JP2009203365A - Method for producing polyester polyol - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing a polyester polyol by which a polyester polyol having a high molecular weight can be produced in a high yield under mild conditions by using an enzyme as a catalyst. <P>SOLUTION: The method for producing the polyester polyol is characterized by reacting a hydroxycarboxylic acid or its ester and a polyhydric alcohol in the presence of cutinase derived from a yeast belonging to the genus Cryptococcus. It is preferable that the hydroxyl group in the hydroxycarboxylic acid or its ester is a secondary hydroxyl group and the carbon number of the hydroxycarboxylic acid or of a portion excluding alcohol residue of the ester of the hydroxycarboxylic acid is ≥15. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a method for producing a polyester polyol using cutinase as a catalyst.

A polyester polyol obtained by a dehydration condensation reaction between a hydroxycarboxylic acid and a polyhydric alcohol can be made into a polyurethane by reacting with an isocyanate, and thus has attracted attention as a raw material for producing a urethane resin.
Under such circumstances, various researches on the production method of polyester polyol have been developed, and since the energy consumption is low, the environmental load is small, and the target product can be obtained more selectively, so the enzyme is used as a catalyst. A method for producing a polyester polyol has been reported.

  For example, Patent Document 1 discloses a method for producing a polyester from a dicarboxylic acid or a derivative thereof and glycol using a lipase derived from Candida antarctica as a catalyst in the absence of a solvent. Patent Document 2 and Non-Patent Document 1 disclose a method for producing a polyester from dicarboxylic acid or a derivative thereof and glycol using hydrolase cutinase as an enzyme catalyst.

Non-Patent Document 2 discloses a method for producing a polyester using ricinoleic acid as a hydroxycarboxylic acid and using lipase as a catalyst. According to this document, a lipase derived from Pseudomonas cepacia (also known as Burkholderia cepacia) is reported to be most suitable for the polycondensation reaction of ricinoleic acid.
Japanese Patent No. 4009317 JP 2005-58228 A Polymer Preprints, Japan, Vol. 56, no. 2, 5630 (2007) H. Ebata, K .; Toshima, S .; Matsumura, Macromol. Biosci. , Vol. 7, 798 (2007)

  However, the method described in Non-Patent Document 2 has problems such as low lipase catalytic activity and a long reaction time. And the conventional manufacturing method of the polyester polyol which uses an enzyme as a catalyst is generally inadequate in reactivity, and there is no practical manufacturing method at present.

  Furthermore, Patent Document 1 does not describe a reaction example using hydroxycarboxylic acid, and according to Non-Patent Document 2, Candida antarctica lipase used in Patent Document 1 has low catalytic activity against hydroxycarboxylic acid. It has been reported.

In Patent Document 2 and Non-Patent Document 1, in the production of polyester from dicarboxylic acid and glycol using cutinase as a catalyst, the presence of water in the reaction system is important, and it is particularly necessary to add water at the beginning of the reaction. It is shown. On the other hand, it has also been shown that in the production of polyester polyol, it is necessary to dehydrate the water content in the reaction system to 500 ppm or less in order to complete the reaction (acid value 1 or less) (Non-patent Document 1).
This is because this reaction is an esterification reaction, and it is necessary to discharge the generated water to the outside of the reaction system, but on the other hand, a water amount sufficient to maintain the catalytic activity of cutinase is required during the reaction. For this reason, it means that it is necessary to remove condensed water while precisely controlling the amount of water in the reaction system, which is extremely undesirable in terms of reaction operation.

  The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a method for producing a high molecular weight polyester polyol in a high yield under mild conditions using an enzyme as a catalyst. .

As a result of intensive studies to solve the above-mentioned problems, the present inventors have demonstrated that yeast-derived cutinase, which is a kind of hydrolase, has a highly active single polycondensation reaction of a ricinoleic acid analog that is a hydroxycarboxylic acid. Found to catalyze. Furthermore, in the polycondensation reaction of hydroxycarboxylic acid, it was found that no addition of water was required at the initial stage of the reaction, and the present invention was completed.
That is, the present invention provides a method for producing a polyester polyol characterized by reacting a hydroxycarboxylic acid or an ester thereof with a polyhydric alcohol in the presence of a cutinase derived from a yeast belonging to the genus Cryptococcus. It is.

  According to the present invention, a polyester polyol can be produced in a high yield under mild conditions. The obtained polyester polyol is suitable for the production of a urethane resin.

  The method for producing a polyester polyol of the present invention is characterized by reacting a hydroxycarboxylic acid or an ester thereof with a polyhydric alcohol in the presence of a cutinase derived from yeast belonging to the genus Cryptococcus. That is, by using cutinase as a catalyst, a polyester polyol is obtained by an esterification reaction between a carboxy group in a hydroxycarboxylic acid and a hydroxyl group in the hydroxycarboxylic acid or a hydroxyl group in a polyhydric alcohol. When a hydroxycarboxylic acid ester is used, a polyester polyol is obtained by a transesterification reaction between the ester and a hydroxyl group in the hydroxycarboxylic acid ester or a hydroxyl group in a polyhydric alcohol.

<Cutinase>
The cutinase used in the present invention is derived from yeast belonging to the genus Cryptococcus. Examples of yeast belonging to the genus Cryptococcus include Cryptococcus sp S-2 (FERM P-15155), Cryptococcus neoformans, Cryptococcus cryptococcus cryptococcus cryptococcus Cryptococcus laurentii and Cryptococcus flavas. Of these, Cryptococcus sp S-2 (Cryptococcus sp S-2; FERM P-15155, hereinafter abbreviated as Cryptococcus sp S-2) is particularly preferable.

  The cutinase derived from yeast belonging to the genus Cryptococcus may be produced by the yeast itself as a protein, or may be produced by another microorganism derived from the yeast and introduced with a gene encoding cutinase.

  The cutinase may be used alone or in combination of two or more. When using 2 or more types together, the kind and usage ratio of these cutinases can be suitably selected according to the purpose.

  The cutinase is preferably an immobilized cutinase immobilized on a solid support. By using the immobilized cutinase, the handleability is improved and the process can be simplified. For example, the cutinase can be easily recovered from the reaction solution after the reaction, the recovered cutinase can be easily washed, and the stable quality cutinase can be repeatedly reused.

  Immobilization of cutinase on a solid phase carrier can be performed by a known method. For example, a method of immobilization by adsorption or the like via a non-covalent bond such as electrostatic attractive force, van der Waals force or hydrophobic bond can be mentioned. Moreover, the method of immobilizing through a covalent bond by performing a chemical reaction between the functional group on the surface of the solid phase carrier and the functional group in cutinase can be mentioned.

  In the case of immobilization via a non-covalent bond, for example, a solution containing cutinase may be brought into contact with a solid phase carrier and washed with an aqueous solution such as a buffer as necessary.

In the case of immobilization via a covalent bond, the reaction is preferably performed under conditions that do not deactivate the cutinase. For example, the amino group in the cutinase and a solid phase carrier that can form a covalent bond with the amino group are used. It is preferable to react the functional group with an aqueous solution.
Preferred examples of the functional group capable of forming a covalent bond with an amino group include an epoxy group, a haloformyl group, an isocyanate group, a carboxy group, a group represented by —CO—O—CO—, a maleimide group, and a formyl group. Among them, a formyl group or an epoxy group is more preferable in consideration of reactivity and stability. The functional group may be present on the entire solid phase carrier, but at least on the surface of the solid phase carrier.
The solid phase carrier may be a commercially available product having the functional group, or may be produced by a known method such as introducing the functional group into a solid phase carrier having no functional group. For example, for a glass-derived solid phase carrier, an epoxy group can be introduced into the solid phase carrier by using various silane coupling agents. Further, in the case of a solid phase carrier derived from an organic substance, for example, the functional group such as an epoxy group can be introduced via a functional group present in the organic substance.

Examples of the material for the solid phase carrier include inorganic substances such as kaolinite and glass, and organic substances such as polyacrylamide and polystyrene, which can be appropriately selected according to the purpose.
Further, the shape of the solid phase carrier is not particularly limited. For example, by using a porous material, the amount of cutinase immobilized per unit volume can be increased, and handling properties are improved by using fine particles.

<Hydroxycarboxylic acid>
The hydroxycarboxylic acid used in the present invention refers to a compound having a hydroxyl group and a carboxy group in one molecule, and a fatty acid having a hydroxyl group (hereinafter abbreviated as hydroxy fatty acid) is preferred. Hydroxycarboxylic acid may be either saturated or unsaturated. The position of the unsaturated bond in the hydroxycarboxylic acid is not particularly limited. For example, in the case of a hydroxy fatty acid, it is preferably not a molecular end.

  The number of carboxy groups in the hydroxycarboxylic acid may be plural, but preferably one. In addition, the position of the carboxy group in the hydroxycarboxylic acid is not particularly limited. For example, in the case of a hydroxycarboxylic acid having a chain structure such as a hydroxy fatty acid, it is preferably a molecular end. When the number of carboxy groups in the hydroxycarboxylic acid is plural, it is preferable that at least one carboxy group is at the molecular end.

The number of hydroxyl groups in the hydroxycarboxylic acid may be plural, but preferably one. Further, the position of the hydroxyl group in the hydroxycarboxylic acid is not particularly limited. For example, in the case of a hydroxycarboxylic acid having a chain structure such as a hydroxy fatty acid, it is preferably other than the molecular end. And when the number of the hydroxyl groups in hydroxycarboxylic acid is plural, it is preferable that at least one hydroxyl group exists in other than a molecule terminal.
The hydroxyl group in the hydroxycarboxylic acid is preferably a primary hydroxyl group or a secondary hydroxyl group, and more preferably a secondary hydroxyl group. When the number of hydroxyl groups in the hydroxycarboxylic acid is plural, at least one is preferably a secondary hydroxyl group, more preferably all secondary hydroxyl groups.

  The hydroxycarboxylic acid preferably has 15 or more carbon atoms, more preferably 15 to 24 carbon atoms. And the hydroxy fatty acid whose carbon number is the said range is more preferable. Such hydroxy fatty acids include pentadecanoic acid, hexadecanoic acid, heptadecanoic acid, octadecanoic acid, nonadecanoic acid, icosanoic acid, docosanoic acid, tetracosanoic acid and the like; one or more saturated bonds of the saturated fatty acid are unsaturated bonds In the unsaturated fatty acid substituted by, one or more hydrogen atoms other than the hydrogen atoms constituting the carboxy group may be substituted with a hydroxyl group.

In this invention, what hydrogenated unsaturated hydroxy fatty acid can also be used as hydroxycarboxylic acid.
In addition, for example, hydroxy fatty acids extracted from natural fats and oils such as castor oil, Dimorphotheca oil, Lesquerella oil, Lesquerella densipila seed oil, or the like can be used.
Furthermore, it is also possible to use those obtained by hydroxylating unsaturated fatty acids having no hydroxyl group such as oleic acid and linoleic acid extracted from soybean oil, linseed oil, olive oil, rice bran oil, palm oil, tall oil and the like. . For example, a hydroxy fatty acid is obtained by epoxidizing a double bond in an unsaturated fatty acid and then hydrolyzing the epoxy group.
In addition, soybean oil, linseed oil, castor oil, etc. contain hydroxy fatty acid esters such as hydroxy fatty acid triglycerides, so that the ester is decomposed after epoxidized soybean oil, epoxidized linseed oil, epoxidized castor oil, etc. Alternatively, a hydroxy fatty acid obtained by hydrolyzing the epoxy group of the obtained epoxidized fatty acid in the same manner as described above may be used.

  In the present invention, particularly preferred hydroxycarboxylic acids include ricinoleic acid and 12-hydroxystearic acid.

<Hydroxycarboxylic acid ester>
In the present invention, instead of the hydroxycarboxylic acid, an ester of the hydroxycarboxylic acid may be used. Here, the ester of hydroxycarboxylic acid refers to an ester in which the carboxy group of hydroxycarboxylic acid forms an ester. The hydroxycarboxylic acid ester may be a hydroxylactone in which one or more hydrogen atoms of the lactone ring are substituted with a hydroxyl group.
When a hydroxycarboxylic acid ester is used, a polyester polyol is obtained by a transesterification reaction between the ester and a hydroxyl group in the hydroxycarboxylic acid ester or a hydroxyl group in a polyhydric alcohol. As the ester of hydroxycarboxylic acid, the ester of hydroxy fatty acid is suitable.

The ester may be either an aliphatic ester derived from an aliphatic alcohol or an aromatic ester derived from an aromatic alcohol, but is preferably an aliphatic ester, more preferably an alkyl ester. In this case, the alkyl group of the alcohol residue constituting the alkyl ester may be linear, branched or cyclic, but is preferably linear or branched, particularly preferably linear.
As the linear or branched alkyl group, those having 1 to 5 carbon atoms are preferable, and specifically, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group. Group, sec-butyl group, tert-butyl group and n-pentyl group. Among them, those having 1 to 3 carbon atoms are more preferable, and a methyl group is particularly preferable.
The cyclic alkyl group preferably has a monocyclic structure and preferably has 5 to 7 carbon atoms, and specific examples include a cyclopentyl group, a cyclohexyl group and a cycloheptyl group.
When the aliphatic ester is an alkenyl ester or an alkynyl ester, the alkenyl group or alkynyl group constituting the ester is preferably linear or branched, and more preferably linear. And what has 2-5 carbon atoms is preferable, and it is so preferable that there are few unsaturated bonds.
Examples of the aromatic group of the alcohol residue constituting the aromatic ester include an aryl group and an arylalkyl group, and those having a monocyclic structure such as a phenyl group and a benzyl group are preferable.

  Particularly preferred hydroxycarboxylic acid esters in the present invention include methyl ricinoleate and methyl 12-hydroxystearate.

  In this invention, hydroxycarboxylic acid and hydroxycarboxylic acid ester may be used individually by 1 type, and may use 2 or more types together. And you may use together hydroxycarboxylic acid and hydroxycarboxylic acid ester. Moreover, when using 2 or more types together, the combination and ratio can be suitably selected according to the objective.

<Polyhydric alcohol>
The polyhydric alcohol used in the present invention is a compound having two or more hydroxyl groups in one molecule.
Examples of the dihydric alcohol include ethanediol, propanediol, butanediol, pentanediol, hexanediol, diethylene glycol, dipropylene glycol, neopentyl glycol, triethylene glycol, polyethylene glycol, polypropylene glycol, heptanediol, octanediol, nonanediol, Examples include aliphatic diols such as decane diol and dodecane diol, aromatic diols such as hydrogenated bisphenol A, bisphenol A, and cyclohexane diol, and alicyclic diols.

  Examples of the trihydric or higher polyhydric alcohol include glycerin, diglycerin, trimethylolethane, trimethylolpropane, trishydroxymethylaminopentane, pentaerythritol, dipentaerythritol, hexamethylolmelamine, hexaethylolmelamine, tetramethylolbenzoguanamine. And tetraethylol benzoguanamine.

  Among these, as the polyhydric alcohol, a dihydric alcohol or a trihydric alcohol is preferable, a dihydric alcohol is more preferable, and an aliphatic diol is particularly preferable. Further, those having at least one hydroxyl group at the molecular end are preferred, those having all hydroxyl groups at the molecular end are more preferred, and particularly preferred are 1,4-butanediol, 1,6-hexanediol, and polyethylene glycol. It can be illustrated.

  In addition to the above, those in which a plurality of hydroxyl groups of the polyhydric alcohol are ester-bonded to a carboxy group of hydroxycarboxylic acid can be used as the polyhydric alcohol. That is, what corresponds to the reaction intermediate formed in the present invention may be used as a raw material from the beginning of the reaction. An example of such a polyhydric alcohol is hydroxy fatty acid triglyceride. For example, it is known that hydroxy fatty acid triglyceride contained in castor oil as a main component usually has a ratio of ricinoleic acid residues of about 80 to 90% in all fatty acid residues, and is rich in ricinoleic acid triglycerides. It is included. Therefore, castor oil can also be used as a raw material polyhydric alcohol.

  In this invention, a polyhydric alcohol may be used individually by 1 type, and may use 2 or more types together. When two or more kinds are used in combination, the combination and ratio can be appropriately selected according to the purpose.

  In the present invention, in addition to the above cutinase, hydroxycarboxylic acid, hydroxycarboxylic acid ester and polyhydric alcohol, the reaction is carried out in the presence of other components as necessary within the range not impeding the effects of the present invention. Also good.

<Other reaction conditions>
What is necessary is just to select suitably the ratio of the usage-amount of hydroxycarboxylic acid or its ester, and a polyhydric alcohol according to these kind. For example, the number of carboxy groups and hydroxyl groups in the hydroxycarboxylic acid, or the number of esters and hydroxyl groups in the hydroxycarboxylic acid ester, and the number of hydroxyl groups in the polyhydric alcohol may be selected. For example, when a hydroxycarboxylic acid having one carboxy group and one hydroxyl group is reacted with a dihydric alcohol, the hydroxycarboxylic acid is preferably used in an amount of 3 to 12 times the amount of the dihydric alcohol. It is more preferable to use the amount, particularly preferably 6 to 8 times the molar amount, and most preferably 6.5 to 7.5 times the molar amount. Also in the case of reacting a hydroxycarboxylic acid ester having one ester bond and one hydroxyl group with a dihydric alcohol, it is preferable to use the hydroxycarboxylic acid ester in the same amount as the hydroxycarboxylic acid.

  The amount of cutinase used is not particularly limited, but is preferably 0.5 to 20% by mass, and preferably 0.5 to 10% by mass with respect to the total amount of hydroxycarboxylic acid and its ester and polyhydric alcohol used. It is more preferable that it is 1-6 mass%, and it is most preferable that it is 2-5 mass%.

  The reaction solvent can be appropriately selected according to the combination of raw materials used. For example, when hydroxycarboxylic acid is used as a raw material, water is generated as the reaction proceeds, and this water is preferably removed from the reaction system in order to suppress the ester hydrolysis reaction. If a high-boiling solvent such as toluene or xylene is used as the solvent and the reaction is carried out while distilling off the solvent under reduced pressure, azeotropic dehydration is preferable.

  In the present invention, for example, when at least a part of the raw material is in a liquid state at the reaction temperature, the reaction can be performed without using a reaction solvent.

The reaction is preferably performed under reduced pressure regardless of the presence or absence of a reaction solvent. When hydroxycarboxylic acid is used, water is generated as the reaction progresses, and when hydroxycarboxylic acid ester is used, alcohol is generated as the reaction proceeds. It is preferable to remove from the reaction system. By performing the reaction under reduced pressure, these water and alcohol can be easily removed.
The pressure in the reaction system at the time of depressurization is not particularly limited, but is preferably 5000 Pa or less, more preferably 2500 Pa or less.
In this case, the reaction is initially performed under normal pressure, and the reduced pressure is preferably 5 to 60 minutes after the start of the reaction, more preferably 10 to 50 minutes, particularly preferably 20 to 40 minutes, and most preferably 25 to 35 minutes. It should be done later.

When the reaction is carried out under reduced pressure, it is preferable to carry out the reaction while supplying an inert gas into the reaction system. Here, examples of the inert gas include nitrogen, argon, and helium.
The supply amount of the inert gas is not particularly limited, but the supply amount per liter of the reactor volume is preferably 0.01 to 0.50 L / min, more preferably 0.05 to 0.10 L / min.

What is necessary is just to adjust reaction temperature suitably according to the raw material to be used, the presence or absence of the use of a reaction solvent, and the kind, when using.
For example, when the hydroxycarboxylic acid or ester thereof is liquid, it is preferably 20 to 80 ° C, more preferably 30 to 70 ° C, and particularly preferably 40 to 60 ° C.
On the other hand, when the hydroxycarboxylic acid or its ester is in a solid form, it is preferable to carry out the reaction at a melting point or higher at the beginning of the reaction. The reaction temperature at this time depends on the melting point, but usually 40 to 80 ° C It is preferable that After the reaction at such a temperature, the reaction temperature may be lowered within the range in which the reaction solution has fluidity, or the reaction may be continued without changing the reaction temperature. When the reaction temperature is lowered, for example, the reaction temperature is preferably lowered so as to be within the temperature range exemplified when the hydroxycarboxylic acid or ester thereof is in a liquid state. The timing for lowering the reaction temperature may be determined according to the progress of the reaction, but usually 5 to 36 hours after the start of the reaction is preferable, 10 to 30 hours are more preferable, and 15 to 30 hours are more preferable. Most preferably after 20 to 25 hours.

  The reaction time may be appropriately adjusted according to other reaction conditions. For example, when the reaction is carried out at the preferred reaction temperature as described above, it is preferably 100 hours or shorter, more preferably 70 hours or shorter, and 50 hours or shorter. Is particularly preferred.

  The progress of the reaction can be followed, for example, by measuring the acid value (AN). In the present invention, the reaction conditions may be adjusted so that the acid value (AN) is preferably 5 or less, more preferably 3 or less, and particularly preferably 1 or less. In the present invention, since the catalytic activity of cutinase is high, the acid value (AN) can be 1 or less. In general, the lower the acid value (AN), the higher the molecular weight polyester polyol.

  After completion of the reaction, the desired polyester polyol is obtained by removing the catalyst by filtration or the like. And you may perform post-processing, such as washing | cleaning, concentration, and refinement | purification as needed.

  According to the present invention, since the catalytic activity of cutinase is high, the reaction can be carried out rapidly under mild reaction conditions. For example, a high molecular weight polyester polyol suitable as a raw material for producing urethane resins can be obtained in high yield. It is done. Specifically, the mass average molecular weight (Mw) is 1000 to 5000, the number average molecular weight (Mn) is 1000 to 4000, and the dispersity (Mw / Mn) is about 1.2 to 2.0 by calculation based on polystyrene standards. A polyester polyol is preferably obtained.

  In the production method of the present invention, a polyester can also be produced by single polycondensation of a hydroxycarboxylic acid in the same manner as in the production method of the above polyester polyol except that no polyhydric alcohol is used.

Hereinafter, the present invention will be described in more detail with reference to specific examples. However, the present invention is not limited to the following examples.
[Example 1]
An immobilized cutinase was prepared by physically adsorbing Cryptococcus sp-2 cutinase on a porous acrylic bead-like solid phase simple substance (Lewatit OC1600, LANXESS).
Subsequently, ricinoleic acid 253.6 was attached to a three-necked flask equipped with a three-way cock connected to one of the vacuum pumps through the cooling trap and the other connected to the vacuum gauge, and an inert gas introduction tube connected to the gas flow rate controller. Part by weight, 10.9 parts by weight of 1,4-butanediol, and 7.9 parts by weight of the immobilized cutinase (3% by weight based on the total amount of monomers) were added and heated to 45 ° C. in an oil bath. And reaction was performed, stirring at about 250 rpm using the mechanical stirrer which attached the stirring blade. 30 minutes after the start of the reaction, the pressure in the reaction system was reduced to 2500 Pa, and nitrogen was supplied as an inert gas at 0.05 L / min. Dehydration was remarkably observed after 30 minutes from the start of the reaction. Seven hours after the start of the reaction, the reaction system was decompressed to 1500 Pa and the reaction was continued. The reaction was traced by acid value (AN) measurement. 48 hours after the start of the reaction, the pressure reduction in the reaction system and the supply of nitrogen were stopped, and the resulting viscous liquid was filtered using a production filter paper (No. 28-3) manufactured by Advantech. The immobilized enzyme was filtered off. Thereby, the polyester polyol resin of yellow viscous liquid was obtained at room temperature. The properties of this polyester polyol resin are shown below. Moreover, the tracking result of reaction is shown in FIG. In FIG. 1, the horizontal axis represents the reaction time, and the vertical axis represents the acid value (AN).
Hydroxyl value (OHv); 31.9
Acid value (AN); 0.96
Molecular weight analysis result by GPC (calculation result by polystyrene standard); Mn 3260, Mw 4440, Mw / Mn 1.36
Viscosity (25 ° C.); 1035 mPa · s

[Example 2]
The reaction was performed in the same manner as in Example 1 except that high-purity ricinoleic acid (ricinoleic acid HP, manufactured by Ogura Gosei Kogyo Co., Ltd.) was used instead of ricinoleic acid. The property of the obtained polyester polyol resin is shown below.
Hydroxyl value (OHv); 53.7
Acid value (AN); 0.21
Molecular weight analysis result by GPC (calculation result by polystyrene standard); Mn3110, Mw4360, Mw / Mn1.40

[Example 3]
The reaction was conducted in the same manner as in Example 1 except that 209.7 parts by mass of methyl ricinoleate (K-PON180HP, manufactured by Ogura Gosei Kogyo Co., Ltd.) and 11.9 parts by mass of 1,6-hexanediol were used instead of ricinoleic acid. went. The reaction was traced by measuring the hydroxyl value (OHv).
The property of the obtained polyester polyol resin is shown below.
Hydroxyl value (OHv); 58.6
Acid value (AN); 0.14
Molecular weight analysis result by GPC (calculation result by polystyrene standard); Mn 1480, Mw 1960, Mw / Mn 1.32

[Example 4]
Instead of ricinoleic acid, 122.6 parts by weight of methyl 12-hydroxystearate (ITOHWAX E-210, manufactured by Ito Oil Co., Ltd.) and 9.1 parts by weight of 1,4-butanediol were used, and the reaction temperature was 60 ° C. The reaction was performed in the same manner as in Example 1 except that. The reaction was traced by measuring the hydroxyl value (OHv). When the reaction was completed, the polyester polyol resin was obtained as a grease-like semisolid when allowed to stand at room temperature. The property of the obtained polyester polyol resin is shown below.
Hydroxyl value (OHv); 40.3
Acid value (AN); 0.21

[Example 5]
The reaction was conducted in the same manner as in Example 1 except that 75.4 parts by mass of castor oil and 82.9 parts by mass of ricinoleic acid were used instead of 1,4-butanediol. The property of the obtained polyester polyol resin is shown below.
Hydroxyl value (OHv); 63.7
Acid number (AN); 3.72

[Comparative Example 1]
The reaction was performed in the same manner as in Example 1 except that immobilized Candida antarctica-derived lipase B (Novozyme 435, manufactured by Novozymes Japan) was used as the enzyme catalyst instead of cutinase. As a result, the reaction progressed to the acid value (AN) 110 after 2 hours from the start of the reaction, but the subsequent reaction progress was extremely slow. The acid value after 48 hours from the start of the reaction was 98, and the acid value after 96 hours was 80. The results of tracking the reaction at this time are shown in FIG.

[Comparative Example 2]
The reaction was performed in the same manner as in Example 1 except that immobilized Burkholderia cepacia lipase (lipase PSC-II, manufactured by Amano Enzyme) was used instead of cutinase as the enzyme catalyst. As a result, the acid value (AN) 25 hours after the start of the reaction was 82. The progress of the reaction was slow, and the reaction was continued for 72 hours from the start of the reaction, but the acid value (AN) was 30. The results of tracking the reaction at this time are shown in FIG.

[Comparative Example 3]
In the same reactor as in Example 1, 146.1 parts by weight of adipic acid, 100.6 parts by weight of 1,4-butanediol, 12.3 parts by weight of immobilized cutinase (5% by weight based on the total amount of monomers) Warm to 45 ° C. in an oil bath. The reaction was carried out while stirring at about 250 rpm using a mechanical stirrer equipped with a stirring blade. 30 minutes after the start of the reaction, the pressure in the reaction system was reduced to 2500 Pa, and nitrogen was supplied as an inert gas at 0.05 L / min. The reaction hardly proceeded, and the acid value 30 hours after the start of the reaction was 230. Thereafter, the reaction was continued up to 55 hours, but the acid value was 220.
From Comparative Example 3, it was confirmed that in the production of polyester from dicarboxylic acid and glycol using cutinase as an enzyme catalyst, it was necessary to add water at the beginning of the reaction.

[Example 6]
The reaction was performed in the same manner as in Example 1. During this time, the reaction was traced, and the reaction solution at each stage having an acid value (AN) of 114, 50, 11 and 0.9 was analyzed by GPC. The result is shown in FIG. In FIG. 2, the horizontal axis represents the retention time, and the vertical axis represents the peak intensity. In FIG. 2, charts of ricinoleic acid and 1,4-butanediol are also shown for comparison.
As is clear from FIG. 2, the peak of 1,4-butanediol has already disappeared at the initial stage of the reaction with an acid value (AN) of 114, and 1,4-butanediol is more than the hydroxyl group in ricinoleic acid. It was confirmed that the hydroxyl groups in them react preferentially. It was confirmed that the peak of ricinoleic acid disappeared with the progress of the reaction, and the intensity of the peak indicating a high molecular weight product corresponding to the polyester polyol was increased.

[Example 7, Comparative Examples 4 to 5]
The reaction was carried out in the same manner as in Example 1 and Comparative Examples 1 and 2 (Example 7-cutinase, Comparative Example 4-Candida antarctica lipase B, Comparative Example 5-Burkholderia cepacia lipase). In Example 7, the reaction time was 48 hours, in Comparative Example 4 the reaction time was 48 hours, and in Comparative Example 5, the reaction time was 72 hours. The result is shown in FIG. In FIG. 3, the horizontal axis represents the retention time, and the vertical axis represents the peak intensity. In FIG. 3, charts of ricinoleic acid and 1,4-butanediol are also shown for comparison.
As is clear from FIG. 3, in Example 7, the peaks of ricinoleic acid and 1,4-butanediol were not observed, and it was confirmed that the reaction was sufficiently advanced and the polyester polyol was produced. .
On the other hand, in Comparative Example 4, no high molecular weight product peak was observed, and it was confirmed that no polyester polyol was produced. And since the peak of 1,4-butanediol has disappeared, it is presumed that the esterification reaction between the hydroxyl group in 1,4-butanediol and the carboxy group in ricinoleic acid has progressed. Was supported by the fact that the progress of the reaction stopped at an acid value (AN) of about 100.
In Comparative Example 5, the peak of 1,4-butanediol disappeared, and the peak of ricinoleic acid and the product of high molecular weight were observed, so that 1,4-butane was more than the hydroxyl group in ricinoleic acid. It was confirmed that the hydroxyl group in the diol preferentially reacted and that the reaction was not completed and ricinoleic acid remained. This was supported by the fact that the progress of the reaction stopped at an acid value (AN) of about 30.

  The present invention can be used for the production of polyester polyols and urethane resins.

It is a graph which shows the tracking result of the reaction in Example 1 and Comparative Examples 1 and 2. 10 is a GPC chart showing a reaction tracking result in Example 6. It is a GPC chart which shows the analysis result of the product in Example 7 and Comparative Examples 4-5.

Claims (4)

  A process for producing a polyester polyol, comprising reacting a hydroxycarboxylic acid or an ester thereof with a polyhydric alcohol in the presence of a cutinase derived from a yeast belonging to the genus Cryptococcus.   The method for producing a polyester polyol according to claim 1, wherein the hydroxyl group in the hydroxycarboxylic acid or ester thereof is a secondary hydroxyl group.   The method for producing a polyester polyol according to claim 1 or 2, wherein the hydroxycarboxylic acid residue of the hydroxycarboxylic acid or ester thereof has 15 or more carbon atoms.   The method for producing a polyester polyol according to any one of claims 1 to 3, wherein the cutinase is immobilized on a solid phase carrier.

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