JP2017066398A - Method for producing polyester - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method capable of efficiently producing a polycondensate of ricinoleic acid, a derivative thereof and the like with a high degree of polymerization even when an inorganic catalyst is used.SOLUTION: The method for producing a polyester comprises polymerizing a raw material including one of ricinoleic acid and derivatives thereof. As a polymerization catalyst, at least one kind of compound selected from titanium, germanium and antimony and at least one kind of compound of a metal selected from Group 2 and Groups 8 to 12 of the periodic table are used. An amount of the titanium atom is 1,000 to 5,000 wt.ppm; an amount of the germanium atom is 100 to 30,000 wt.ppm; an amount of the antimony atom is 100 to 30,000 wt.ppm; and a ratio (X/Y) of the total mol number (X) of metal atoms derived from the compounds of metals of Group 2 and Groups 8 to 12 of the periodic table to the total mol number (Y) of the titanium atom, the germanium atom and the antimony atom is in a range of 0.05 to 0.5.SELECTED DRAWING: None

Description

  The present invention relates to a method for producing a polyester which is a ricinoleic acid polymer.

In recent years, from the viewpoint of global warming issues, renewable energy, resource recycling, resource circulation, etc., material development based on natural product-derived raw materials replacing petroleum raw materials has become active.
As the circulation type material, many techniques relating to biodegradable polyester, especially aliphatic polyester, have been disclosed. For example, development of a thermoplastic biodegradable aliphatic polyester composed of an aliphatic dicarboxylic acid or an ester thereof, an aliphatic diol or an alicyclic diol, a naturally derived unsaturated fatty acid or an ester thereof is known. A typical example is a polycondensate containing lactic acid. On the other hand, a method using ricinoleic acid obtained by a method such as hydrolysis of castor oil or a derivative thereof has also been studied. Specifically, the method disclosed in Patent Documents 1 to 3 can be mentioned. I can do it.

  Patent Document 1 discloses that when a copolycondensation of ricinoleic acid, lactone, or lactide or a copolycondensation of ricinoleic acid and lactic acid is performed, it tends to be difficult to obtain a polymer having a high molecular weight.

  Patent Document 1 discloses a method of performing polycondensation using a supported enzyme in which ribose or the like is supported on a support such as synthetic zeolite as a catalyst. Enzymes tend to have a lower temperature range in which catalytic action is exhibited than inorganic catalysts, which may make industrialization of technologies using enzymes somewhat difficult. It is disclosed that the temperature range in which the enzyme action is expressed can be increased by using the carrier of the supported enzyme as a specific carrier.

Patent Documents 2 and 3 each disclose a technique using a ricinoleic acid polymer as a component of an elastomer or lubricating oil.
In the production examples of polycondensates using ricinoleic acid in Patent Documents 2 and 3, an enzyme is used as a catalyst.

International Publication 2008/029805 Pamphlet Japanese Patent No. 5373435 Japanese Patent No. 5398708

  The present inventors proceeded with polycondensation reaction while examining polycondensation using a diolic acid such as ricinoleic acid, butanediol and dicarboxylic acid such as sebacic acid using a known titanium compound as a catalyst. We faced the problem that it was difficult to increase the molecular weight of the resulting polyester. In addition to the effect of the purity of ricinoleic acid, which is a raw material derived from natural products, this problem is low in reactivity to ricinoleic acid or the rate of condensation reaction and hydrolysis reaction when a conventional metal catalyst is used as a base. I guessed that the difference was not so large.

From these facts, an object of the present invention is to find a method capable of efficiently producing a polycondensate such as ricinoleic acid having a high degree of polymerization and a derivative thereof even if an inorganic catalyst is used.
Another object of the present invention is to provide a polyester having a specific structure and preferably a high molecular weight.

  As a result of investigations to solve the above-mentioned problems, the present inventors have combined a plurality of specific metal-containing compounds at a specific ratio when polycondensation is performed using a compound containing ricinoleic acid or a derivative thereof. It was found that a polycondensate containing a structural unit derived from ricinol having a high molecular weight can be produced at a high temperature suitable for industrialization, and the present invention was completed.

That is, the present invention
[1] A method for producing a polyester by polymerizing a raw material containing at least one selected from ricinoleic acid and derivatives thereof,
As a polymerization catalyst, using at least one compound selected from a titanium compound, a germanium compound, and an antimony compound, and at least one compound selected from the group 2 and groups 8 to 12 of the periodic table,
The content of the metal derived from the titanium compound, germanium compound and antimony compound with respect to the produced polyester is:
When using the titanium compound, the amount of titanium atoms is 1,000 to 5,000 wtppm with respect to the amount of polyester produced,
When using the germanium compound, the amount of germanium atoms is 100 to 30,000 wtppm with respect to the amount of polyester produced,
When using the antimony compound, the amount of antimony atoms is 100 to 30,000 wtppm with respect to the amount of polyester produced,
And the total number of moles (X) of metal atoms derived from the compounds of metals of Groups 2 and 8-12 of the periodic table, and titanium atoms, germanium atoms and antimony derived from the titanium compounds, germanium compounds and antimony compounds. A method for producing a polyester having a ratio (X / Y) to the total number of moles of atoms (Y) in the range of 0.05 to 0.5;
[2] The molar ratio of ricinoleic acid and derivatives derived from the ricinoleic acid and derivatives thereof contained in the produced polyester is a structural unit derived from ricinoleic acid and derivatives thereof contained in the produced polyester, a structural unit derived from dicarboxylic acid, and The manufacturing method of the polyester of Claim 1 which is 10-100 mol% with respect to the sum total of the structural unit derived from diol;
[3] The process for producing a polyester according to claim 1, wherein the raw material contains at least one selected from dicarboxylic acids having 2 to 12 carbon atoms and diol components having 2 to 12 carbon atoms;
[4] (I) 10-80 mol% of structural units derived from ricinoleic acid and its derivatives,
(II) 10 to 45 mol% of structural units derived from a dicarboxylic acid having 2 to 12 carbon atoms and (III) 10 to 45 mol% of structural units derived from a diol having 2 to 12 carbon atoms.
(However, the total of structural units (I), (II), and (III) is 100 mol%)
Polyester containing;
[5] a metal selected from titanium, germanium, antimony, and a metal selected from Group 2 and Group 8-12 metals of the Periodic Table,
As the metal,
When the titanium is included, the titanium content is 1,000 to 5,000 wtppm,
When the germanium is included, the germanium content is 100 to 30,000 wtppm,
When the antimony is included, the content of antimony is 100 to 30,000 wtppm,
And the total number of moles (X) of the metals in groups 2 and 8 to 12 of the periodic table, and the total number of moles of titanium atoms, germanium atoms and antimony atoms derived from the titanium compounds, germanium compounds and antimony compounds (Y). And the ratio (X / Y) is in the range of 0.05 to 0.5,
(I) 10 to 100 mol% of structural units derived from ricinoleic acid and its derivatives,
(II) 0 to 45 mol% of structural units derived from a dicarboxylic acid having 2 to 12 carbon atoms and (III) 0 to 45 mol% of structural units derived from a diol having 2 to 12 carbon atoms.
(However, the total of structural units (I), (II), and (III) is 100 mol%)
A polyester characterized by comprising;
[6] (I) 10-80 mol% of structural units derived from ricinoleic acid and its derivatives,
(II) 10 to 45 mol% of structural units derived from a dicarboxylic acid having 2 to 12 carbon atoms and (III) 10 to 45 mol% of structural units derived from a diol having 2 to 12 carbon atoms.
(However, the total of structural units (I), (II), and (III) is 100 mol%)
The polyester according to claim 5, comprising:
[7] The polyester according to any one of [4] to [6], wherein the weight average molecular weight measured by GPC method is 90,000 to 500,000.

  By using the production method of the present invention, a relatively high molecular weight polycondensate containing a structural unit derived from ricinoleic acid having a high molecular weight can be efficiently obtained in a relatively short time under a high temperature environment advantageous for industrialization. I can do it.

  The polyester of the present invention has a high molecular weight, tends to have a strong interaction with various substances, and may exhibit excellent properties such as adhesiveness.

  The polyester production method of the present invention comprises at least one selected from ricinoleic acid and derivatives thereof as an essential component, and, if necessary, a raw material containing diol, dicarboxylic acid or a derivative thereof, and presence of a catalyst containing a specific metal compound. It is characterized by a polymerization reaction below.

  The production method and each component used in this production method will be described in detail. In the present invention, polymerization is a concept including polycondensation, and also includes copolymerization and copolycondensation.

(Ricinolic acid and its derivatives)
Examples of the derivative of ricinoleic acid include an ester of ricinoleic acid and 12-hydroxystearic acid obtained by hydrogenating ricinoleic acid. These compounds can be polymerized relatively easily by esterification or transesterification in the presence of a catalyst described later.

  Ricinoleic acid or a derivative thereof can be used alone or in combination of two or more thereof, but can also be used in combination with a diol compound or a dicarboxylic acid compound. In this case, it is also possible to adjust the terminal structure and molecular weight of the polymer obtained by the ratio of using the diol compound or dicarboxylic acid compound.

  In the present invention, when the total molar amount of terminal hydroxyl groups contained in each raw material used is (OH) and the total molar amount of terminal carboxyl groups is (COOH), the molar ratio (hereinafter referred to as OH / COOH ratio). The preferred range is from 1.0 to 5.0, more preferably from 1.0 to 3.0. When the OH / COOH ratio is 1.0 or more and 5.0 or less, sufficient hydroxyl group ends are formed in the low-molecular oligomer prepared in the esterification or transesterification reaction described later, and the reaction during polycondensation described later Tend to improve. On the other hand, when the OH / COOH ratio exceeds 5.0, a part of the excess raw material diol compound contributes to the decomposition of the resin, and the reactivity during polycondensation may be lowered.

(Diol compound)
As the diol compound, a known diol compound can be used without limitation, and an alkylene diol compound is preferable.
Specific examples of the alkylene diol include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8- Octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 2,2-dimethyl-1,3-propanediol, 2-ethyl-2- Aliphatic diols such as butyl-1,3-propanediol, 3-methyl-1,5-pentanediol, 2,4-diethyl-1,5-pentanediol, diethylene glycol and triethylene glycol, 2,2-bis [ 4 ′-(2 ″ -hydroxyethoxy) phenyl] propane, 4,4′-bis (2 ″ -hydroxyethoxy) phenyl sulfide, 4,4′-bis (2 ″ -hydroxyethoxy) phenylsulfone, 9,9-bis [4 ′-(2 ″ -hydroxyethoxy) phenyl] fluorene, 1,4-bis (2′-hydroxyethoxy) benzene, etc. Ethylene oxide adduct of an aromatic dihydroxy compound, tricyclo [5.2.1.0 (2,6)] decanedimethanol, 1,4-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanedi Mention may be made of alicyclic diols such as methanol, 1,3-cyclohexanedimethanol, 2,2-bis (4′-hydroxycyclohexyl) propane (hydrogenated bisphenol A).

These diol compounds are preferably primary alcohols. If the diol compound is a secondary or higher alcohol, the polycondensation reactivity may decrease.
Among these, a diol compound having 2 to 12 carbon atoms is preferable. A diol compound having 2 to 6 carbon atoms, particularly preferably 2 to 4 carbon atoms is more preferable. If the diol compound has too many carbon atoms, the polycondensation reactivity may decrease. Specifically, aliphatic diols such as ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, and 1,6-hexanediol are preferable. More preferred are ethylene glycol, 1,3-propanediol and 1,4-butanediol having a relatively small number of carbon atoms. When the biodegradability of the polycondensate is expected, the preferred diol compound is 1,4-butanediol available from natural esters.
These diol compounds can be used in combination of two or more. Moreover, it is also possible to use as an ester body with the above-mentioned ricinoleic acid or a low condensation compound.

(Dicarboxylic acid compound)
As the dicarboxylic acid compound, a known dicarboxylic acid compound can be used without limitation, and an aliphatic dicarboxylic acid compound is preferable.

  Examples of the aliphatic dicarboxylic acid compound include linear or branched fatty acids such as succinic acid, malonic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedicarboxylic acid, and dodecanedicarboxylic acid. Aliphatic dicarboxylic acids; and lower alkyl esters of these aliphatic dicarboxylic acids.

Among these, a C2-C12 dicarboxylic acid compound is preferable. More preferred is a dicarboxylic acid compound having 6 to 10 carbon atoms, particularly preferably 9 to 10 carbon atoms. If the carbon number of the dicarboxylic acid compound becomes too large, the polycondensation reactivity may decrease. Examples of the dicarboxylic acid compound having 9 to 10 carbon atoms include sebacic acid and azelaic acid having a structure relatively similar to ricinoleic acid.
These dicarboxylic acid compounds can be used in combination of two or more. Moreover, it is also possible to use as an ester body with the above-mentioned ricinoleic acid, or a low condensation compound.

(Other copolymer components)
The polyester of the present invention may contain a copolymer component other than the above-described dicarboxylic acid compound and diol compound within a range that does not impair the object of the present invention. Specific examples of the copolymer component include glycolic acid, 4-hydroxybenzoic acid, hydroxycarboxylic acid such as 4- (2′-hydroxyethoxy) benzoic acid, trimellitic acid, trimesic acid, pyromellitic acid, and naphthalenetetracarboxylic acid. , Trifunctional or polyfunctional components such as trimethylolethane, trimethylolpropane, glycerol, pentaerythritol and the like.

(Metal compound)
The production method of the present invention is characterized in that at least two metal compounds are used in combination as a catalyst.
The first metal compound is at least one compound selected from a titanium compound, an antimony compound, and a germanium compound. As these metal compounds, those conventionally known to be suitably used as a polymerization catalyst for polyesters can be used. Titanium compounds and antimony compounds are preferred, and titanium compounds are more preferred. Specific examples of the titanium compound include tetrabutyl titanate, tetra-iso-propyl titanate, and acetyl tri-iso-propyl titanate. Examples of the antimony compound include antimony acetate, and examples of the germanium compound include germanium dioxide. The titanium compound, the antimony compound, and the germanium compound may be two or more types of titanium compounds, two or more types of antimony compounds, and two or more types of germanium compounds, respectively.

  The usage-amount of a titanium compound is 1,000-5,000 wtppm in metal conversion with respect to the polyester manufactured, ie, titanium conversion. A preferred lower limit is 2,000 wtppm, and a more preferred lower limit is 3,500 wtppm. A preferable upper limit is 4,500 wtppm, and a more preferable upper limit is 4,000 wtppm.

  The usage-amount of an antimony compound is 100-30,000 wtppm in metal conversion with respect to polyester manufactured, ie, antimony conversion. A preferred lower limit is 1,000 wtppm, and a more preferred lower limit is 5,000 wtppm. A preferable upper limit is 20,000 wtppm, and a more preferable upper limit is 15,000 wtppm.

  The usage-amount of a germanium compound is 100-30,000 wtppm in metal conversion with respect to polyester manufactured, ie, germanium conversion. A preferred lower limit is 1,000 wtppm, and a more preferred lower limit is 5,000 wtppm. A preferable upper limit is 20,000 wtppm, and a more preferable upper limit is 15,000 wtppm.

  In addition, the usage-amount of the said titanium compound, an antimony compound, and a germanium compound, ie, the content rate with respect to manufactured polyester of the metal derived from a titanium compound, a germanium compound, and an antimony compound is only about the 1st metal compound used. It goes without saying that it applies. For example, when only the titanium compound is used as the first metal compound, the amount of the titanium compound used may be within the range of the amount used for the titanium compound, and the use of the germanium compound and the antimony compound. The amount doesn't matter. Moreover, when using only a titanium compound and a germanium compound as a 1st metal compound, the usage-amount of the titanium compound is in the range of the usage-amount shown about the said titanium compound, and the usage-amount of the germanium compound However, the amount of the antimony compound is not a problem as long as it is within the range of the amount used for the germanium compound. When a titanium compound, a germanium compound, and an antimony compound are used as the first metal compound, the usage amount of the titanium compound is within the range of the usage amount indicated for the titanium compound, and the usage amount of the germanium compound. However, it is necessary to be within the range of the use amount shown for the germanium compound, and the use amount of the antimony compound needs to be within the range of the use amount shown for the antimony compound.

  As these first metal compounds, two or more of titanium compounds, antimony compounds and germanium compounds may be used in combination. In this case, the total amount of the titanium compound, the antimony compound and the germanium compound is preferably 1,500 to 60,000 wtppm as the total of the respective metal conversions with respect to the polyester to be produced. A preferred lower limit is 2,000 wtppm, and a more preferred lower limit is 3,000 wtppm. On the other hand, a preferable upper limit is 30,000 wtppm, a more preferable upper limit is 20,000 wtppm, and a still more preferable upper limit is 15,000 wtppm.

Examples of means for controlling the ratio of the first metal compound to the produced polyester include the following methods.
For example, during a polymerization reaction by a reaction between a normal polycarboxylic acid and a polyhydric alcohol, a predetermined small amount of the reaction solution is collected from the reaction vessel, separated from the polymer, and then washed. The reaction time is adjusted while calculating the content of the metal component in the polymer from the polymer concentration obtained from the polymer and the concentration of the catalyst component, or the raw material polycarboxylic acid or polyhydric alcohol is added. Etc. can be mentioned.

  In addition, in the case of a polycondensation reaction using esterified polyvalent carboxylic acid as a raw material, the metal content of the raw material is confirmed by a technique such as ICP, and the charged amount of the reaction and the desorbed polyhydric alcohol component By measuring the amount, the content of the metal component in the polymer can be determined from these information.

  As another method, while measuring the metal component content of the polymer in the reaction solution withdrawn in a small amount directly by ICP method or the like, the timing for terminating the reaction is determined, or if necessary, the acid of the raw material, There is also a method of adding an alcohol compound.

  If the ratio of the titanium compound, antimony compound and germanium compound to the acid or alcohol is too low, the reaction rate may decrease or the molecular weight may not be sufficiently high. If the ratio of the metal compound to the acid or alcohol is too high, the reaction rate may decrease or the molecular weight may not be sufficiently high. This is presumably because the presence of excess metal causes partial hydrolysis and side reactions described later.

  The second metal compound is at least one metal compound selected from Group 2 and Group 8 to 12 elements of the periodic table. Specific examples include compounds such as calcium, magnesium, cobalt, and zinc. Preferred are compounds of Group 2 elements of the periodic table called alkaline earth metals, and more preferred are calcium compounds and magnesium compounds. Examples of calcium compounds include calcium acetate, magnesium compounds, magnesium acetate, cobalt compounds, cobalt acetate, and zinc compounds, for example, zinc acetate.

  The first metal compound and the second metal compound are used in combination at a specific ratio. The ratio of the total number of moles (X) of metal atoms derived from the second metal compound to the total number of moles (Y) of titanium, germanium and antimony atoms derived from the first metal compound (hereinafter referred to as X / Y (Sometimes referred to as a ratio) is 0.05 to 0.5. A preferable lower limit value of the X / Y ratio is 0.07, and a more preferable lower limit value is 0.1. On the other hand, a preferable upper limit is 0.4, and a more preferable upper limit is 0.3.

  As apparent from the value of the X / Y ratio, the production method of the present invention is characterized in that a relatively small amount of the second metal compound is used as compared with the first metal compound. From this point of view, the present inventors have made the following assumptions regarding the function of the second metal compound.

  Interaction occurs between the second metal compound and the first metal compound, which is the main catalyst such as a titanium compound, and the coordination or bond structure of the main catalyst changes. As a result, specific active sites are formed so that the molecules of the reaction raw material can interact with the metal atoms of the main catalyst during the reaction.

  In addition, due to the interaction between the second metal compound and the main catalyst compound, the nature of the acid or base at the specific active site of the main catalyst is suppressed. Thereby, an unnecessary side reaction and the accompanying by-product are suppressed.

As a result of these, it is speculated that the second metal compound improves the polycondensation reaction catalytic ability of the first metal compound.
In addition, the following assumptions are also made. That is, when an excessive amount of the second metal compound is added, unnecessary side reactions such as a dehydration reaction of the secondary hydroxyl group of ricinoleic acid are promoted due to excessive catalytic activity. As a result, the production of by-products such as the end-capping compound becomes excessive, so that the first metal compound does not exhibit good polymerization activity. Therefore, it is presumed that the second metal compound is preferably used in a small amount within a certain range as described above as compared with the first metal compound.

(Polymerization process)
Polymerization of the raw material containing at least one selected from ricinoleic acid and derivatives thereof can be performed under known conditions. Specifically, as the polymerization in the previous stage, at least one selected from ricinoleic acid and derivatives thereof, a diol and dicarboxylic acid used as necessary, and the plurality of types of metal compounds as a catalyst are used as a reactor. Water and alcohol produced while charging and heating are removed to proceed with esterification or transesterification to synthesize a low molecular weight oligomer. Thereafter, as the subsequent polymerization, the polycondensation reaction proceeds under reduced pressure, and the generated alcohol compound is removed to increase the molecular weight. A specific preferred temperature range when synthesizing a low molecular weight oligomer by an esterification reaction or a transesterification reaction, which is the preceding polymerization, is 200 to 250 ° C, more preferably 210 to 230 ° C. The specific preferred temperature range of the polycondensation reaction, which is the latter polymerization, is 220 to 250 ° C., more preferably 220 to 230 ° C., and the pressure in the reaction apparatus is preferably 400 Pa (3 Torr) or less, more preferably 133 Pa (1 Torr) or less. It is obvious that a lower pressure in the reactor is preferable, but considering the production cost, the lower limit of the pressure is preferably 0.05 Torr, more preferably 0.1 Torr.

  Of course, the polymerization reaction can be carried out in the presence of a known additive. For example, a phosphorus compound or the like may be allowed to coexist in the polymerization reaction solution as a heat resistance stabilizer. Specific examples of heat stabilizers include phosphate esters such as trimethyl phosphate, triethyl phosphate, tri-n-butyl phosphate, trioctyl phosphate, triphenyl phosphate; triphenyl phosphite, trisdodecyl phosphite, trisnonyl phenyl phosphate. Phosphites such as phytates; acidic phosphates such as methyl acid phosphate, ethyl acid phosphate, isopropyl acid phosphate, butyl acid phosphate, phenyl acid phosphate, dibutyl phosphate, monobutyl phosphate, dioctyl phosphate, orthophosphoric acid, polyphosphorus In addition to acids, etc., phenylphosphonic acid, PEP-36, Irgafos 168, Sumilizer GP, PEP-8, P-EPQ, Ir Phosphorus compounds such as gamod 295 and triphenylphosphine are included.

  Further, within the range in which the characteristics of the present invention are not impaired, hindered phenolic antioxidants such as Irganox 1076, Irganox 1010, Irganox 245, Irgamod 3114, Sumilizer GS, tetratetraethylammonium hydroxide, tetramethylammonium hydroxide, etc. PH stabilizers, amine stabilizers such as Irgastab FS 301FF, metal supplements such as CDA-1, benzotriazole, Irganox MD 1024, and Naugaard XL-1, oxazoline compounds or isocyanate compounds, epoxy compounds, carbodiimides Polymerization may be performed in the presence of a chain extender such as a compound, a glycidyl compound, or a caprolactam compound.

(polyester)
The polyester obtained by the production method of the present invention has a higher molecular weight than the polyester obtained when a conventional inorganic catalyst is used. Specifically, the molecular weight of the polyester obtained by the production method of the present invention is preferably 30,000 to 500,000, and more preferably 90, as a weight average molecular weight in terms of polystyrene measured by the GPC method described later. 1,000 to 500,000, more preferably 100,000 to 500,000.

  In the polyester obtained by the production method of the present invention, the content ratio of the structural unit derived from the ricinoleic acid and its derivative is preferably 10 to 100 mol%. The minimum with the said preferable content rate is 30 mol%, and a more preferable minimum is 50 mol%. Moreover, the preferable upper limit is 80 mol%, and a more preferable upper limit is 70 mol%.

  The content ratio of the structural unit derived from the dicarboxylic acid compound is preferably 0 to 45 mol%. The minimum with the said preferable content rate is 10 mol%, and a more preferable minimum is 15 mol%. Moreover, the preferable upper limit is 35 mol%, and a more preferable upper limit is 25 mol%.

  The content ratio of the structural unit derived from the diol compound is preferably 0 to 45 mol%. The minimum with the said preferable content rate is 10 mol%, and a more preferable minimum is 15 mol%. Moreover, the preferable upper limit is 35 mol%, and a more preferable upper limit is 25 mol%.

  The content ratio of the structural unit derived from the dicarboxylic acid compound and the diol compound such as ricinoleic acid is a numerical value when the total of the structural units derived from the dicarboxylic acid compound and the diol compound such as ricinoleic acid is 100 mol%. .

The polyester obtained by the production method of the present invention may contain, for example, a carbon-carbon double bond based on a structural unit derived from ricinoleic acid. The polyester obtained by the production method of the present invention can be subjected to a hydrogenation reaction using a known hydrogenation catalyst, if necessary.
By using the production method of the present invention, a polymer having a high molecular weight can be produced efficiently.

The first polyester according to the present invention is:
(I) 10-80 mol% of structural units derived from ricinoleic acid and its derivatives,
(II) 10 to 45 mol% of structural units derived from a dicarboxylic acid having 2 to 12 carbon atoms and (III) 10 to 45 mol% of structural units derived from a diol having 2 to 12 carbon atoms.
(However, the total of structural units (I), (II), and (III) is 100 mol%)
It is characterized by including. A more preferable range of each structural unit is the same as the range described in the description of the polyester obtained by the production method.

The second polyester of the present invention includes a metal selected from titanium, germanium, antimony, and a metal selected from Group 2 and Group 8-12 metals of the periodic table,
As the metal,
When the titanium is included, the titanium content is 1,000 to 5,000 wtppm,
When the germanium is included, the germanium content is 100 to 30,000 wtppm,
When the antimony is included, the content of antimony is 100 to 30,000 wtppm,
And the total number of moles (X) of the metals in groups 2 and 8 to 12 of the periodic table, and the total number of moles of titanium atoms, germanium atoms and antimony atoms derived from the titanium compounds, germanium compounds and antimony compounds (Y). And the ratio (X / Y) is in the range of 0.05 to 0.5,
(I) 10 to 100 mol% of structural units derived from ricinoleic acid and its derivatives,
(II) 0 to 45 mol% of structural units derived from a dicarboxylic acid having 2 to 12 carbon atoms and (III) 0 to 45 mol% of structural units derived from a diol having 2 to 12 carbon atoms.
(However, the total of structural units (I), (II), and (III) is 100 mol%)
It is characterized by including. The preferred range of the metal content is the same as the range disclosed in the description of the production method, and the preferred range of the content of the structural unit is the same as the range disclosed in the description of the polyester obtained by the production method. is there. Moreover, the content rate of the said metal can be computed from the preparation amount of the said acid compound, diol compound, etc. which are the said catalyst and raw material. Moreover, it can also measure using conventional methods, such as ICP method.

  The first polyester and the second polyester of the present invention preferably have a polystyrene-equivalent weight average molecular weight of 90,000 to 500,000 as measured by GPC method. The more preferable range of the weight average molecular weight is the same as the range disclosed in the description of the polyester obtained by the production method.

  The first and second polyesters of the present invention contain (I) a structural unit derived from ricinoleic acid and a derivative thereof, (II) a structural unit derived from a dicarboxylic acid, and (III) a structural unit derived from a diol. Preferably, a specific compound may be included in a specific content range. For this reason, the molecular weight tends to be high and the interaction with various substances tends to be strong. For example, it may exhibit excellent properties such as adhesiveness. Moreover, the tendency may become so remarkable that there are few carbon numbers of (II) dicarboxylic acid and (III) diol.

Moreover, the polyester of this invention can also contain the structural unit derived from the polyfunctional component more than trifunctional described by the said manufacturing method.
The polyester of the present invention is preferably produced by the production method described above.

  The first and second polyesters according to the present invention, including the polyester obtained by the production method of the present invention, are known various additives such as antioxidants, crystal nucleating agents, flame retardants, antistatic agents, mold release agents. It can be used in a mode like a composition in combination with an agent, an ultraviolet absorber and the like and other known polymers. In this case, the content of the additive is preferably less than 50% of the total, more preferably less than 20%, even more preferably less than 5%, particularly preferably less than 1%, particularly preferably less than 0.3%. is there. The weight ratio of the other polymer to the polymer obtained by the production method of the present invention is the weight of the polymer obtained by the production method of the present invention (A), and the weight of the other polymer (B). (A) / (B) is 95/5 to 5/95, more preferably 80/20 to 20/80, and still more preferably 70/30 to 30/70. Of course, it goes without saying that the preferred ratio varies depending on the application to be applied.

  The polyester obtained by the production method of the present invention can be used for various known applications. Specific examples include lubricants, plasticizers, emulsifiers, dispersants, surfactants, and the like. As a preferable use, the elastomer use etc. of patent document 2 etc. can be illustrated.

Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to these examples. The measuring method of each physical property is as follows.
<Weight average molecular weight (Mw)>
The obtained polyester was dissolved in a 1: 1 mixed solution of chloroform and hexafluoroisopropanol, and further diluted with chloroform to prepare a 0.1% (w / v) solution, and gel permeation. Chromatography [Waters GPC system, detector: RI (Waters 2414), column: PLgel 5μ MIXED-D (Polymer Laboratories), column temperature: 40 ° C., flow rate: 1 ml / min, solvent: chloroform] Thus, the weight average molecular weight was calculated based on the polystyrene standard sample.

<Intrinsic viscosity (IV)>
The obtained polyester was dissolved in a mixed solvent having a mass ratio of 1: 1 of phenol and 1,1,2,2-tetrachloroethane to prepare a solution. The flow down time of the obtained solution at 25 ° C. was measured using an Ubbelohde viscometer, and applied to the following formula to calculate the intrinsic viscosity.
[Η] = ηSP / [C (1 + KηSP)]
[Η]: Intrinsic viscosity (dl / g)
ηSP: specific viscosity C: sample concentration (g / dl)
K: Constant viscosity (specific viscosity ηSP of samples having different sample concentrations C (3 or more)) was measured based on the following formula, and the sample concentration C was plotted on the horizontal axis and ηSP / C plotted on the vertical axis. Tilt)
t: Number of seconds that the sample solution flows (seconds)
t0: The number of seconds during which the solvent flows (seconds)
ηSP = (t−t0) / t0

<Polyester composition>
The composition of the polyester was analyzed by the following procedure.
1) An ECA500 nuclear magnetic resonance apparatus manufactured by JEOL Ltd. was used, and deuterated chloroform was used as a solvent. The sample concentration was 35 mg / 0.5 mL, and the measurement temperature was 50 ° C.
The observation nucleus is ¹ H (500 MHz), the sequence is a single pulse, the pulse width is 6.3 μs (45 ° pulse), the repetition time is 8.5 seconds, the integration number is 394 times, and the hydrogen signal of tetramethylsilane is chemically It was measured as a reference value for shift. Each peak was assigned by a conventional method.
2) The obtained measurement data was analyzed, the carboxylic acid and alcohol component which comprise polyester were identified, and those component ratios were calculated | required.

<Element content>
Sulfuric acid was added to the polyester obtained, and nitric acid was added dropwise with heating to decompose the organic matter. The obtained decomposition solution was made up with pure water, and the content of each metal element contained in the catalyst was measured with an ICP emission spectrometer (ICPS-8100, manufactured by Shimadzu Corporation). The content of each metal element was determined by preparing a calibration curve using a sample whose content is known and comparing it with the calibration curve.

<Polymerization reaction rate>
The polymerization reaction rate in the polycondensation reaction step after completion of the esterification reaction was measured by the following method.
The intrinsic viscosity (dl / g) of the obtained polyester is determined as the time (h) required for the polycondensation reaction after the end of the esterification reaction (the time from when the specified polycondensation temperature is reached until the end of the polycondensation reaction) ) To obtain a polymerization reaction rate ((dl / g) / h). The end point of the polycondensation reaction was the point at which the stirring torque of the stirrer stopped increasing.

[Example 1]
Into a 500 ml glass polymerization reaction flask, 0.04 part by mass of ricinoleic acid, 13.6 parts by mass of sebacic acid, and 9.7 parts by mass of 1,4-butanediol were added with a 20 wt% aqueous solution of calcium acetate monohydrate. 26 parts by mass was added, and the temperature was raised from room temperature to 210 ° C. over 30 minutes. After reaching 210 ° C., 0.20 parts by mass of titanium tetrabutoxide and 0.03 parts by mass of a 20 wt% aqueous solution of tetratetraethylammonium hydroxide were added and held at 210 ° C. for 5 hours for esterification reaction. .

  After completion of the esterification reaction, 1.36 parts by mass of titanium tetrabutoxide was added, and the pressure was reduced to 0.133 kPa (1 Torr) while increasing the temperature to 230 ° C., which is a polycondensation temperature, over 60 minutes, and a polycondensation reaction was performed. It was. A small amount of the reaction product was withdrawn periodically and the viscosity was measured. The reaction was terminated when the viscosity change was within 0.01 dl / g. After completion of the reaction, the produced polyester was extracted from the reaction vessel within 10 minutes.

[Example 2]
Into a 500 ml glass polymerization reaction flask, 0.04 part by mass of ricinoleic acid, 13.6 parts by mass of sebacic acid, and 9.7 parts by mass of 1,4-butanediol were added with a 20 wt% aqueous solution of calcium acetate monohydrate. 31 mass parts, 0.27 mass part of 20 wt% aqueous solution of magnesium acetate tetrahydrate was added, and it heated up from normal temperature to 210 degreeC over 30 minutes. Thereafter, a polyester was obtained in the same manner as in Example 1.

[Example 3]
Into a 500 ml glass polymerization reaction flask, 0.04 part by mass of ricinoleic acid, 13.6 parts by mass of sebacic acid, and 9.7 parts by mass of 1,4-butanediol were added with a 20 wt% aqueous solution of calcium acetate monohydrate. 88 mass parts, 0.27 mass part of 20 wt% aqueous solution of magnesium acetate tetrahydrate was added, and it heated up from normal temperature to 210 degreeC over 30 minutes. Thereafter, a polyester was obtained in the same manner as in Example 1.

[Example 4]
Into a 500 ml glass polymerization reaction flask, 0.04 part by mass of ricinoleic acid, 13.6 parts by mass of sebacic acid, and 9.7 parts by mass of 1,4-butanediol were added with a 20 wt% aqueous solution of calcium acetate monohydrate. 88 parts by mass, 0.88 parts by mass of a 20 wt% aqueous solution of magnesium acetate tetrahydrate was added, and the temperature was raised from room temperature to 210 ° C. over 30 minutes. Thereafter, a polyester was obtained in the same manner as in Example 1.

[Example 5]
In a 500 ml glass polymerization reaction flask, 40.0 parts by mass of ricinoleic acid, 13.6 parts by mass of sebacic acid, 9.7 parts by mass of 1,4-butanediol, 0.05 parts by mass of magnesium acetate tetrahydrate, 0.30 mass part of 20 wt% aqueous solution of cobalt acetate tetrahydrate was added, and it heated up from normal temperature to 210 degreeC over 30 minutes. Thereafter, a polyester was obtained in the same manner as in Example 1.

[Example 6]
Into a 500 ml glass polymerization reaction flask was added 0.04 part by mass of a 20 wt% aqueous solution of magnesium acetate tetrahydrate to 40.0 parts by mass of ricinoleic acid, 13.6 parts by mass of sebacic acid, and 9.7 parts by mass of 1,4-butanediol. 27 parts by mass and 0.24 parts by mass of a 20 wt% aqueous solution of zinc acetate dihydrate were added, and the temperature was raised from room temperature to 210 ° C. over 30 minutes. Thereafter, a polyester was obtained in the same manner as in Example 1.

[Example 7]
Into a 500 ml glass polymerization reaction flask, 0.04 part by mass of ricinoleic acid, 13.6 parts by mass of sebacic acid, and 9.7 parts by mass of 1,4-butanediol were added with a 20 wt% aqueous solution of calcium acetate monohydrate. 31 mass parts, 0.27 mass part of 20 wt% aqueous solution of magnesium acetate tetrahydrate was added, and it heated up from normal temperature to 210 degreeC over 30 minutes. After reaching 210 ° C., 0.20 parts by mass of titanium tetrabutoxide and 0.03 parts by mass of a 20 wt% aqueous solution of tetraethylammonium hydroxide were added and held at 210 ° C. for 5 hours to carry out an esterification reaction.

  After completion of the esterification reaction, 1.36 parts by mass of titanium tetrabutoxide and 4.24 parts by mass of a 5 wt% butanediol solution of antimony acetate were added. Thereafter, a polyester was obtained in the same manner as in Example 1.

[Example 8]
Into a 500 ml glass polymerization reaction flask, 0.04 part by mass of ricinoleic acid, 13.6 parts by mass of sebacic acid, and 9.7 parts by mass of 1,4-butanediol were added with a 20 wt% aqueous solution of calcium acetate monohydrate. 31 mass parts, 0.27 mass part of 20 wt% aqueous solution of magnesium acetate tetrahydrate was added, and it heated up from normal temperature to 210 degreeC over 30 minutes. After reaching 210 ° C., 0.20 parts by mass of titanium tetrabutoxide and 0.03 parts by mass of a 20 wt% aqueous solution of tetraethylammonium hydroxide were added and held at 210 ° C. for 5 hours to carry out an esterification reaction.

  After completion of the esterification reaction, 1.36 parts by mass of titanium tetrabutoxide and 1.98 parts by mass of a 5 wt% butanediol solution of germanium dioxide were added. Thereafter, a polyester was obtained in the same manner as in Example 1.

[Example 9]
In a 500 ml glass polymerization reaction flask, 30.5 parts by mass of ricinoleic acid, 20.6 parts by mass of sebacic acid, 13.3 parts by mass of 1,4-butanediol were added with a 20 wt% aqueous solution of calcium acetate monohydrate. 31 mass parts, 0.27 mass part of 20 wt% aqueous solution of magnesium acetate tetrahydrate was added, and it heated up from normal temperature to 210 degreeC over 30 minutes. Thereafter, a polyester was obtained in the same manner as in Example 1.

[Example 10]
In a 500 ml glass polymerization reaction flask, 30.5 parts by mass of ricinoleic acid, 16.9 parts by mass of terephthalic acid and 29.9 parts by mass of 1,4-butanediol were added with a 20 wt% aqueous solution of calcium acetate monohydrate. 31 mass parts, 0.27 mass part of 20 wt% aqueous solution of magnesium acetate tetrahydrate was added, and it heated up from normal temperature to 210 degreeC over 30 minutes. Thereafter, a polyester was obtained in the same manner as in Example 1.

[Example 11]
Into a 500 ml glass polymerization reaction flask, 0. 5 wt% aqueous solution of calcium acetate monohydrate was added to 30.5 parts by mass of ricinoleic acid, 20.6 parts by mass of sebacic acid, and 17.5 parts by mass of 1,6-hexanediol. 31 mass parts, 0.27 mass part of 20 wt% aqueous solution of magnesium acetate tetrahydrate was added, and it heated up from normal temperature to 210 degreeC over 30 minutes. Thereafter, a polyester was obtained in the same manner as in Example 1.

[Example 12]
In a 500 ml glass polymerization reaction flask, 30.5 parts by mass of ricinoleic acid, 20.6 parts by mass of sebacic acid, 9.2 parts by mass of ethylene glycol and 0.31 part by mass of a 20 wt% aqueous solution of calcium acetate monohydrate, 0.27 parts by mass of a 20 wt% aqueous solution of magnesium acetate tetrahydrate was added, and the temperature was raised from room temperature to 210 ° C. over 30 minutes. Thereafter, a polyester was obtained in the same manner as in Example 1.

[Comparative Example 1]
Into a 500 ml glass polymerization reaction flask, 0.04 part by mass of ricinoleic acid, 13.6 parts by mass of sebacic acid, and 9.7 parts by mass of 1,4-butanediol were added with a 20 wt% aqueous solution of calcium acetate monohydrate. 04 parts by mass and 0.03 parts by mass of a 20 wt% aqueous solution of magnesium acetate tetrahydrate were added, and the temperature was raised from room temperature to 210 ° C. over 30 minutes. After reaching 210 ° C., 0.20 parts by mass of titanium tetrabutoxide and 0.03 parts by mass of a 20 wt% aqueous solution of tetraethylammonium hydroxide were added and held at 210 ° C. for 5 hours to carry out an esterification reaction.

  After completion of the esterification reaction, the pressure was reduced to 0.133 kPa (1 Torr) while raising the temperature to 230 ° C. over 60 minutes, and a polycondensation reaction was performed. A small amount of the reaction product was withdrawn periodically and the viscosity was measured. The reaction was terminated when the viscosity change was within 0.01 dl / g. Polyester was extracted from the reaction vessel within 10 minutes after completion of the reaction.

[Comparative Example 2]
Into a 500 ml glass polymerization reaction flask, 0.04 part by mass of ricinoleic acid, 13.6 parts by mass of sebacic acid, and 9.7 parts by mass of 1,4-butanediol were added with a 20 wt% aqueous solution of calcium acetate monohydrate. 42 parts by mass and 0.36 parts by mass of a 20 wt% aqueous solution of magnesium acetate tetrahydrate were added, and the temperature was raised from room temperature to 210 ° C. over 30 minutes. After reaching 210 ° C., 0.20 parts by mass of titanium tetrabutoxide and 0.03 parts by mass of a 20 wt% aqueous solution of tetraethylammonium hydroxide were added and held at 210 ° C. for 5 hours to carry out an esterification reaction.

  After completion of the esterification reaction, 1.95 parts by mass of titanium tetrabutoxide was added, and the pressure was reduced to 0.133 kPa (1 Torr) while raising the temperature to 230 ° C. over 60 minutes, and a polycondensation reaction was performed. A small amount of the reaction product was withdrawn periodically and the viscosity was measured. The reaction was terminated when the viscosity change was within 0.01 dl / g. Polyester was extracted from the reaction vessel within 10 minutes after completion of the reaction.

[Comparative Example 3]
40.0 parts by mass of ricinoleic acid, 13.6 parts by mass of sebacic acid, and 9.7 parts by mass of 1,4-butanediol are mixed in a 500 ml glass polymerization reaction flask, and the temperature is raised from room temperature to 210 ° C. over 30 minutes. did. After reaching 210 ° C., 0.20 parts by mass of titanium tetrabutoxide and 0.03 parts by mass of a 20 wt% aqueous solution of tetraethylammonium hydroxide were added and held at 210 ° C. for 5 hours to carry out an esterification reaction. Thereafter, a polyester was obtained in the same manner as in Example 1.

[Comparative Example 4]
In a 500 ml glass polymerization reaction flask, 10.0 parts by mass of ricinoleic acid, 13.6 parts by mass of sebacic acid, and 9.7 parts by mass of 1,4-butanediol were mixed with a 20 wt% aqueous solution of calcium acetate monohydrate. 23 parts by mass and 1.24 parts by mass of a 20 wt% aqueous solution of magnesium acetate tetrahydrate were added, and the temperature was raised from room temperature to 210 ° C. over 30 minutes. Thereafter, a polyester was obtained in the same manner as in Example 1.

[Comparative Example 5]
A 500 ml glass polymerization reaction flask was prepared by adding 10.0 parts by mass of ricinoleic acid, 13.6 parts by mass of sebacic acid, and 9.7 parts by mass of 1,4-butanediol to a 20 wt% aqueous solution of magnesium acetate tetrahydrate. 24 parts by mass and 2.07 parts by mass of a 20 wt% aqueous solution of cobalt acetate tetrahydrate were added, and the temperature was raised from room temperature to 210 ° C. over 30 minutes. Thereafter, a polyester was obtained in the same manner as in Example 1.

[Comparative Example 6]
A 500 ml glass polymerization reaction flask was prepared by adding 10.0 parts by mass of ricinoleic acid, 13.6 parts by mass of sebacic acid, and 9.7 parts by mass of 1,4-butanediol to a 20 wt% aqueous solution of magnesium acetate tetrahydrate. 24 parts by mass and 2.07 parts by mass of a 20 wt% aqueous solution of zinc acetate dihydrate were added, and the temperature was raised from room temperature to 210 ° C. over 30 minutes. Thereafter, a polyester was obtained in the same manner as in Example 1.

[Comparative Example 7]
40.0 parts by mass of ricinoleic acid, 13.6 parts by mass of sebacic acid, and 9.7 parts by mass of 1,4-butanediol are mixed in a 500 ml glass polymerization reaction flask, and the temperature is raised from room temperature to 210 ° C. over 30 minutes. did. After reaching 210 ° C., 0.20 parts by mass of titanium tetrabutoxide and 0.03 parts by mass of a 20 wt% aqueous solution of tetraethylammonium hydroxide were added and held at 210 ° C. for 5 hours to carry out an esterification reaction.

  After completion of the esterification reaction, 1.36 parts by mass of titanium tetrabutoxide and 4.24 parts by mass of a 5 wt% butanediol solution of antimony acetate were added. Thereafter, a polyester was obtained in the same manner as in Example 1.

[Comparative Example 8]
40.0 parts by mass of ricinoleic acid, 13.6 parts by mass of sebacic acid, and 9.7 parts by mass of 1,4-butanediol are mixed in a 500 ml glass polymerization reaction flask, and the temperature is raised from room temperature to 210 ° C. over 30 minutes. did. After reaching 210 ° C., 0.20 parts by mass of titanium tetrabutoxide and 0.03 parts by mass of a 20 wt% aqueous solution of tetraethylammonium hydroxide were added and held at 210 ° C. for 5 hours to carry out an esterification reaction.

  After completion of the esterification reaction, 1.36 parts by mass of titanium tetrabutoxide and 1.98 parts by mass of a 5 wt% butanediol solution of germanium dioxide were added. Thereafter, a polyester was obtained in the same manner as in Example 1.

[Comparative Example 9]
A 500 ml glass polymerization reaction flask was mixed with 30.5 parts by mass of ricinoleic acid, 20.6 parts by mass of sebacic acid, and 13.3 parts by mass of 1,4-butanediol, and the temperature was raised from room temperature to 210 ° C. over 30 minutes. did. Thereafter, a polyester was obtained in the same manner as in Example 1.

[Comparative Example 10]
A 500 ml glass polymerization reaction flask was mixed with 30.5 parts by mass of ricinoleic acid, 16.9 parts by mass of terephthalic acid, and 29.9 parts by mass of 1,4-butanediol, and the temperature was raised from room temperature to 210 ° C. over 30 minutes. did. Thereafter, a polyester was obtained in the same manner as in Example 1.

[Comparative Example 11]
A 500 ml glass polymerization reaction flask was mixed with 30.5 parts by mass of ricinoleic acid, 20.6 parts by mass of sebacic acid, and 17.5 parts by mass of 1,6-hexanediol, and the temperature was raised from room temperature to 210 ° C. over 30 minutes. did. Thereafter, a polyester was obtained in the same manner as in Example 1.

[Comparative Example 12]
A 500 ml glass polymerization flask was mixed with 30.5 parts by mass of ricinoleic acid, 20.6 parts by mass of sebacic acid, and 9.2 parts by mass of ethylene glycol, and the temperature was raised from room temperature to 210 ° C. over 30 minutes. Thereafter, a polyester was obtained in the same manner as in Example 1.

  The evaluation results of Examples 1 to 12 are shown in Tables 1 and 3, and the evaluation results of Comparative Examples 1 to 12 are shown in Tables 2 and 4. In Tables 1 and 2, titanium, antimony, and germanium are referred to as main catalyst metal (Y), and a metal selected from Group 2 or Groups 8-12 of the periodic table is referred to as promoter metal (X). In the table, the main catalyst metal amount and the cocatalyst metal amount indicate the amount of the catalyst metal used relative to the produced polyester.

  On the other hand, in Tables 3 and 4, titanium, antimony, and germanium are referred to as metal (Y), and a metal selected from Group 2 or Groups 8-12 of the periodic table is referred to as promoter metal (X). In the table, the amount of metal (Y) and the amount of metal (X) indicate the content of each metal obtained by measuring the obtained polyester with ICP.

Claims (7)

A method for producing a polyester by polymerizing a raw material containing at least one selected from ricinoleic acid and derivatives thereof,
As a polymerization catalyst, using at least one compound selected from a titanium compound, a germanium compound, and an antimony compound, and at least one compound selected from the group 2 and groups 8 to 12 of the periodic table,
The content of the metal derived from the titanium compound, germanium compound and antimony compound with respect to the produced polyester,
When using the titanium compound, the amount of titanium atoms is 1,000 to 5,000 wtppm with respect to the amount of polyester produced,
When using the germanium compound, the amount of germanium atoms is 100 to 30,000 wtppm with respect to the amount of polyester produced,
When using the antimony compound, the amount of antimony atoms is 100 to 30,000 wtppm with respect to the amount of polyester produced,
And the total number of moles (X) of metal atoms derived from the compounds of metals of Groups 2 and 8-12 of the periodic table, and titanium atoms, germanium atoms and antimony derived from the titanium compounds, germanium compounds and antimony compounds. A method for producing a polyester, wherein the ratio (X / Y) to the total number of moles of atoms (Y) is in the range of 0.05 to 0.5.   The molar ratio of the structural unit derived from ricinoleic acid and its derivative contained in the produced polyester is derived from the structural unit derived from ricinoleic acid and its derivative contained in the produced polyester, the structural unit derived from dicarboxylic acid and the diol. The manufacturing method of the polyester of Claim 1 which is 10-100 mol% with respect to the sum total of a structural unit.   The manufacturing method of the polyester of Claim 1 in which the said raw material contains at least 1 sort (s) chosen from a C2-C12 dicarboxylic acid and a C2-C12 diol component. (I) 10-80 mol% of structural units derived from ricinoleic acid and its derivatives,
(II) 10 to 45 mol% of structural units derived from a dicarboxylic acid having 2 to 12 carbon atoms and (III) 10 to 45 mol% of structural units derived from a diol having 2 to 12 carbon atoms.
(However, the total of structural units (I), (II), and (III) is 100 mol%)
Including polyester. A metal selected from titanium, germanium, antimony, and a metal selected from Group 2 and Group 8-12 metals of the Periodic Table,
As the metal,
When the titanium is included, the titanium content is 1,000 to 5,000 wtppm,
When the germanium is included, the germanium content is 100 to 30,000 wtppm,
When the antimony is included, the content of antimony is 100 to 30,000 wtppm,
And the total number of moles (X) of the metals in groups 2 and 8 to 12 of the periodic table, and the total number of moles of titanium atoms, germanium atoms and antimony atoms derived from the titanium compounds, germanium compounds and antimony compounds (Y). And the ratio (X / Y) is in the range of 0.05 to 0.5,
(I) 10 to 100 mol% of structural units derived from ricinoleic acid and its derivatives,
(II) 0 to 45 mol% of structural units derived from a dicarboxylic acid having 2 to 12 carbon atoms and (III) 0 to 45 mol% of structural units derived from a diol having 2 to 12 carbon atoms.
(However, the total of structural units (I), (II), and (III) is 100 mol%)
Including polyester. (I) 10-80 mol% of structural units derived from ricinoleic acid and its derivatives,
(II) 10 to 45 mol% of structural units derived from a dicarboxylic acid having 2 to 12 carbon atoms and (III) 10 to 45 mol% of structural units derived from a diol having 2 to 12 carbon atoms.
(However, the total of structural units (I), (II), and (III) is 100 mol%)
The polyester according to claim 5, comprising:   The polyester according to any one of claims 4 to 6, which has a weight average molecular weight of 90,000 to 500,000 as measured by GPC method.