JP2021138816A - Method of producing polyester - Google Patents

Abstract

To provide a method of producing polyester where a molecular weight increases with time since a molecular weight occasionally does not increase with time in a method of producing polyester by polymerizing ricinoleic acid or hydrocarbyl ester of a derivative thereof.SOLUTION: Polymerization is performed in a range satisfying a relation of a catalyst concentration of recinoleic acid or hydrocarbyl ester of a derivative thereof at a specific temperature.SELECTED DRAWING: None

Description

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

In recent years, from the viewpoints of global warming, renewable energy, resource recycling, resource recycling, etc., material development based on natural material-derived raw materials instead of petroleum raw materials has become active.
As a recyclable material, many techniques related to biodegradable polyesters, particularly aliphatic polyesters, are disclosed. For example, the development of thermoplastic biodegradable aliphatic polyesters composed of aliphatic dicarboxylic acids or esters thereof, aliphatic diols or alicyclic diols, naturally occurring unsaturated fatty acids or esters thereof is known. A typical example thereof is a polycondensate containing lactic acid. On the other hand, a method using ricinoleic acid or a derivative thereof obtained by a method such as hydrolysis of castor oil has also been studied, and specific examples thereof include the techniques disclosed in Patent Documents 1 to 3. You can.

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

Further, Patent Document 1 discloses a method of performing polycondensation using a supported enzyme in which a carrier such as synthetic zeolite is supported, such as ribase, as a catalyst. Enzymes tend to have a lower temperature range in which catalytic action is exhibited than inorganic catalysts, which may make it somewhat difficult to industrialize techniques using enzymes. It is disclosed that by using a carrier of a supported enzyme as a specific carrier, it is possible to increase the temperature range in which the enzymatic action is exhibited.

Patent Document 2 and Patent Document 3 each disclose techniques for using a ricinoleic acid-based polymer as a component of an elastomer or a lubricating oil.
In the production examples of the polycondensate using ricinoleic acid in Patent Documents 2 and 3, an enzyme is used as a catalyst.
The present inventors have reported that a high polymer can be obtained by polycondensing ricinoleic acid in combination with a specific alcohol using a specific metal compound as a catalyst. (Patent Document 4)
When the ricinoleic acid polycondensate is hydrogenated, it becomes a polymer of 12-hydroxystearic acid.

International Publication 2008/029805 Pamphlet Japanese Patent No. 5373435 Japanese Patent No. 5398708 Japanese Unexamined Patent Publication No. 2017-66698

As can be seen from the above patent documents, the polymer of ricinoleic acid and the polymer of 12-hydroxystearic acid which is a hydrogenator thereof tend to be more difficult to obtain a polymer having a high molecular weight than other polyesters. .. Regarding this cause, it is possible that the polycondensation reaction is unlikely to occur, and that the polycondensation reaction is generally a parallel reaction, so that a relatively fast depolymerization reaction may occur at the same time.
In Patent Document 4, it was demonstrated that a high polymer of ricinoleic acid or a derivative thereof can be obtained with a specific metal compound catalyst. On the other hand, according to subsequent studies, in the polycondensation reaction using hydrocarbyl ester of ricinol acid or its derivative, even if the above metal compound is used, the molecular weight tends to increase at a relatively early stage of the polycondensation reaction. , I found a problem that the molecular weight may decrease over time.

In general, the polycondensation method using a hydrocarbyl ester of a polyvalent carboxylic acid tends to remove the alcohol by-produced during the polycondensation reaction more easily than the reaction using a polyvalent carboxylic acid (water by-produces). .. Therefore, the method of using the above ester for producing polyester is one of the preferable methods. However, from the above problems, it can be said that it is an undesired method for stably obtaining ricinoleic acid having a high molecular weight or a derivative thereof.
Therefore, it is an object of the present invention to provide a method for producing a polyester which can easily control the molecular weight and obtain a high polymer by a polycondensation reaction using ricinoleic acid or a hydrocarbyl ester of a derivative thereof.

As a result of studies to solve the above problems, the present inventors have determined that the amount of catalyst and the reaction temperature are different in the process of performing a polycondensation reaction on hydrocarbyl ester of ricinol acid or its derivative in the presence of a metal compound catalyst. We found that the molecular weight tends to increase over time during the polycondensation reaction when certain relationships are met. The present invention has been completed.

That is, the present invention has the following configurations [1] to [4].
[1] A method for producing a polyester, which polymerizes a raw material containing at least one selected from ricinoleic acid and hydrocarbyl esters of its derivatives.
At least one selected from ricinoleic acid and its derivatives hydrocarbyl ester under the conditions satisfying the following formulas (A) and (B) in the presence of at least one compound selected from titanium compounds, germanium compounds and antimony compounds. A method for producing a polyester in which a raw material containing is polymerized.
When the content (ppm) of titanium, germanium and antimony is M and the polycondensation reaction temperature (° C.) is T,
(A) When 0 <M ≦ 1200, 195 ≦ T ≦ 233, and
(B) When 1200 <M ≦ 5000
-0.0067xM + 203≤T≤-0.0067xM + 241.
[2] The molar ratio of the structural unit derived from the hydrocarbyl ester of ricinolic acid and its derivative contained in the produced polyester is the structural unit derived from the hydrocarbyl ester of ricinolic acid and its derivative contained in the produced polyester, dicarboxylic acid. The method for producing a polyester according to the above [1], wherein the total of the structural units derived from the acid and the structural units derived from the diol is 100 mol%, which is 10 to 100 mol%.
[3] The method for producing a polyester according to the above [2], wherein the dicarboxylic acid is a dicarboxylic acid having 2 to 12 carbon atoms and the diol is a diol having 2 to 12 carbon atoms.
[4] The produced polyester is
(I) Structural units derived from ricinoleic acid and its derivatives hydrocarbyl ester 10-80 mol%,
(II) 10-45 mol% of structural unit derived from a dicarboxylic acid having 2 to 12 carbon atoms and (III) 10-45 mol% of structural unit derived from a diol having 2 to 12 carbon atoms.
(However, the total of the structural units of (I), (II), and (III) is 100 mol%)
The method for producing the polyester according to the above [3], which is a polyester satisfying the above conditions.

By using the production method of the present invention, it is possible to easily control the molecular weight and produce a high polymer even in a polycondensation reaction using ricinoleic acid and a hydrocarbyl ester of a derivative thereof as raw materials.

As described above, according to the studies by the present inventors, it has been found that in the polycondensation reaction of ricinoleic acid and its derivative hydrocarbyl ester by a conventional method, the molecular weight may decrease with time. .. It is considered that this is because depolymerization becomes predominant for some reason after the polycondensation reaction proceeds over time. This phenomenon is considered to be a problematic method for controlling the molecular weight of the polycondensate. The present invention provides a manufacturing method that solves this problem.
Hereinafter, the method for producing the polyester of the present invention will be described.
In the method for producing a polyester of the present invention, a specific metal compound catalyst is used in the process of obtaining a high polymer of hydrocarbyl ester of ricinol acid or a derivative thereof, and the amount of the catalyst and the polycondensation reaction temperature satisfy a specific relationship. It is a method characterized by that.
According to the present invention, even in a polycondensation reaction using ricinol acid and a hydrocarbyl ester of a derivative thereof as a raw material, the molecular weight at the time of the polycondensation reaction is satisfied by satisfying a specific relationship between the amount of the catalyst and the polycondensation reaction temperature. Can be carried out in a reaction in which the molecular weight of the ester increases with time, and the molecular weight of the reaction is generally easy to control.

The method for producing a polyester of the present invention contains at least one selected from ricinoleic acid and a hydrocarbyl ester of a derivative thereof as an essential component, and optionally contains a raw material containing a diol, a dicarboxylic acid or a derivative thereof, and a specific metal compound. It is characterized by a polymerization reaction in the presence of a catalyst.

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.

(Hydrocarbyl ester of ricinoleic acid and its derivatives)
Examples of the hydrocarbyl ester of ricinoleic acid and its derivative include a hydrocarbyl ester of ricinoleic acid and a hydrocarbyl ester of 12-hydroxystearic acid obtained by hydrogenating ricinoleic acid. These compounds proceed with a polycondensation reaction by utilizing a transesterification reaction or the like in the presence of a catalyst described later.

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

In the present invention, when the total molar amount of the terminal hydroxyl groups contained in each raw material used is (OH) and the total molar amount of the terminal carboxyl groups is (COOH), the molar ratios (hereinafter referred to as OH / COOH ratio) are used. The preferred range of) is 1.0 to 5.0, and more preferably 1.0 to 3.0. In the present invention, the terminal carboxyl group includes an ester group (COOR). 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 weight oligomer prepared in the esterification or transesterification reaction described later, and the reaction during polycondensation described later. There is a tendency for sex 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, so that the reactivity at the time of polycondensation may decrease.

(Diol compound)
As the diol compound, a known diol compound can be used without limitation, and an alkylene diol compound can be preferably used.
Specific examples of the alkylene diol include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, and 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) phenyl sulfone, 9,9- Ethylene oxide adducts of aromatic dihydroxy compounds such as bis [4'-(2 "-hydroxyethoxy) phenyl] fluorene, 1,4-bis (2'-hydroxyethoxy) benzene, tricyclo [5.2.1.0" (2,6)] Decandimethanol, 1,4-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 2,2-bis (4'-hydroxy) An alicyclic diol such as cyclohexyl) propane (hydroxidated bisphenol A) can be mentioned.

Primary alcohols are preferable as these diol compounds. If the diol compound is a secondary or higher alcohol, the reactivity of polycondensation may decrease.
Among these, a diol compound having 2 to 12 carbon atoms is preferable. A diol compound having 2 to 6 carbon atoms is more preferable, and a diol compound having 2 to 4 carbon atoms is particularly preferable. If the carbon number of the diol compound becomes too large, the reactivity of polycondensation 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 preferably, ethylene glycol, 1,3-propanediol and 1,4-butanediol having a relatively small number of carbon atoms are used. If biodegradability of the polycondensate is expected, the preferred diol compound is 1,4-butanediol, which is available from natural esters.
These diol compounds can also be used in combination of two or more. It can also be used as an ester with the above-mentioned ricinoleic acid or as 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 can be preferably used.

Examples of the aliphatic dicarboxylic acid compound include linear or branched fats such as succinic acid, malonic acid, glutaric acid, adipic acid, pimeric acid, suberic acid, azelaic acid, sebacic acid, undecandicarboxylic acid, and dodecanedicarboxylic acid. Group dicarboxylic acids; and lower alkyl esters of these aliphatic dicarboxylic acids.

Among these, a dicarboxylic acid compound having 2 to 12 carbon atoms is preferable. It is more preferably a dicarboxylic acid compound having 6 to 10 carbon atoms, and particularly preferably 9 to 10 carbon atoms. If the number of carbon atoms of the dicarboxylic acid compound becomes too large, the reactivity of polycondensation may decrease. Examples of the dicarboxylic acid compound having 9 to 10 carbon atoms include sebacic acid and azelaic acid, which have a structure relatively similar to that of ricinoleic acid.
These dicarboxylic acid compounds can also be used in combination of two or more. It can also be used as an ester with the above-mentioned ricinoleic acid or as a low-condensation compound.

(Other copolymerization components)
In the method for producing a polyester of the present invention, a copolymerization component other than the above-mentioned dicarboxylic acid compound and diol compound may be contained within a range that does not impair the object of the present invention. Specific examples of the copolymerization component include hydroxycarboxylic acids such as glycolic acid, 4-hydroxybenzoic acid and 4- (2'-hydroxyethoxy) benzoic acid, trimellitic acid, trimellitic acid, pyromellitic acid and naphthalenetetracarboxylic acid. , Trimethylol ethane, trimethylol propane, glycerol, pentaerythritol and other trifunctional or higher polyfunctional components.

(Metal compound)
In the production method of the present invention, one kind of metal compound may be used as a catalyst, or two kinds of metal compounds may be used in combination. Hereinafter, representative metal compounds will be introduced with reference to the first metal compound and the second metal compound.
The first metal compound is at least one compound selected from a titanium compound, an antimony compound and a germanium compound, and is an essential component in the present invention. As these metal compounds, those conventionally known to be suitably used as a polymerization catalyst for polyester can be used. A titanium compound and an antimony compound are preferable, and a titanium compound is more preferable. Specific examples of the titanium compound include tetrabutyl titanate, tetra-iso-propyl titanate, and acetyltri-iso-propyl titanate. Examples of the antimony compound include antimony acetate, and examples of the germanium compound include germanium dioxide. The titanium compound, antimony compound and germanium compound may be two or more kinds of titanium compounds, two or more kinds of antimony compounds and two or more kinds of germanium compounds, respectively.

In the method for producing a polyester of the present invention, the amounts of the titanium, germanium, and antimony compounds used are characterized in that they have a specific relationship with the polycondensation reaction temperature as described later, but the general amounts used are as follows. It is preferably in the range of.
The amount of the titanium compound used is preferably 50 to 5,000 wtppm in terms of metal, that is, in terms of titanium, with respect to the produced polyester. A more preferable lower limit is 70 wtppm, and a more preferable lower limit is 80 wtppm. A more preferred upper limit is 4,500 wtppm, and a more preferred upper limit is 4,000 wtppm.

The amount of the antimony compound used is preferably 50 to 5,000 wtppm in terms of metal, that is, in terms of antimony, with respect to the produced polyester. A more preferable lower limit value is 80 wtppm, and a more preferable lower limit value is 80 wtppm. A more preferable upper limit value is 4,500 wtppm, and a more preferable upper limit value is 4,000 wtppm.

The amount of the germanium compound used is preferably 50 to 5,000 wtppm in terms of metal, that is, in terms of germanium, with respect to the produced polyester. A more preferable lower limit value is 70 wtppm, and a more preferable lower limit value is 80 wtppm. A more preferable upper limit value is 4,500 wtppm, and a more preferable upper limit value is 4,000 wtppm.

The amount of the titanium compound, antimony compound and germanium compound used, that is, the content of the metal derived from the titanium compound, the antimony compound and the antimony compound in the produced polyester is limited to the first 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 indicated for the titanium compound, and the germanium compound and the antimony compound may be used. The amount does not matter. When only the titanium compound and the germanium compound are used as the first metal compound, the amount of the titanium compound used is within the range of the amount shown for the titanium compound, and the amount of the germanium compound used. However, the amount of the antimony compound used does not matter as long as it is within the range of the amount used shown for the germanium compound. When a titanium compound, a germanium compound and an antimony compound are used as the first metal compound, the amount of the titanium compound used is within the range of the amount shown for the titanium compound, and the amount of the germanium compound used. However, it is necessary that the usage amount of the germanium compound is within the range of the usage amount shown for the antimony compound, and the usage amount of the antimony compound is within the range of the usage amount shown for the antimony compound.

As the first metal compound, two or more of a titanium compound, an antimony compound and a germanium compound may be used in combination. In this case, the total amount of the titanium compound, the antimony compound and the germanium compound is preferably 50 to 5,000 wtppm in terms of each metal with respect to the produced polyester. A more preferable lower limit value is 70 wtppm, and a more preferable lower limit value is 80 wtppm. On the other hand, a more preferable upper limit value is 4,500 wtppm, and a more preferable upper limit value is 4,000 wtppm.
In the production of polyester, the entire amount of the catalyst component is usually incorporated into the resin, so the content of the above metal compound is the metal relative to ricinolic acid and its derivatives hydrocarbyl ester and other so-called raw materials in the polymerization reaction. The metal atom-based content of the compound is preferably in the same range.

As a means for controlling the ratio of these first metal compounds to the produced polyester, the following methods can be mentioned.
For example, in the case of a polymerization reaction by a reaction of a normal polyvalent carboxylic acid and a polyhydric alcohol, a predetermined small amount of reaction solution is collected from the reaction vessel, the polymer is separated, and then washing or the like is performed. Adjust the reaction time 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 add the raw materials polyvalent carboxylic acid and polyhydric alcohol. There are methods such as polymerizing.

Further, in the case of a polycondensation reaction using an esterified polyvalent carboxylic acid as a raw material, the metal content of the raw material is confirmed by a method such as ICP, and the amount of the reaction charged and the polyhydric alcohol component to be desorbed are checked. The amount can be measured and the content of the metal component in the polymer can be determined from this information.

As another method, the metal component content of the polymer in the reaction solution extracted in a small amount is directly measured by the ICP method or the like to determine the timing at which the reaction is terminated, 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 also decrease or the molecular weight may not be sufficiently high. It is considered that this is because the presence of excess metal causes partial hydrolysis and side reactions described later.

The second metal compound is at least one of the metal compounds selected from the Group 2 and Group 8 to Group 12 elements of the periodic table. Specific examples thereof include compounds such as calcium, magnesium, cobalt and zinc. It is preferably a compound of a Group 2 element of the periodic table called an alkaline earth metal, and more preferably a compound of calcium or a compound of magnesium. Examples of the calcium compound include calcium acetate, examples of the magnesium compound include magnesium acetate, examples of the cobalt compound include, for example, cobalt acetate, and examples of the zinc compound include zinc acetate. This second metal compound is an arbitrary component.

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

As is clear from the value of the X / Y ratio, in the production method of the present invention, it is preferable to use the second metal compound in a relatively small amount as compared with the first metal compound. From this point of view, the present inventors make the following inferences regarding the function of the second metal compound.

An interaction occurs between the second metal compound and the first metal compound which is a main catalyst such as a titanium compound, and the coordination or bond structure of the main catalyst is changed. As a result, specific active sites are formed during the reaction that allow the molecules of the reaction source to interact with the metal atoms of the main catalyst.

In addition, the interaction between the second metal compound and the main catalyst compound suppresses the acid or base properties of specific active sites of the main catalyst. This suppresses unwanted side reactions and associated by-products.

As a result of these, it is presumed that the second metal compound improves the polycondensation reaction catalytic ability of the first metal compound.
Furthermore, the following assumptions are made. That is, when the second metal compound is excessively added, the excessive catalytic activity promotes the progress of unnecessary side reactions such as the dehydration reaction of the secondary hydroxyl group of ricinoleic acid. As a result, the production of by-products such as the end-sealing 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 smaller amount within a certain range as described above, as compared with the first metal compound.

(Polymerization process)
The production method of the present invention is characterized in that, in the polymerization of a raw material containing at least one selected from ricinoleic acid and hydrocarbyl esters of its derivatives, the amount of the metal compound catalyst and the polycondensation temperature satisfy a specific relationship. And.
In the method for producing a polyester of the present invention, when the content (ppm) of titanium, germanium and antimony is M and the polycondensation reaction temperature (° C.) is T, the following two conditions must be satisfied. ..
(A) When 0 <M ≦ 1200, 195 ≦ T ≦ 233, and
(B) When 1200 <M ≦ 5000
-0.0067xM + 203 ≦ T ≦ −0.0067xM + 241.
The left side of the equation of the above requirement (B) is preferably "-0.0067xM + 204", and more preferably "-0.0067xM + 205".
On the other hand, the right side of the equation of the above requirement (B) is preferably "-0.0067xM + 240", and more preferably "-0.0067xM + 238".
When polymerizing a hydrocarbyl ester of ricinol acid or a derivative thereof, the polycondensation temperature is particularly high as the amount of the catalyst component used increases, and the molecular weight may decrease over time when the amount of catalyst is relatively large. We found this as a new subject of the present invention.

The above formula is, for example, a formula showing that the polycondensation reaction temperature tends to be restricted as the amount of the catalyst used increases. In other words, the above formula can be said to be a formula showing that the amount of the catalyst used becomes restricted as the polycondensation reaction temperature increases.
As long as the above formula is satisfied, the molecular weight tends to increase with time during the polycondensation reaction. In other words, under conditions outside the above range, the molecular weight tends to decrease with time, or the molecular weight is sufficient. It may not increase.

The reason why the reaction in which the molecular weight can be easily controlled proceeds within the range of the above conditions is not clear at present, but the present inventors speculate as follows.
As described above, hydrocarbyl alcohol derived from ricinoleic acid and its derivative hydrocarbyl ester is produced as a by-product during the progress of the polycondensation reaction. It is preferable to proceed the reaction while removing this hydrocarbyl alcohol by means such as reduced pressure conditions, but it is considered that there is a component that stays inside the polycondensate and in the vicinity of the catalyst component, although it is probably a trace amount. This trace amount of alcohol component may increase the tendency to promote the depolymerization of the produced polyester under specific conditions, for example, the high content of the catalyst component and at a high temperature, and the depolymerization reaction rate may exceed the growth reaction rate. Will occur. In order to prevent such a reversal of the reaction rate, it is considered that the amount of catalyst and the polycondensation reaction temperature need to satisfy a specific relationship.

If the above conditions are satisfied, known polycondensation reaction conditions and polycondensation methods can be used without limitation for other conditions. Specifically, as the first-stage polymerization, at least one selected from hydrocarbyl esters of ricinol acid and its derivatives, diols and dicarboxylic acids used as necessary, and the plurality of metal compounds as catalysts are used. It is charged in a reactor, and the alcohol produced while heating is removed to proceed with an esterification reaction or a transesterification reaction to synthesize a low molecular weight oligomer. Then, as the polymerization in the latter stage, the polycondensation reaction is allowed to proceed under reduced pressure, and the generated alcohol compound is removed to promote the molecular weight increase. The specific preferable temperature range for synthesizing a low molecular weight oligomer by the esterification reaction or transesterification reaction, which is the polymerization in the previous stage, is 200 to 250 ° C, more preferably 210 to 230 ° C.

In the present invention, the temperature range of the polycondensation reaction, which is the so-called subsequent polymerization, is not limited as long as the above conditions are satisfied, but is preferably 190 to 235 ° C, more preferably 195 to 230 ° C.
The pressure in the reactor in the polyester production method of the present invention is preferably 400 Pa (3 Torr) or less, more preferably 133 Pa (1 Torr) or less. It is obvious that the pressure in the reactor is preferably low, but considering the production cost and the like, the lower limit of the pressure is preferably 6.7 Pa (0.05 Torr), more preferably 13.3 Pa (0.1 Torr). ).
The polycondensation reaction time in the method for producing a polyester of the present invention is also not particularly limited, but is preferably 3 hours to 20 hours. A more preferable lower limit is 4 hours, and even more preferably 5 hours. On the other hand, a more preferable upper limit value is 15 hours, and even more preferably 12 hours.

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 coexist in the polymerization reaction solution as a heat-resistant stabilizer. Specific examples of the heat-stabilizing agent include phosphoric acid esters such as trimethyl phosphate, triethyl phosphate, tri-n-butyl phosphate, trioctyl phosphate, and triphenyl phosphate; triphenyl phosphate, trisdodecyl phosphate, and trisnonylphenyl phos. Subphosphoric acid esters such as phyto; acidic phosphoric acid esters such as methyl acid phosphate, ethyl acid phosphate, isopropyl acid phosphate, butyl acid phosphate, phenyl acid phosphate, dibutyl phosphate, monobutyl phosphate, dioctyl phosphate, and orthophosphate, polyphosphorus. In addition to acids and the like, phosphorus compounds such as phenylphosphonic acid, PEP-36, Irgafos 168, Sumilizer GP, PEP-8, P-EPQ, Irgamod 295 and triphenylphosphine are included.

Further, as long as the properties 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 and the like, etc. PH adjusters, amine-based stabilizers such as Irgastab FS 301FF, metal supplements such as CDA-1, benzotriazole, Irganox MD 1024, and Nowgard XL-1, as well as oxazoline-based compounds or isocyanate-based compounds, epoxy-based compounds, and carbodiimide-based compounds. The polymerization may be carried out in the coexistence 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 can have a relatively high molecular weight. Specifically, the molecular weight of the polyester obtained by the production method of the present invention is preferably 30,000 to 500,000, more preferably 90, as the polystyrene-equivalent weight average molecular weight measured by the GPC method described later. It can be between 000 and 500,000, more preferably 100,000 and 500,000.
The preferred intrinsic viscosity of the polyester is 0.15 dl / g to 0.80 dl / g. A more preferable lower limit value is 0.18 dl / g, and a more preferable upper limit value is 0.19 dl / g. On the other hand, a more preferable upper limit value is 0.70 dl / g, and a more preferable upper limit value is 0.60 dl / g.

In the polyester obtained by the production method of the present invention, the content ratio of the structural unit derived from the hydrocarbyl ester of ricinoleic acid and its derivative is derived from the structural unit derived from ricinoleic acid and its derivative contained in the produced polyester, dicarboxylic acid. The ratio is preferably 10 to 100 mol% with respect to the total of the structural units of the above and the structural units derived from the diol. The preferable lower limit of the content ratio is 30 mol%, and the more preferable lower limit is 50 mol%. The preferred 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%. A more preferable lower limit of the content ratio is 10 mol%, and a more preferable lower limit is 15 mol%. A more preferable upper limit value is 35 mol%, and a further preferable upper limit value is 25 mol%.

The content ratio of the structural unit derived from the diol compound is preferably 0 to 45 mol%. A more preferable lower limit of the content ratio is 10 mol%, and a more preferable lower limit is 15 mol%. A more preferable upper limit value is 35 mol%, and a further preferable upper limit value is 25 mol%.

The content ratio of the structural units derived from the dicarboxylic acid compound and the diol compound such as the above-mentioned ricinoleic acid hydrocarbyl ester is 100 mol% when the total of the structural units derived from the dicarboxylic acid compound and the diol compound such as the hydrocarbyl ester such as ricinoleic acid is 100 mol%. It is a numerical value of.

The polyester obtained by the production method of the present invention may contain a carbon-carbon double bond based on a structural unit derived from a hydrocarbyl ester such as 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 efficiently produced.

The polyester obtained by the method of the present invention is preferably
(I) Structural units derived from ricinoleic acid and its derivatives hydrocarbyl ester 10-80 mol%,
(II) 10-45 mol% of structural unit derived from a dicarboxylic acid having 2 to 12 carbon atoms and (III) 10-45 mol% of structural unit derived from a diol having 2 to 12 carbon atoms.
(However, the total of the structural units of (I), (II), and (III) is 100 mol%)
including. The more preferable range of each structural unit is the same as the range described in the description of the polyester obtained by the above-mentioned production method.
Further, preferably, a specific compound may be contained in a specific content range. Therefore, the polyester obtained by the method of the present invention tends to have a high molecular weight and a strong interaction with various substances. For example, it may exhibit excellent properties such as adhesiveness. Further, the tendency may become more remarkable as the number of carbon atoms of (II) dicarboxylic acid and (III) diol is smaller.
Further, the polyester obtained by the method of the present invention can also contain a structural unit derived from a trifunctional or higher functional component described in the above-mentioned production method.

The polyester obtained by the production method of the present invention is combined with various known additives such as antioxidants, crystal nucleating agents, flame retardants, antistatic agents, mold release agents, ultraviolet absorbers and other known polymers. Therefore, it can be used in an aspect such as a composition. In this case, the content of the additive is preferably less than 50%, more preferably less than 20%, still more preferably less than 5%, particularly preferably less than 1%, particularly preferably less than 0.3%. be. The mass ratio of the other polymer to the polyester obtained by the production method of the present invention was such that the mass of the polyester obtained by the production method of the present invention was (A) and the mass of the other polymer was (B). In some cases, as (A) / (B), 95/5 to 5/95, more preferably 80/20 to 20/80, and even more preferably 70/30 to 30/70 can be exemplified. Of course, it goes without saying that the preferable ratio differs depending on the application.

The polyester obtained by the production method of the present invention can be used for various known uses. Specific examples thereof include lubricants, plasticizers, emulsifiers, dispersants, and surfactants. As a preferable use, the elastomer use described in Patent Document 2 and the like can be exemplified.

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 measurement method of each physical property is as follows.

<Intrinsic viscosity (IV)>
The obtained polyester was dissolved in a mixed solvent of phenol and 1,1,2,2-tetrachloroethane in a mass ratio of 1: 1 to prepare a solution. The number of seconds of flow of the obtained solution at 25 ° C. was measured using an Ubbelohde viscometer, and the intrinsic viscosity was calculated by applying the following formula.
[Η] = ηSP / [C (1 + KηSP)]
[Η]: Intrinsic viscosity (dl / g)
ηSP: Specific viscosity C: Sample concentration (g / dl)
K: The straight line of the graph when the specific viscosity ηSP of samples with different sample concentrations C (3 points or more) is measured based on the following formula, and the sample concentration C is plotted on the horizontal axis and ηSP / C is plotted on the vertical axis. Tilt)
t: Number of seconds (seconds) of flow of the sample solution
t0: Number of seconds for solvent to flow (seconds)
ηSP = (t−t0) / t0

<Polyester composition>
The composition of the polyester was analyzed by the following procedure.
1) An ECA500 type 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 μsec (45 ° pulse), the repetition time is 8.5 seconds, the number of integrations is 394, and the hydrogen signal of tetramethylsilane is chemical. It was measured as a reference value for the shift. Each peak was assigned by a conventional method.
2) The obtained measurement data was analyzed, the carboxylic acid and alcohol components constituting the polyester were identified, and their composition ratios were determined.

<Elemental content>
Sulfuric acid was added to the obtained polyester, and nitric acid was added dropwise while heating to decompose organic substances. The obtained decomposition liquid was conditioned 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 having a known content and collating it with the calibration curve.

<Calculation of polycondensation rate (ΔIV / t)>
Polycondensation was carried out under various conditions, and the polycondensation rate was calculated by the formula 1 from IV (a) after 5.0 hours and IV (b) after 10.0 hours.
ΔIV / t = (IV (b) -IV (a)) / 5 ... Equation 1
As a condition in which depolymerization is suppressed, the polycondensation rate from 5.0 hours to 10.0 hours is ≧ 0 dl / g · hr, and in consideration of productivity, IV after 5.0 hours of polycondensation is obtained. The condition of ≧ 0.15 dl / g was regarded as acceptable.

[Example 1] Ti: 2,000 ppm, 220 ° C.
To a 500 mL glass reactor, 100.10 g (62.7 parts by mass) of methyl ricinoleic acid, 31.90 g (20.0 parts by mass) of sebacic acid, 25.72 g (16.1 parts by mass) of 1,4-butanediol and 0.0594 g (0.04 parts by mass) of a 20 wt% aqueous solution of tetratetraethylammonium hydroxide was added, and the temperature was raised from room temperature to 200 ° C. over 40 minutes. After reaching 200 ° C., after confirming that sebacic acid was dissolved, stirring was started, and the mixture was kept at 200 ° C. for 5.0 hours to carry out an esterification reaction.
After completion of the esterification reaction, 1.86 g (1.16 parts by mass) of titanium tetrabutoxide was added at 200 ° C., the pressure was reduced to 1.0 Torr (133 Pa) or less over 60 minutes, and the temperature was raised to 220 ° C. Then, the polycondensation reaction was carried out at 220 ° C. On the way, after a vacuum break for 5.0 hours, polyester was sampled, the pressure was further reduced to 1.0 Torr or less, and a polycondensation reaction was carried out for a total of 10.0 hours. After completion of the reaction, nitrogen was passed through the system to return the pressure to normal pressure, and then the polyester was extracted from the glass reactor within 10 minutes.

[Example 2] Ti: 100 ppm, 230 ° C.
The same procedure as in Example 1 was carried out except that 0.10 g (0.06 parts by mass) of titanium tetrabutoxide was used and the polycondensation temperature after heating was set to 230 ° C.

[Example 3] Ti: 400 ppm, 230 ° C.
The same procedure as in Example 1 was carried out except that the amount of titanium tetrabutoxide was 0.38 g (0.24 parts by mass) and the polycondensation temperature after temperature rise was 230 ° C.

[Example 4] Ti: 1000 ppm, 230 ° C.
The same procedure as in Example 1 was carried out except that the amount of titanium tetrabutoxide was 0.92 g (0.58 parts by mass) and the polycondensation temperature after temperature rise was 230 ° C.

[Example 5] Ti: 4000 ppm, 210 ° C.
The same procedure as in Example 1 was carried out except that the amount of titanium tetrabutoxide was 3.91 g (2.31 parts by mass) and the polycondensation temperature after heating was 210 ° C.

[Example 6] Ti: 2000 ppm, 180 ° C. * Estimated not performed The same procedure as in Example 1 was carried out except that the temperature was lowered to 180 ° C. and the polycondensation temperature was set to 180 ° C. after the esterification reaction.

[Example 7] Ti: 100 ppm, 200 ° C.
The same procedure as in Example 1 was carried out except that 0.10 g (0.06 parts by mass) of titanium tetrabutoxide was used and the polycondensation temperature was 200 ° C.

[Example 8] Ti: 400 ppm, 200 ° C.
The same procedure as in Example 1 was carried out except that the amount of titanium tetrabutoxide was 0.38 g (0.24 parts by mass) and the polycondensation temperature was 200 ° C.

[Example 9] Ti: 4000 ppm, 180 ° C. * Estimated not yet performed Titanium tetrabutoxide was 3.91 g (2.31 parts by mass), and after the esterification reaction, the temperature was lowered to 180 ° C and the polycondensation temperature was 180 ° C. Except for the above, the same procedure as in Example 1 was carried out.

[Comparative Example 1] Ti: 2000 ppm, 230 ° C.
The same procedure as in Example 1 was carried out except that the polycondensation temperature after the temperature was raised was set to 230 ° C.

[Comparative Example 2] Ti: 400 ppm, 240 ° C.
The same procedure as in Example 1 was carried out except that the amount of titanium tetrabutoxide was 0.38 g (0.24 parts by mass) and the polycondensation temperature after temperature rise was 240 ° C.

[Comparative Example 3] Ti: 2000 ppm, 170 ° C. * Estimated not performed The same procedure as in Example 1 was carried out except that the temperature was lowered to 170 ° C. and the polycondensation temperature was set to 170 ° C. after the esterification reaction.

[Comparative Example 4] Ti: 400 ppm, 190 ° C. * Estimated not yet performed Titanium tetrabutoxide was 0.38 g (0.24 parts by mass), and after the esterification reaction, the temperature was lowered to 190 ° C. and the polycondensation temperature was set to 190 ° C. Except for the above, the same procedure as in Example 1 was carried out.

Claims (4)

A method for producing a polyester by polymerizing a raw material containing at least one selected from ricinoleic acid and hydrocarbyl esters of its derivatives.
At least one selected from ricinoleic acid and its derivatives hydrocarbyl ester under the conditions satisfying the following formulas (A) and (B) in the presence of at least one compound selected from titanium compounds, germanium compounds and antimony compounds. A method for producing a polyester in which a raw material containing is polymerized.
When the content (ppm) of titanium, germanium and antimony is M and the polycondensation reaction temperature (° C.) is T,
(A) When 0 <M ≦ 1200, 195 ≦ T ≦ 233, and
(B) When 1200 <M ≦ 5000
-0.0067xM + 203 ≦ T ≦ −0.0067xM + 241. The molar ratio of the structural unit derived from the hydrocarbyl ester of ricinolic acid and its derivative contained in the produced polyester is derived from the structural unit derived from hydrocarbyl ester of ricinolic acid and its derivative contained in the produced polyester, dicarboxylic acid. The method for producing a polyester according to claim 1, wherein the total of the structural unit and the structural unit derived from the diol is 100 mol%, which is 10 to 100 mol%. The method for producing a polyester according to claim 2, wherein the dicarboxylic acid is a dicarboxylic acid having 2 to 12 carbon atoms, and the diol is a diol having 2 to 12 carbon atoms. The produced polyester
(I) Structural units derived from ricinoleic acid and its derivatives hydrocarbyl ester 10-80 mol%,
(II) 10-45 mol% of structural unit derived from a dicarboxylic acid having 2 to 12 carbon atoms and (III) 10-45 mol% of structural unit derived from a diol having 2 to 12 carbon atoms.
(However, the total of the structural units of (I), (II), and (III) is 100 mol%)
The method for producing a polyester according to claim 3, wherein the polyester satisfies the above conditions.