight 144.21) was used instead of 59.34 g of methyl caprylate (Pastel M-08, manufactured by Lion Corporation, molecular weight 158.24). ) The reaction was carried out in the same manner as in Example 1 except that 53.7 g was used and the reaction time was changed from 10 hours to 5 hours. The catalyst was filtered off and the reaction solution was measured. As a result, it was found that trimethylolpropane monocaprylate was obtained with a selectivity of 56%, and trimethylolpropane dicaprylate was obtained with a selectivity of 9%.

(Comparative Example 3)
In Example 1, except that the reaction temperature was changed from 65 ° C. to 110 ° C., the reaction was carried out in the same manner as in Example 1, the catalyst was filtered off, and the remaining methyl caprylate was removed by simple distillation. The liquid was measured. As a result, it was found that trimethylolpropane monocaprylate was obtained with a selectivity of 56%, and trimethylolpropane dicaprylate was obtained with a selectivity of 44%.

(Comparative Example 4)
In Example 1, the reaction was carried out in the same manner as in Example 1 except that the degree of vacuum was changed from the reduced pressure condition of 3.5 kPa to the normal pressure (101.3 kPa), and the reaction was performed, and the catalyst was filtered off and remained. Methyl caprylate was removed by simple distillation, and the reaction solution was measured. It was found that trimethylolpropane monocaprylate was obtained with a selectivity of 9%, and trimethylolpropane dicaprylate was obtained with a selectivity of 2%.

(Comparative Example 5)
In Example 1, instead of 59.34 g of methyl caprylate (Pastel M-08, manufactured by Lion Corporation, molecular weight 158.24) 59.34 g, oleic acid (oleic acid, manufactured by Kanto Chemical Co., Inc., molecular weight 282.46) 105. The reaction was performed in the same manner as in Example 1 except that 92 g was used, the catalyst was filtered off, and the reaction solution was measured. Trimethylolpropane monooleate was obtained with a selectivity of 1% and trimethylolpropanediolate was obtained with a selectivity of 1%.

(Comparative Example 6)
In Example 1, instead of 59.34 g of methyl caprylate (Pastel M-08, manufactured by Lion Corporation, molecular weight 158.24), 12-hydroxystearic acid (12-hydroxystearic acid, manufactured by Tokyo Chemical Industry Co., Ltd.) The reaction was conducted in the same manner as in Example 1 except that 112.68 g of molecular weight 300.48) was used. As a result, since 12-hydroxystearic acid had a melting point of 78 ° C., it did not dissolve during the reaction.

(Comparative Example 7)
In Example 4, instead of 59.34 g of methyl caprylate (Pastel M-08, manufactured by Lion Corporation, molecular weight 158.24), 12-hydroxystearic acid (12-hydroxystearic acid, manufactured by Tokyo Chemical Industry Co., Ltd.) The reaction was conducted in the same manner as in Example 4 except that 112.68 g of molecular weight 300.48) was used. As a result, trimethylolpropane mono-12-hydroxystearate was obtained with a selectivity of 47%, and trimethylolpropane di-12-hydroxystearate was obtained with a selectivity of 27%.

In Table 1, the result about Examples 1-7 and Comparative Examples 1-7 is shown.
In the column of “hindered polyol” in Table 1, “TMP” represents trimethylolpropane, and “NP” represents neopentyl glycol.

Table 1 shows that trimethylolpropane and a fatty acid methyl ester were reacted with lipase under solvent-free conditions, under reduced pressure conditions of 1 kPa to 90 kPa, and at 20 ° C to 100 ° C. In Examples 1 to 5 and 7, the selectivity of either monoester or diester is 65% or more, and the polyol partial ester is selectively produced.
In addition, Example 6 in which neopentyl glycol and fatty acid methyl ester were reacted with lipase under a solvent-free condition, under a reduced pressure condition of 1 kPa to 90 kPa under reduced pressure, and under a temperature condition of 20 ° C. to 100 ° C. Then, the selectivity of the monoester is 65% or more, and the polyol partial ester is selectively produced.
On the other hand, in Comparative Examples 1-7, the selectivity of both monoester and diester is less than 65%, and the polyol partial ester is not selectively produced.

  The polyol partial ester produced by the method for producing a polyol partial ester of the present invention is used for various industrial uses, for example, for lubricating oils and resin additives.

Claims (3)

  It comprises reacting a hindered polyol with a fatty acid methyl ester using a lipase under a solvent-free condition, under a reduced pressure condition of 1 kPa to 90 kPa under reduced pressure, and under a temperature condition of 20 ° C. to 100 ° C. A method for producing a polyol partial ester.   The method for producing a polyol partial ester according to claim 1, wherein the fatty acid methyl ester is a saturated or unsaturated methyl ester having 6 to 18 carbon atoms.   The method for producing a polyol partial ester according to claim 1, wherein the hindered polyol is trimethylolpropane or neopentyl glycol.