JPH054138B2 - - Google Patents

Description

[Detailed description of the invention]

(Industrial Application Field) The present invention relates to a highly active catalyst used for esterification reactions and transesterification reactions, and a method for producing the same. (Prior art and its problems) Conventionally, in the esterification reaction, a dehydration esterification catalyst is added to organic acids and alcohols, and the water produced by heating is removed azeotropically to effect esterification. Organic acids such as toluenesulfonic acid, inorganic acids such as sulfuric acid and hydrochloric acid, alkalis, and tetraalkoxytitanium are used. For example, plasticizers for plastics such as dioctyl phthalate (DOP) and dioctyl adipate (DOA) are manufactured industrially through esterification reactions, and various catalysts are used in this process, but the following problems arise. I am holding. Catalysts used in these industrial esterification reactions are naturally required to have high activity for practical purposes, but the acid, alkali, and alkoxytitanium catalysts mentioned above can suppress the reaction between acid and alcohol by approximately 100%. It is very difficult to cause the reaction to occur to a similar degree. When using a large amount of these catalysts for the purpose of increasing the reaction rate, the larger the amount of catalyst used, the more problematic the removal of catalyst residue becomes. In particular, in order to improve the electrical properties and thermal stability of plastic compositions containing plasticizers, the removal of residual acids and catalysts requires an acid value of 0.1, or even lower, according to standards. For this reason, a highly active catalyst that is highly active even at low concentrations is desired. In the case of para-toluenesulfonic acid catalysts, the catalytic activity is sufficiently rapid at low temperatures, but there are difficulties in removing catalyst residues, and in the case of alkoxy titanium catalysts, as with acid catalysts, it is difficult to remove catalyst residues (catalyst decomposition and removal). If the acid value cannot be sufficiently lowered by (including the following), a neutralization and water washing step is essential. At that time, the unreacted acid used in the esterification reaction becomes a salt and acts as a surfactant.
This poses a new problem of poor separation between the ester layer and the aqueous layer. In particular, the more complex the acid, the more difficult it is to remove it, and the less the acid value of the esterification reaction product can be achieved. Recently, a method using a chelating agent as a method for removing catalyst residue from a titanium catalyst (US Pat. No. 4,506,091)
Research is also being conducted on heterogeneous solid catalysts in which the catalyst components are minimally dissolved in the reaction system. For example, a catalyst for esterification reaction supported on a carrier has been proposed [CA131919h (1984)],
After the esterification reaction has been sufficiently carried out, the acid component must be removed by alkaline washing as in the conventional method, which is not satisfactory. In addition, as a heterogeneous titanium catalyst that can be used in trace amounts and minimizes the loss of catalyst dissolution in the esterification reaction, a tetraalkoxytitanate polymer is hydrolytically treated with peroxide in the presence of an alkali. It has been proposed to then reflux the treated product in a monoalcohol (monohydric alcohol such as n-butyl alcohol or heptanol) (Japanese Patent Application Laid-Open No. 53-94296), but the catalyst preparation process is complicated. However, it is difficult to design optimal catalyst characteristics for various esterification reactions. Additionally, U.S. Pat. No. 3,194,764 and related U.S. Pat. No. 2,643,262 disclose that orthotitanate esters and glycols are used to prepare complex esters useful in synthetic lubricating oils from monoalcohols, dicarboxylic acids, and glycols. It has been disclosed that the reaction product (glycol titanate) with These documents state that the properties of glycol titanate as a catalyst are a complex of a monomer and a polymer, that it is a liquid or a solid, and that it is suitable for reaction systems. It is disclosed that they are compatible (solubility, miscibility, dispersibility). Furthermore, although there are some doubts about the structure of the catalyst species, it is also disclosed that the hydroxyl group of the glycol used in the preparation of the catalyst is a chelate compound coordinated to a titanium atom. However, when carrying out an esterification reaction using this catalyst system, the insolubilization and crosslinking of the catalyst are insufficient, resulting in insufficient catalytic activity, making it impossible to obtain an esterification reaction product with a low acid value. (Problems to be Solved by the Invention) The present invention aims to provide a novel, highly active titanium heterogeneous catalyst that improves the drawbacks of the conventional catalysts for esterification reactions and transesterification reactions. It is something. (Specific means for solving the problem) ● [Background of the invention] The present inventor believes that if it is possible to make a polyol polytitanate represented by the following formula, it will be possible to make it into a polymer and crosslink it. Therefore, we thought that insolubilization in the reaction system (reaction liquid) of the esterification reaction and removal of the catalyst residue could be achieved simply by filtration, and we conducted extensive studies. [Here, R and R' represent R=monofunctional alcohol residue, R'=polyhydric alcohol residue. The above formula shows a reaction with a tetrahydric alcohol. ] That is, if an alcohol exchange reaction occurs between an alkoxy titanium such as butyl titanate (or tetrabutoxy titanium) and a polyhydric alcohol, a polyol polytitanate is produced according to the above formula, and at the same time a stoichiometric amount of It is thought that alcohol is produced. In fact, when equimolar amounts of tetrafunctional tetrabutoxytitanium (butyl titanate) and pentaerythritol, a tetrafunctional polyol, are mixed and reacted by heating at 120°C, the polyol does not dissolve, but a large amount of reaction product forms around it. A gel-like swollen precipitate is formed. As the reaction continues, liquid tetrabutoxytitanium gradually decreases, and with prolonged heating, butanol, one of the reaction products, begins to reflux and is distilled out. After removing the butanol by distillation, the remaining solid product is heated to 120-180°C to generate butanol from the precipitated solid, and by heat treatment under reduced pressure, the solid becomes a porous and relatively hard hardened product. At the same time, it was found that the amount of butanol produced was commensurate with the amount of butyl titanate used. Considering this reaction process and reaction products, it is found that an intermolecular alcohol exchange reaction easily occurs between titanate and alcohol by heating, and then by heating, especially heat treatment under reduced pressure, a three-dimensional steric reaction occurs. Although the details of the structure have not been completely elucidated, it is thought that chain-like, and perhaps mainly highly cross-linked, polyol polytitanate is produced. The present inventor has discovered that the solid product thus obtained has a catalytic effect on the esterification reaction or the transesterification reaction as expected, and also significantly reduces the acid value after the reaction, and the present invention is based on the present invention. I was able to complete it. ● [Specific Structure of the Invention] To summarize the present invention, the first invention relates to a catalyst for esterification reaction and transesterification reaction consisting of a solid, highly crosslinked polyol polytitanate; The second invention relates to a manufacturing method in which the catalyst is manufactured from a reaction between alkoxy titanium and a polyol. Hereinafter, the structure of the present invention will be explained in detail, but for convenience of explanation, the method for producing the catalyst will be explained first. The catalyst for esterification reaction and transesterification reaction according to the present invention is produced by reacting alkoxy titanium with a polyol as described above, and subjecting the reaction product to dealcoholization treatment to form a highly crosslinked product. First, what kind of substance is used in the reaction between alkoxy titanium and polyol will be explained. It is naturally expected that a partial alcohol exchange reaction will proceed in the reaction between alkoxytitanium and alcohol, but it is expected that alkoxytitaniums are trivalent to tetravalent polyfunctional and alcohols are polyfunctional. In this case, since the three-dimensional structure of the reaction product becomes three-dimensionally complex, it is difficult to imagine that the dealcoholization reaction in the next step will proceed easily. However, contrary to expectations, when the dealcoholization reaction is forcibly carried out at high temperatures, especially under reduced pressure, the dealcoholization reaction easily occurs from within the solid product, resulting in highly crosslinked products. It turned out that. From this, the polyol component and alkoxytitanium component used in the production of the catalyst of the present invention are not particularly limited, and for example, the following are used. <Polyol component> Difunctional polyols such as Γ ethylene glycol, 1,2-propanediol, 1,3 and 1,4-butanediol, polyethylene glycol, polypropylene glycol, Γ glycerin, diglycerin, 1,2,6- hexanetriol, trimethylolpropane, trimethylolbutane, pentaerythritol,
such as dipentaerythritol, sorbitol, sorbitan, and sugars and polyhydric or high molecular weight polyhydric alcohols such as cellulose and polyvinyl alcohol. <Alkoxytitanium component> Γtetrabutoxytitanium and its tetramer (tetramer), tetraisopropyloxytitanium,
Alcohol solution of tetrafunctional tetraalkoxytitaniums such as tetraethoxytitanium and tetraoctyloxytitanium, Γ titanium trichloride, and titanium tetrachloride Γ Compounds also called orthotitanic acid esters (for example, butyl titanate, etc.) Reaction of the above two components In some cases, simple mixing and heating may be sufficient, but it is preferable to gradually react while dissolving in a solvent, and as much as possible, after reacting a part of the alkoxy of the alkoxy titanium with the polyol,
Heating in two steps to produce polyol polytitanate through alcohol exchange reaction, then heating,
It is desirable to perform the dealcoholization reaction sufficiently under reduced pressure to achieve high-order hypercrosslinking. Generally, when butyl titanate is used, the first stage reaction is completed by heating a mixed solution with butanol, which is generated by adding a polyol and reacting, to 60 to 160°C for about 4 hours. Then, after distilling off the produced butanol, the heating temperature was lowered.
After raising the temperature to 160 to 180°C to remove the generated alcohol, and further heating under reduced pressure, preferably 10 mmHg or less, for 2 hours to remove the alcohol generated by dealcoholization, the solid product is pulverized to obtain the desired product. Catalysts can be manufactured. On the other hand, the relationship between the alcohol equivalent (OH equivalent) and the alkoxy titanium equivalent (OR equivalent) used in the catalyst production reaction of the present invention has a large influence on the activity of the produced catalyst. That is, the catalyst activity can be increased by controlling the ratio of alkoxy equivalent to OH equivalent, and the equivalent relationship is preferably (OH equivalent/OR equivalent =) 1.8 to 0.9:1, but Too much OH equivalent is also not good. When a solid catalyst is prepared with a high OH equivalent, that is, using a large amount of a polyol component, when this catalyst is applied to an ester reaction, there is a high possibility that the polyol component will be eluted from the catalyst, and as a result, the polyol component will be involved in the esterification reaction. This is undesirable because the esters (composite esters, polyesters) that have entered the process become by-products. In addition, if a large amount of polyol component is used, oligomers derived from titanium compounds will be generated during catalyst preparation, and these oligomers will be dissolved in the esterification reaction product, causing an increase in the acid value of the product. Too much is not a good thing. Furthermore, as a method for highly activating the catalyst other than the method for highly activating the catalyst by adjusting the equivalent weight of alcohol and the equivalent weight of alkoxytitanium described above, there is a method of treating the highly crosslinked solid catalyst produced with water. This high activation method is
Although it varies depending on the catalyst composition and catalyst manufacturing conditions, it is an effective high activation method. A preferred method for highly activating the catalyst according to the present invention is to react the OH equivalent of alcohol with the alkoxy equivalent of titanium in a ratio of about 1.5 to 0.9:1, and sufficiently perform alcohol exchange reaction and dealcoholization reaction to form a polymer. By obtaining a crosslinked product and further post-treating it by leaving it at room temperature or heating it with an alcohol containing water, the alkoxyl groups on the titanium atoms remaining unreacted on the solid surface of the polyol polytitanate can be hydrolyzed. Therefore, it is converted into an OH group. In other words, through this activation treatment with water, the OR group on the titanium atom of polyol polytitanate (polyol polytitanate ester) becomes an OH group (to form a polyol polytitanic acid structure) through hydrolysis, and becomes an effective catalytically active species. . In addition, in the activation treatment by hydrolysis, if oligomers such as Ti(OH) ₄ derived from the titanium compound are generated, the catalytic activity of the initial dehydration esterification reaction will improve, but the esterification reaction and transesterification reaction will be Care must be taken because this will cause a phenomenon in which the acid value of the product does not decrease, and its characteristics as a catalyst will be halved. A major feature of the solid catalyst of the present invention is that it has selectivity to acids involved in the esterification reaction. When using alkoxytitaniums such as benzyl, 2-ethylhexyl, and cyclohexyl, which have a sterically larger space compared to butoxytitanium, the disadvantage is that polymerization due to dealcoholization during catalyst preparation is slow and many alcohol groups remain. ,
When performing sufficient dealcoholization, phthalic acid,
The reaction rate is high for esterification of bulky benzenecarboxylic acids such as benzoic acid and terephthalic acid. For example, when a polyol polytitanate is made from normal butanol or alkoxytitanium of a lower alcohol and activated by water treatment, the esterification reaction rate is very fast with adipic acid, which is a linear acid, but with phthalic acid. is still insufficient. On the other hand, Tetra
A catalyst prepared from 2-ethylhexyloxytitanium has large pores and very high activity, and can be made to have a low acid value in a short time. These titanium compounds of higher alcohols can be prepared by adding an equivalent or excess amount of higher alcohol to butoxytitanium or isopropoxytitanium, which is alkoxytitanium of lower alcohols, and performing an alcohol exchange reaction by simply heating. I can do it. The present invention relates to a method of reacting alkoxy titanium with a polyfunctional polyol to produce a solid product having a sufficiently polymerized and crosslinked polyol polytitanate skeleton through alcohol exchange reaction and dealcoholization reaction, and using the solid product as a catalyst. However, by reacting with monoalcohol during the esterification reaction to give an ester product with a low acid value and without converting into soluble titanium alkoxide, and removing the solid catalyst by filtration etc. Therefore, the present invention provides a technique that allows post-processing steps to be omitted or easily performed. In the esterification reaction using these solid catalysts having a polyol polytitanate skeleton, 99.9% of the acid can be esterified in just 3 to 4 hours. The solid catalyst of the present invention has a polyol polytitanate skeleton that is polymerized and highly crosslinked as described above. I will say more about this point. When an alkoxytitanium having a bulky alcohol residue with a large steric space such as 2-ethylhexyl is reacted with a polyol, and then polymerization and crosslinking are performed by dealcoholization, the dealcoholization rate is slow and crosslinking is not achieved. In sufficient cases the product will be soluble in the solvent. The higher the boiling point of the alcohol residue of the alkoxy titanium is, the higher the alcohol becomes, the more soluble it becomes in a solvent, for example, the more soluble it becomes in a solvent such as octanol when heated. When the insufficiently crosslinked octanol-soluble portion and the highly crosslinked insoluble portion are separated and subjected to stirring treatment at 80°C for 1 hour using water-saturated butanol, that is, activation treatment, both A solid product is obtained which is insoluble or sparingly soluble in octanol. Comparing the activity of esterification reactions to prepare phthalate esters using these solid products,
Catalysts obtained from fully crosslinked insoluble moieties have very high activity and rapid reaction rates. In contrast, catalysts obtained from insufficiently crosslinked soluble parts are clearly less active. This indicates that the titanium polymer having a highly crosslinked polyol polytitanic acid skeleton has a higher activity. In addition, when a catalyst is prepared by reacting alkoxytitanium with a lower alcohol residue such as isopropyl with a polyol, the dealcoholization reaction is relatively quick and polymerization and crosslinking are likely to proceed, but the solvent-soluble portion is In order to reduce the amount, it is necessary to make the temperature, time, and degree of vacuum of the dealcoholization reaction sufficiently high. If the dealcoholization is insufficient, the catalyst activity will be significantly reduced. (Prior art and its problems), US Pat. titanium compounds have been described, but such titanium compounds can be said to be a type of insufficiently crosslinked polyol polytitanate esters. In the present invention, in addition to sufficiently polymerizing and crosslinking by dealcoholization reaction, the crosslinking density is increased by using not only bifunctional but also polyfunctional polyol as the alcohol component, and the esterification reaction is carried out. It is characterized by the fact that it sometimes produces insoluble and highly active solid catalysts. As a method for preparing the solid catalyst of the present invention, a polyol component is adsorbed on various carriers such as silica, zeolite, molecular sieve, etc., and then treated with an alkoxytitanium component to form a composite matrix type that encapsulates the carrier. In particular, sparingly soluble catalysts can be prepared even from diols of low functionality. Of course, the method described above may be reversed, that is, the alkoxytitanium component may be first adsorbed onto various carriers and then treated with the polyol component. The catalyst of the present invention is a dehydration esterification reaction using a Γ dibasic acid, a tribasic acid, a tetrabasic acid, and a monohydric alcohol, a polyester production reaction in which a Γ dicarboxylic acid, diols, and a monoalcohol coexist, and a Γ polyol bisalkyl reaction. Dehydration esterification and transesterification reactions during complex ester production reactions such as adipate, esterification and transesterification reactions of Γ fatty acids, esterification and esterification of dibasic acids and fatty acids with polyols such as Γ alkyd paints and modified polyester paints. It is useful as a catalyst for various esterification reactions and transesterification reactions, such as exchange reactions. Hereinafter, the present invention will be explained in more detail based on Examples, but the present invention is not limited to the catalyst formulations, combinations, and reaction examples described in these Examples unless it deviates from the technical idea thereof. do not have. (Examples) Example 1 23 g of tetrabutoxytitanium was placed in a 300 ml eggplant-shaped flask, 9.2 g of pentaerythritol was added, and the mixture was heated to 120°C. After 2 hours, a solid containing a gel-like precipitate was obtained. Next, the oil bath was raised to 180°C and heating was continued under reduced pressure until no butanol was distilled out.19g of butanol (95g of theoretical value)
% yield) was obtained. Thereafter, the mixture was further heated for 2 hours, then taken out and pulverized to obtain 13 g of yellowish fine powder. The catalyst thus obtained is abbreviated as P-Ti. 146 g (1 mol) adipic acid and 222 g (3 mol)
mol) of butanol was placed in a three-necked flask and dehydrated by azeotropy. As a catalyst, the P-
When 0.5g of Ti was added and the reaction was carried out while checking the amount of water distilled, approximately half of the calculated amount was distilled after 5 hours.
After 18 hours, approximately 36 ml of water was distilled out. Titration amount per g (acid value) after 21 hours of reaction (1/20
It is expressed as the number of ml titrated per 1 g of sample of N alkaline solution. ) was 5.25, and the acid value gradually decreased over time, reaching 0.06 after 46 hours. The amount of catalyst recovered was 0.53g, a recovery rate of approximately 100%. In addition,
The remaining acid has an acid value of 0.1 and the reaction weight is 350 g.
0.09%, and an acid value of 0.06 indicates a residual amount of 0.05%, meaning that 99.95% of the acid has reacted. [Comparative Experiment Example] A dehydration esterification reaction was carried out by adding 0.3g of tetrabutoxytitanium, which is a normal dehydration esterification catalyst, to a system of 146g (1 mol) of adipic acid and 222g (3 mol) of butanol. Ivy. (The dehydration esterification reaction ends at a higher acid value as the amount of Ti(OBU) ₄ increases.
In this control example, the amount of catalyst of Example 1 was
Instead of 0.5g, 0.3g was used. ) In this dehydration esterification reaction, the reaction temperature is low in proportion to the amount of butanol added, and the reaction rate is therefore slow, but after 5 hours, half of the calculated amount of water has distilled, and after another 30 hours, nearly 36 ml of water has distilled. I put it out. that time,
The acid value was 1.8. In addition, when the acid value was measured after reacting for a longer time, the values were 0.7 after 60 hours and 0.6 after 80 hours, but the desired low acid value was not achieved. Although it was expected that reducing the amount of catalyst would result in a lower acid value, it was not possible to achieve an acid value of 0.1 as in Example 1. Example 2 10 g of pentaerythritol was placed in 20 ml of water together with 20 g of molecular sieve 13X, heated to dissolve, and then allowed to stand. Insoluble pentaerythritol was washed with warm water and then dried under heat in a vacuum dryer to obtain 24.5 g of adsorbent. Tetrabutoxytitanium commensurate with adsorbed pentaerythritol
After adding 11.5g and heating at 120-180℃ and then removing the butanol produced under reduced pressure, the solid
26.0g was obtained. Therefore, 30% P- for the molecular sieve
A catalyst with fixed Ti was obtained. Adipic acid 146g (1 mole) and butanol 222g
(3 moles) was added with 1.7 g of the catalyst immobilized on the molecular sieve to perform a dehydration esterification reaction. As a result, after 3 and a half hours, about 18ml of water,
After 16 hours, 36 ml of water was distilled off, and the acid value of the ester produced at that time was 0.44. As a result of further heating and stirring for 34 hours, the acid value decreased to 0.04, the weight of the catalyst solid recovered by filtration was 1.5 g, and the recovery rate was 88.
%(1.5/1.7×100) hot. Example 3 13.2 g of polyvinyl alcohol powder (commercially available) having a molecular weight of 2000 was added to 17 g of tetrabutoxytitanium and heated to 120 to 180°C, and the produced butanol was removed. Then under a reduced pressure of 10 mmHg,
Heating was continued at 180°C for 2 hours to obtain 15g of brownish fine powder.
The amount of butanol recovered was 14 g, which was a nearly quantitative reaction. This catalyst is abbreviated as PVA-Ti. Adipic acid 146g (1 mole) and butanol 148g
(2 mol) and 0.5 g of PVA-Ti were added to perform a dehydration esterification reaction. The distillation time of 18 ml of water by azeotropic distillation was a little less than 3 hours, and the calculated amount was distilled after 18 hours, but the reaction temperature rose with the reaction of butanol, making it possible to speed up the reaction rate somewhat. did it. After 15 hours, the reaction temperature was increased to approximately 200℃ (190~
As a result of continuing the reaction at 205℃, after 22 hours,
The acid value decreased to 0.13 and 0.09 after 26 hours. Example 4 0.5 g of PVA in a mixture of 146 g (1 mole) of adipic acid and 325 g (2.5 mole) of 2-ethylhexanol
-Ti was added to perform a dehydration esterification reaction.
The reaction temperature is high at 170-180℃ and the reaction rate is fast.
After an hour, half of the water, 18 ml, was distilled off, and after 6 hours, an approximately calculated amount of 36 ml was distilled off. Acid value after 5 hours
It was 0.12, 0.04 after 10 hours, and 0.02 after 14 hours. Example 5 0.5 to a mixture of 148 g (1 mol) of phthanolic anhydride and 325 g (2.5 mol) of 2-ethylhexanol
g of PVA-Ti was added to perform a dehydration esterification reaction. After about 1 hour, 9 ml of water was distilled out, and after 5 hours, 18 ml of water, which was approximately the calculated amount, was distilled out. The acid value after 5 hours was 0.12, 0.4 after 10 hours, and 0.09 after 15 hours. Example 6 Adipic acid 292g (2 mol), 1.4-butanediol 81g (0.9 mol), 1.3-butanediol 81g
(0.9 mol) and 58 g (0.64 mol) of butanol were added with 0.53 g of PVA-Ti to perform dehydration and esterification. (The purpose of this example is to produce polyester with an average molecular weight of 2100.) For the theoretical dehydration amount of 81.4 g, 40 g of water was distilled out after 1 hour, and 81 ml of water was distilled out after 18 hours. did. As a result of adding butanol and heating and stirring to keep the reaction temperature at about 200-205℃, the acid value after 20 hours was
0.2 and then undergo transesterification under reduced pressure.
Debutanol was removed at 180°C and 20 mmHg for 3 hours. The acid value at that time was 0.15. Examples 7-9 Catalyst Activity Improvement Test Attempts were made to improve catalyst activation by varying the molar ratio of polyol to titanate. Example 7 6 g (0.033 mol) of d-sorbitol and 17 g (0.05 mol) of tetrabutoxytitanium were mixed with 60 ml of butanol.
After refluxing for 6 hours, butanol was removed by distillation, and then the butanol was removed under heating and reduced pressure of 20 mmHg for 3 hours. The product amount was 10.2 g compared to the calculated amount of 8.4 g, resulting in insufficient debutanolization of the catalyst. Adipic acid 146g (1 mol), butanol 148g
(2 mol) was added with 0.5 g of the above catalyst to carry out a dehydration esterification reaction. 16 ml (half volume) of water distilled out after 2.5 hours, 36 ml (calculated amount distilled) after 14 hours.
It was hot hours later. The acid value reached 2.0 after 15 hours and 0.10 after 30 hours. Example 8 7.2 g (0.039 mol) of d-sorbitol and 17 g (0.05 mol) of tetrabutoxytitanium were refluxed in 10 ml of butanol for 6 hours, and then a crosslinking reaction was carried out under reduced pressure for 3 hours. The product weighs 10.6 g and has not yet been completely debutanolized. 0.5g of this catalyst is 1
A dehydration esterification reaction was carried out by adding mol of adipic acid and 2 mol of butanol. The amount of water distilled out was 16 ml after 2 hours and 36 ml after 14 hours.
The acid value after hours was 0.08. Example 9 9 g (0.049 mol) of d-sorbitol and 17 g (0.05 mol) of tetrabutoxytitanium were refluxed in 60 ml of butanol, and after 6 hours, a crosslinking treatment was performed at 180° C. under reduced pressure for 3 hours. The product is 12g and the calculated amount is 11.6g.
It is thought that 1/3 of the OH is present on the catalyst surface. In the presence of 1 mol of adipic acid and 2 mol of butanol, 0.5 g of the above catalyst was added to carry out a dehydration esterification reaction, and after 2 hours.
16 ml of water was distilled off, and after 8 hours a calculated amount of 36 ml of water was distilled off. The acid value of the esterified product at that time was 1.0,
The acid value after 12 hours was 0.2, and the acid value after 16 hours was 0.08. To summarize the results of Examples 7 to 9 above, the first
It will look like a table.

[Table] Example 10 Using 0.5g of the sorbitol-polytitanate catalyst prepared in Example 9, 146g of adipic acid
(1 mol) and 32.5 g (2.5 g) of 2-ethylhexanol
A dehydration esterification reaction was carried out with (mol). The catalytic activity was significantly improved, and the amount of water distilled out was half, 18 ml, after 40 minutes, and 36 ml, approximately the calculated amount, after 2 hours, and the acid value was 3.71. When the reaction continues, the acid value after 4 hours is 0.17, and the acid value after 6 hours is 0.17.
It dropped to 0.03. Example 11 Test for improving catalyst activity A test for improving catalyst activation by water treatment was conducted. The reaction product of equal amounts of polyol and titanate used in Example 7 was poured into water, stirred for 2 hours, filtered and dried to prepare 0.5 g of polytitanate surface hydrate catalyst. Using this catalyst, an experiment for producing dioctyl adipate was conducted in the same manner as in Example 10. The reaction rate was almost as fast as in Example 10. That is, after 2 hours, approximately the calculated amount of water was distilled off, and after 6 hours, the acid value had dropped to 0.04. Example 12 <Production Example 1 of Composite Ester> 74 g (0.5 mol) of phthanolic anhydride was added to 387 g (1.5 mol) of dibutyl adipate, and then 1.4
Butanediol (0.5 mol) was added and stirred at 125°C. Thirty minutes after addition of the diol, the amount of phthalic anhydride was measured by titration, and it was found that 95% had reacted. After 1 hour, 0.5 g of PVA-Ti (described in Example 3) was added, and while adding 37 g (0.5 mol) of butanol as a calculated amount and 30 g of butanol as a surplus for azeotrope during the reaction, the reaction temperature was increased to 165 ~ The temperature was raised to 185°C to perform a dehydration esterification reaction. After removing the theoretical amount of water, the acid value is 1.2 after 13 hours and 0.24 after 20 hours.
It was hot. Further under reduced pressure 160-185℃/200mmHg
After performing the transesterification reaction at ~10 mmHg and recovering butanol, the acid value was 0.23 ml/g. After washing with water and washing with alkali, excess dibutyl adipate was distilled under reduced pressure to obtain 164 g of 1.4-butanediol butyl adipate butyl phthalate as a distillation residue. The viscosity of this product at 21°C is 102.5 centipoise, and liquid chromatography analysis shows that more than half of it is 1.4 butanediol butyl adipate butyl phthalate [C ₄ H ₉ OCO (CH ₂ ) ₄ COO
(CH ₂ ) ₄ OCOC ₆ H ₄ COOC ₄ H ₉ ] and was a mixture of high molecular weight esters containing three other high molecular weight oligomers. When this reaction product is used as a plasticizer for polyvinyl chloride, it can impart the same degree of flexibility as conventional DOP with approximately the same amount added. On the other hand, the loss on heating at 170°C is approximately 1/3 the amount of DOP, significantly improving heat resistance. From the above results, it can be seen that the above-mentioned composite ester reaction product can be used as a plasticizer having excellent plasticity. Example 13 <Production Example 2 of Composite Ester> 10 g of trimethylolpropane was dissolved in 30 ml of acetone, and Chromosoph W (manufactured by Gascro Kogyo Co., Ltd.) was added as a carrier made of diatomaceous earth and china clay.
5g was added and left to absorb. The acetone solution was filtered, washed with a small amount of acetone, and then dried under reduced pressure to produce a trimerolpropane adsorption carrier. The adsorption amount was 0.5 g, and 80 g of a xylene solution containing 1.05 g of tetrabutoxytitanium was added to this and refluxed. After 1 hour, the solvent and the butanol produced were removed, and the temperature was further raised to 180°C and 20 mm under reduced pressure.
The butanol produced was completely removed by heating with Hg for 3 hours. In this way, 5.7 g of supported catalyst was prepared. Adipic acid 306.6g (2.1mol), 1,3-butanediol 63g (0.7mol) and butanol 52g
(0.7 mol), add 1.5 g of the catalyst,
Dehydration and esterification reaction was carried out under azeotropic conditions. amount of calculation
The dehydration reaction was carried out while adding 207 g (2.8 mol) of butanol from the point at which 19 ml of water, equivalent to 25%, was distilled out. As a result, the acid value after 16 hours was 1.0, which means that approximately 98.5% of the reaction was calculated. . The acid value after 24 hours is
It became 0.20. The reaction product produced at this time is considered to be a mixture of 0.7 mol of butyl adipic acid, 1.3 butanediol ester, and 1.4 mol of dibutyl adipate. After removing unreacted butanol from the reaction solution under slight vacuum, the temperature was raised to 180°C and the produced butanol was distilled out under reduced pressure (final 20 mmHg), yielding 48 g of butanol, which was close to the calculated amount. It was confirmed that the above catalyst allowed the transesterification reaction to proceed sufficiently. This transesterification reaction produced 0.7 mol of 1.3-butanediol bisbutyl adipate and 0.7 mol of dibutyl adipate, but 200 g (0.77 mol) of dibutyl adipate was actually recovered as a result of vacuum distillation. The acid value after transesterification is
It was 0.15. After filtering the catalyst, it was possible to very easily reduce the acid value (0.03) by washing with alkaline water, and the reaction product was separated by distillation. The viscosity of the product obtained by distillation to remove dibutyl adipate is 70 centipoise.
It was a mixed ester containing three types of oligomers, mainly 1.3-butanediol bisbutyl adipate. As a result of distillation, the residual mixture (reaction product) is approximately
79% is 1.3 butanediol bisbutyl adipate with a high boiling point of 228-233°C/0.3mmHg. This reaction product can be used as an excellent plasticizer for vinyl chloride, showing approximately the same plasticity as DOP at an amount of 95%, and the volatility is reduced to approximately 10% of DOP.
That is, a polyvinyl chloride sheet using the above reaction product as a plasticizer was heated at 80°C for 8 weeks, and then at 100°C.
It has excellent heat resistance with almost no change in hardness even after two weeks of heating. On the other hand, with DOP, over 30% of the plasticizer volatilizes after 7 weeks and the hardness decreases.
Become 95 or higher. Example 14 34 g (0.1 mol) of tetrabutoxytitanium with 2-
Add 52 g (0.4 mol) of ethylhexanol, heat under reflux in an oil bath at 180-190°C for 1 hour, and distill the produced butanol under normal pressure to 25 mmHg reduced pressure to recover 27.6 g (93%) and tetra Octyloxytitanium was obtained. Next, 13.6 g (0.1 mol) of pentaerythritol was added in a ratio of 1:1 to the alkoxy equivalent of tetraoctyloxytitanium, heated at 180-190°C for 2.5 hours, and then heated under reduced pressure of 30 mmHg and then 1 mmHg. After heat treatment for 2 hours, the produced 2-ethylhexanol was removed by distillation, and a solid pentaerythritol polytitanate was obtained. Next, 50 g of a butanol solution containing 10 g of water was added and stirred at 80° C. for 2 hours to carry out activation treatment. After suction filtration, the filtrate was thoroughly washed with butanol to remove octanol, and then dried under reduced pressure to obtain 24.6 g of solid material. The acid adsorption amount of monooctyl phthalate in octanol of this solid compound was 0.117 mM/g. 0.5 moles of phthalic anhydride and 1.25 moles of 2
- When a dehydration esterification reaction is carried out using ethylhexanol in the presence of 0.8 g of the solid catalyst, the acid value shows a value of 0.08 after 3 hours and 0.05 after 3 and a half hours, resulting in a low acid value in a short time. An esterification reaction product of is obtained. Colorless DOP was obtained by filtration using activated clay as a filter aid. Similarly, using 0.5 mol of adipic acid and 1.25 mol of butanol in the presence of 0.8 g of the solid catalyst,
When the esterification reaction is carried out by partially adding butanol at 160 to 190℃, the acid value decreases to 0.5 after 7 hours and 0.03 after 10 and a half hours.Then, the acid value is filtered using activated clay as a filter aid. Very low acid value dibutyl adipate was obtained. In addition, an esterification reaction was carried out using 0.5 mol of phthalic anhydride and 1.25 mol of butanol in the presence of 0.8 g of the solid catalyst at 160 to 190°C by partially adding butanol. The price is
It became 0.05. Although the selectivity to phthalic acid is not yet sufficient for this esterification reaction, the activity of this solid catalyst has been improved to the same level as that of a soluble titanium catalyst, and low acid value esters can be obtained. I was able to do it. Example 15 2-
Add 52 g (0.4 mol) of ethylhexanol, heat under reflux in an oil bath at 180-190°C for 1 hour, and distill the produced butanol under normal pressure to 25 mmHg reduced pressure to recover 27.6 g (93%) and tetra Octyloxytitanium was obtained. Next, 1.4-butanediol 18 (0.2 mol) with a 1:1 ratio of alkoxy equivalent to alcohol equivalent was added, and after heating at 180 to 190°C for 2 hours, the 2-ethylhexanol produced was distilled under reduced pressure of 30 mmHg to form a solid product. I got it. Next, add 45g of 2-ethylhexanol and place in an oil bath.
The mixture was heated at 180 to 190°C for 1 hour, and the dissolving portion was separated using a hot gradient. 50 g of butanol and 10 g of water were added to the insoluble portion, heated and stirred at 80° C. for 1 hour, filtered, washed with hot butanol, and then dried under reduced pressure to obtain 10.5 g of a solid catalyst. On the other hand, the solid obtained by concentrating the solvent of the portion dissolved in 2-ethylhexanol under reduced pressure was added to a mixture of 10 g of water and 50 g of butanol at 80°C in the same manner as above.
After heating and stirring for a period of time, the mixture was filtered, washed with warm butanol, and dried under reduced pressure to obtain 11.5 g of a solid catalyst. 0.8 g of each of the solid catalysts was added to 0.5 mol of phthalic anhydride and 1.1 mol of 2-ethylhexanol, and an azeotropic dehydration esterification reaction was carried out at 190 to 210° C. in the presence of a small amount of toluene. The former (activated product of the insoluble part) had an acid value of 0.10 after 2 hours, 0.06 after 3 hours, and 0.04 after 4 hours, while the latter had values of 0.30, 0.15, and 0.10, respectively. There is a large difference in speed, and in particular, the rate at which the acid value decreases after 2 hours is extremely poor in the latter case. After the esterification reaction, a small amount of activated clay was added as a filter aid and filtered, and the remaining 2-ethylhexanol was distilled under reduced pressure to obtain colorless low acid value DOP. Note that catalyst residue removal was extremely easy. Said
A sheet was made using DOP as a plasticizer for polyvinyl chloride, and a heat test was conducted at 100℃ for 1,500 hours to compare the performance with a sheet using a commercially available plasticizer, but there was no difference in colorability. No difference was observed. (Effects of the Invention) The catalyst for esterification reactions and transesterification reactions made of solid highly crosslinked polyol polytitanate according to the present invention has a large catalytic action,
It is particularly large on the high temperature side (180 to 220°C), and the acid value of the reaction product can be made extremely low. This has great industrial significance; the catalyst residue (solid) can be removed by simple filtration, and the reaction products of esterification and transesterification produced in the presence of the catalyst of the present invention have extremely low acid values. Since the amount is low, the step of washing the reaction product can be omitted.

Claims (1)

[Claims] 1. A catalyst for esterification and transesterification reactions comprising highly crosslinked polyol polytitanate. 2 React alkoxy titanium and polyol,
A method for producing a highly crosslinked polyol polytitanate used as a catalyst for esterification reactions and transesterification reactions, characterized in that the reaction product is then highly crosslinked by dealcoholization treatment. 3. The highly crosslinked polyol according to claim 2, wherein the polyol or alkoxytitanium is adsorbed onto a carrier such as silica, alumina, zeolite, molecular sieve, or activated carbon, and then the alkoxytitanium or polyol is reacted with the polyol or alkoxytitanium. Method of manufacturing polytitanate. 4. The highly crosslinked material according to claim 2 or 3, characterized in that the ratio of the alkoxy equivalent of the alkoxy titanium to the OH equivalent of the polyol is OH equivalent/alkoxy equivalent = 1.8 to 0.9/1. Method for producing polyol polytitanate. 5. Claims 2, 3, or 4, characterized in that the alkoxy titanium is made by adding a higher alcohol to a lower alcohol alkoxy titanium and heating it to form a higher alcohol alkoxy titanium. A method for producing a highly crosslinked polyol polytitanate as described in Section 1. 6. The highly crosslinked polyol polytitanate according to claim 2, 3, 4, or 5, characterized in that the highly crosslinked polyol polytitanate is made into a hydrate by water treatment. Production method.