JPS62140651A - Catalyst for esterification reaction and ester interchange reaction - Google Patents

Abstract

PURPOSE:To obtain a highly activated solid catalyst by allowing alkoxytitanium to react with water and using highly polymerized and highly crosslinked polytitanic acid as a catalyst for esterification reaction and ester interchange reaction. CONSTITUTION:Polytitanic acid which is produced by allowing alkoxytitanium to react with water and highly polymerizing and highly crosslinking the product is used as a catalyst for esterification reaction and ester interchange reaction. In such a way, a highly activated solid-like catalyst is obtained and also acid value of a reaction product can remarkably be lowered. Therefore since the residue of the catalyst is excellently treated by only simple filter operation and the acid value of the reaction product is low, the washing process of the reaction product can be omitted.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a highly active solid catalyst used for esterification and transesterification reactions, and a method for producing the same.

[Prior art and its problems]

Hitherto, for esterification and transesterification reactions, fijaM such as para-toluenesulfonic acid, sulfuric acid, hydrochloric acid, alkaline, tetraalkoxydine, etc. have been used. For example, useful plasticizers for plastics such as dioctyl phthalate (hereinafter abbreviated as DOP) and dioctyl adipate (hereinafter abbreviated as DOA) are industrially produced through esterification reactions. I have a similar problem.

Catalysts used in these industrial esterification reactions are naturally required to have a high activity for practical purposes, but the catalysts used in these industrial esterification reactions are required to have a high activity, but the reaction rate of the acid and alcohol is close to 1%. (It is very difficult to do so, and the problem is whether to use a large amount of catalyst to speed up the reaction, or to remove the remaining catalyst. In order to improve the electrical properties and thermal stability of plastic compositions containing plasticizers, the removal of golic acid requires M f+1fiO,1, or even a lower value, according to the standard. A highly active catalyst that has high activity at low concentration is desired.In the case of para-toluenesulfonic acid catalyst, the catalytic activity is sufficiently fast at low humidity, but there are problems in terms of removing catalyst residue, and alkoxy titanium In the case of catalysts, as in the case of acid catalysts, if the acid value cannot be lowered sufficiently by removing catalyst residues (including decomposition and removal of catalysts), a neutralization and washing step is essential, and separation of the ester layer and aqueous layer is necessary. This raises a new problem: defects.

Recently, a method using a chelating agent as a method for removing catalyst residue from a titanium catalyst (US Patent No. 4.06.091) has been proposed.
In addition, research on heterogeneous catalysts in which catalyst components are minimally dissolved in the reaction system is also actively being conducted.

For example, catalysts for esterification reactions supported on carriers have been proposed. [C, A, 131919h (1984)
Ko.

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, the hand coalescence of tetraalkoxy titanate is hydrolytically treated with peroxide in the presence of an alkali. It has been proposed that the treated product is then refluxed in a monoalcohol (monohydric alcohol such as n-butyl alcohol or heptatool) (Japanese Unexamined Patent Publication No. 53-94296). This is difficult because it is complicated and it is difficult to design the optimal catalyst properties for various esterification reactions.

[Problem that the invention seeks to solve]

The present invention aims to provide a novel, highly active titanium-based solid catalyst that improves the drawbacks of the conventional catalysts for esterification and transesterification reactions.

(Intangible means for solving the problem)・Background of the invention> The present inventor first reacted alkoxy titanium with a polyol and then highly crosslinked the obtained reaction product to form a titanium-based solid. Product (polyol polytitanate)
was found to be extremely useful as a catalyst for esterification and transesterification reactions, and a patent application was filed. (
(Japanese Patent Application No. 60-219140).

The present inventor further studied the polyol polytitanate ester catalyst, and based on the idea that water could be considered as a bifunctional diol as a polyol component to be reacted with alkoxytitanium, the inventors discovered that alkoxytitanium and water As a result of pursuing this reaction, it was discovered that a useful titanium-based solid catalyst could also be obtained, leading to the present invention.

That is, the present inventor has developed a polyol polytitanate solid catalyst/8:1 which is useful in the reaction of alkoxytitaniums and polyfunctional polyols as described above, and subsequently reacted with water instead of the polyol component. We proceeded with our research with the expectation that even in such cases, useful substances with catalytic activity would be produced.

However, in contrast to the reaction between alkoxytitaniums and polyfunctional polyols, water does not necessarily move divalently; for example, when alkoxytitanium is reacted with an excess amount of water, that is, 4 moles of water, water acts as a monovalent, Ti(O
H) A hydroxide corresponding to 4 is produced. Even if an attempt is made to produce polytitanic acid by the action of divalent water, it is not always easy to control the molecular weight because a trivalent or tetravalent butane compound is used. In particular, during the process of forming polytitanic acid, oligomers are always generated based on the molecular weight (a), but when this oligomer is hydrolyzed by adding excess water during the activation treatment (a), the hydrolysis is excessive and the Ti (OH)4, or something that dissolves in the esterification reaction liquid that is the target of the catalytic action, is generated, which prevents the acid value of the esterification reaction product from decreasing. I started it.

Therefore, by pursuing a method for synthesizing polytitanic acid that minimizes the formation of oligomer components, it is possible to create an esterification reaction product that has sufficient catalytic activity in the esterification reaction and has a low acid value in the early stages of the esterification reaction. I thought of it as something that could be wandered around.

This way of thinking can be schematically explained by the following equation.

Polytitanium oxidation reaction> [A] [B] That is, 1 mol of alkoxy titanium is equivalent to 4 alkoxy titanium, and 2 mol of water is equivalent to 40H (alkoxy titanium equivalent to OH equivalent - 1 to 1). When reacted, first a tank structure compound [A] is produced, and this reaction product [A] is further subjected to a dealcoholization reaction to produce polytitanic acid having the structure [B].For convenience, this will be described below. The reaction is called the polytitanium oxidation reaction (7Sζ).This polytitanium oxidation reaction proceeds by a dealcoholization reaction, and the reaction can be accelerated by heating in a solid state, in a solvent, or in the alcohol produced. In particular, by heating while removing the alcohol produced under reduced pressure, [8] produced by the polytitanium oxidation reaction can be polymerized and crosslinked.

For the reasons mentioned above, the product of lipolytitanium oxidation reaction [B]
When polymerizing a material, it is extremely important to minimize the production of oligomers, and the higher the polymerization, the more difficult it is to produce oligomers.

When a method of reacting alkoxytitaniums in a large amount of water in one step is adopted, a large amount of monomolecules expressed by Ti (OH)4 or hydrates of oligomers soluble in the solution of the esterification reaction are generated. I don't like it. That is, when it is not possible to uniformly react and produce polymerized polytitanium M[B] during the production of a titanium-based solid catalyst, many of the monomolecular or oligomer hydrates are produced as by-products, and this leads to the formation of esters. As a result, the acid value of the reaction product does not decrease. Therefore, in the polytitanium oxidation reaction, it is important how to obtain polymerized polytitanium 1 (the above-mentioned [B] compound), and the present invention overcomes this problem.

・〈Specific structure of the invention〉 To summarize the present invention, it is an invention relating to a method for producing polytitanic acid used as a catalyst for esterification and transesterification reactions, wherein the polytitanic acid is produced by reacting water with alkoxytitanium. 'lAJm' is obtained by polymerizing and highly cross-linking.

Hereinafter, the configuration of the present invention will be explained in detail.

In the production of the [A] compound in the polytitanium oxidation reaction described above, the reaction of the titanium compound simultaneously proceeds between titanium molecules, resulting in dimerization and further multimerization reactions of titanium alkoxide as shown in the following formula. These reactions also occur, and these reactions proceed simultaneously with the production of [A].

In terms of the relationship with water, if 1 mole of tetraalkoxy titanium has 172 moles of water, it is a diploid, or 1/2 to 1/2 of water.
When the amount of 1 mole is equivalent to 2 moles of water, if the dealcoholization reaction is allowed to proceed completely, the reaction [A] or [B] will proceed. Polytitanic acid is produced.

Is it possible to make a diploid or even a tetraploid from tetraalkoxytitanium as described above? If it does not contain alkoxytitanium monomer, excess water compared to the equivalent amount of alkoxytitanium is used. can be reacted with.

When using tetrabutoxytitanium tetramer (tetraploid) [Tokyo Kasei Co., Ltd. product], the alkoxytitanium equivalent is 10
Even if the amount of water used is increased by 1.5 times, not only those caused by Ti(OH)A but also A
Ribomer does not produce a low molecular weight titanide that is soluble in the esterification reaction product, and when such a polytitanium oxidation reaction product is used as an esterification catalyst, there are many surface OH groups and the activity is relatively high. A low acid value esterification reaction product is produced.

However, the purification of Tetramer requires a corresponding amount of expense, and the use of Tetramer as a starting material is not necessarily a prerequisite, since the same or greater effect can be obtained using Tetramer. isn't it.

Stepwise reaction of 1 mol of titanium compound with 172 mol of water produces a diploid, further reaction with 174 mol of water produces a tetraploid, and reaction with 178 mol of water produces an octaploid, 1716 mol of water. When producing a 16-mer by reacting with alkoxy titanium, the reaction may be avoided by sequentially adding up to 2 molar equivalents of water to the equivalent of alkoxytitanium.

In fact, the objective can be achieved by sufficiently carrying out the polytitanium oxidation reaction after reacting at an equivalent ratio of 1:1.

The solid [8] produced by the polytitanium oxidation reaction has unreacted alkoxytitanium groups at the ends. Therefore [
The more complex the polymer B] is, the more bulky the alkoxy group is, the more difficult it is for polymerization and hypercrosslinking to proceed through dealcoholization, but dealcoholization should be carried out sufficiently under reduced pressure. The dealcoholization can be carried out substantially quantitatively by methods such as the following. Generally, the catalyst product 1 becomes heavier because unreacted alkoxy groups remain.

By hydrolyzing this terminal alkoxy group with excess water, OHM on the surface of the solid catalyst can be increased and the catalytic activity can be increased. At this time, the amount of water used is from the same number of moles as the alkoxy equivalent to about twice that of the alkoxy equivalent, and if a large excess of water is used, the hydrolysis will not be completed, and the esterification reaction will occur. Ti(OH)4, which is negative to the low acid value of the material, is generated.

In addition, since the solid catalyst is highly cross-linked, it is difficult for internal alkoxy groups to be removed, so by water treatment to a -El number equal to the skewer of water used in the polytitanium oxidation reaction,
The purpose of high activation can be fully achieved. The reaction with water can be achieved by heating with hydrous alcohol or by leaving it for a long time.This water treatment increases the number of OH groups on the surface of polytitanic acid (solid catalyst) and increases the activity of the catalyst. become.

The polytitanium oxidation reaction described above can be carried out on a carrier. When a carrier is used, the catalyst becomes heat resistant and filtering of the catalyst after esterification and transesterification becomes easier, so it is preferable to carry out the polytitanium oxidation reaction in the coexistence of various porous carriers and fine powder.

Another advantage of using a carrier is that the composite matrix of the carrier and solid catalyst minimizes the elution of the polytitanic acid delta oligomer, thus allowing the esterification reaction product to have a low acid value. Note that as the carrier, silica, alumina, reolite, diatomaceous earth, molecular sieve, activated carbon, etc. are used.

In the polytitanium oxidation reaction described above, the steric groove JA of the alkoxy group of the butane compound used as a starting material has a large influence on the reaction. Tetraalkoxytitanium containing a higher alcohol residue can be easily synthesized from a lower alcohol titanium compound. For example, by simply adding 4 moles of 2-ethylhexanol, dirucohol, cyclohexanol, etc. to 1 mol of a lower alcohol titanium compound such as butyl butanate or tetraisopropoxy titanium, and heating to reflux, a low boiling point compound can be obtained. of alcohol will be distilled out, so this can be completely reduced.
When the 4 lower alcohols (butanol, isopropanol, etc.) produced by heating are removed, the higher alcohol tetratitanate is produced.

Using the thus obtained tetra-2-ethylhexyloxytitanium (octyl titanate) as a starting material,
Assuming that water is divalent, the ratio is 1 to 0.5 (-1 to 0.5 in the -sil ratio).
When pair 1) is added and heated, most of the butanoic acid ester polymer produced is b, which is mainly composed of dimers, so that most of it dissolves.

Next, when an equivalent ω ratio of 0.5 (1 mol of alkoxy titanium: 1 mol of water) is added, partial crosslinking occurs, and a precipitate corresponding to [A] is added to the polytitanium oxidation reaction. However, if a sufficient polytitanium oxidation reaction is carried out, the polymerization reaction is slow, but the de-2-ethylhexyl alcohol reaction proceeds, and a porous solid catalyst having voids is formed in the produced solid. As a result, it exhibits superior catalytic activity compared to solid catalysts made from butyl or isopropyl titanate; for example, the esterification rate of adipic acid is fast with the latter, but not sufficiently with phthalic acid, whereas the esterification rate of octyl titanate with the former is fast. The produced solid catalyst exhibits excellent high activity for any acid esterification reaction.

This is because when the pores on the solid catalyst have small pore sizes, the esterification reaction of adipic acid is fast, but phthalic acid is slow. By enlarging the pores, phthalic acid can be easily adsorbed, resulting in a highly active esterification reaction. It is thought that it became a solid catalyst. Therefore, the use of higher alkoxy titanium in polytitanium oxidation reactions is important for producing highly active solid catalysts.

Next, in addition to the above overview of the present invention, the method for producing the polytitanic acid solid catalyst according to the present invention will be explained in more detail.

In the polytitanium oxidation reaction, when butanol containing the maximum amount of water is added little by little to tetrabutyl ditanate, a white cloudy layer is formed immediately after mixing at the beginning of addition, but this quickly dissolves. As the amount of water increases, an oily substance and a colorless precipitate form.

The rate of precipitate formation varies depending on the temperature and addition rate, and the higher the alkoxy group, the slower the precipitate formation becomes, resulting in an oily substance. Butylditanate detramer becomes a solid relatively quickly, but some oily precipitation can be seen.On the other hand, when tetrabutoxytitanium is present in excess water, it quickly becomes a solid mainly T1(OH)4. A precipitate is obtained. When water is added and the mixed solution is left as is or heated and refluxed in butanol or higher alcohol, almost all of the alkoxytitanium is converted to polytitanic acid and alcohol is produced. If butanol produced using butoxytitanium as a starting material is distilled and measured, the amount added to the addition of water and the amount produced from the titanium compound can be obtained approximately as a constant.
The alcohol is recovered by distillation under reduced pressure. In the polytitanium oxidation reaction, the reaction time naturally varies depending on the reaction temperature, but after solids are formed in the liquid alcohol, the alcohol is removed by distillation, and then 1j11 heat is applied under reduced pressure to sufficiently dealcoholize. Or preferable. If you concentrate without producing enough solids, oily oligomers will remain together with the solids, or if you heat it to 160-200'C under reduced pressure, dealcoholization will occur from the oils and even the solids, and the oils will also be removed. It turns into a solid with voids, and when taken out and crushed, it can be easily reduced to an extremely fine powder, indicating that it is highly crosslinked and that the alcohol has volatilized from inside to form a polymer.

Next, the general method for activation will be explained. It is sufficient to dissolve the same amount of water used in the polytitanium oxidation reaction in butanol, isopropanol, etc. and heat reflux for 1 hour. Higher alcohols produced by dealcoholization from solid catalysts dissolve in butanol, isopropanol, etc.

The activated product is filtered, washed with butanol, etc., and then dried by heating under reduced pressure to be used as a solid catalyst.

When the titanium-based solid catalyst produced in the present invention is used in an esterification reaction, the adsorption of alcohol components in the esterification reaction is very rapid, and although it is difficult to consider that the absorption of acid components is primary, the reaction increases in proportion to the concentration of acid. proceed. The rate of esterification reaction can be approximately estimated by the rate of water dehydration, but after a quantitative amount of water is removed by azeotropic distillation, a catalyst with low activity will have a concentration of 0.1 or less after several hours to more than ten hours. It becomes an ester mixture with a low acid value. Acid value is usually KO + per 1g
It is defined as my number, but in this description it is 1/g per gram.
If expressed as the number of mL of 2ON K OH titration, then (if you use direct and the reactant is known, the acid (curve x 1/2)
0000 x reaction ♀ x 1/2 can be calculated as 81 points because of the dibasic acid remaining in the reaction solution, and in the octyl esterification of adipic acid, the reaction rate of 1 mole is 450 g.
Assuming that the acid value is 1, the number of moles of residual adipic acid is 1.12.
5x 10 mol, 1.125x 10- for 0.1
The esterification reaction is (1-L 125x 1
0 ) x 100 = 99.88% or more will react. This esterification reaction is carried out by adding Natlab 1 hexytitanium to an alcoholic solution containing a large amount of water, filtering the resulting precipitate, collecting it, and drying it under reduced pressure.
) When carried out using a solid hydration product considered as 4, the dehydration rate of the esterification reaction is relatively low or the final acid value does not decrease. That is, the acid value does not become less than 1 even after a long period of time.

The activity of the polytitanic acid solid catalyst of the present invention appears to be proportional to the number of OH on the solid catalyst. By using the polymerized polytitanic acid solid catalyst of the present invention, the acid value of the esterification reaction product can be gradually lowered to 0.1 or less with the reaction time. Activation can significantly shorten the time it takes to reach 0.1 or less, and it is possible to achieve this within 3 hours. From the viewpoint of activity alone, the titanium hydrate (Ti(OH>4>) also has sufficient activity, but if it is mixed in the catalyst or remains as an oligomer, it will cause esterification. There is a drawback that the acid value reached by the reaction product increases.

Therefore, water 2 for 1 mole of tetraalkoxy titanium
The mole polytitanium oxidation reaction is carried out by cold addition/Itl followed by gradual wetting of IJ11 to polymerize, partial addition of water and final dealcoholization, and further crosslinking. There is a method of reacting in an aqueous system containing a small amount of polyol, but the key is to use pure Ti(OH).
It is necessary to take a method to prevent the generation of 4.

Furthermore, as the titanium compound used as a starting material for the polytitanium oxidation reaction of the present invention, those commercially available as tetraalkoxytitanium can be used regardless of the type of alcohol group, and also titanium compounds such as 2Ii form, 4 monomer, etc. It can also be used as an oligomer.

Further, in the case of a titanium compound containing an alkoxy group or a lower alcohol component, a higher alcohol titanium compound may be prepared by reacting with a higher alcohol, and this may be used as a starting material. In particular, in the case of a higher alcohol titanium compound, it is reacted with a polytitanate ester oligomer solution by reaction with 174 molar amount of water, and then reacted with an equal molar equivalent of water. When activated by further treatment with water, a solid catalyst with sufficient reaction activity against many acids can be obtained.

The polytitanic acid solid catalyst of the present invention can perform a dehydration esterification reaction between an acid and an alcohol (for example, an esterification reaction between a monobasic acid, a dibasic acid, and a polybasic acid and a 1-12- and polyfunctional polyol). Reaction) Polyester production reaction in which 02 hydrochloric acid, diols, and alcohols coexist, ○ Dehydration esterification and transesterification reaction during the production reaction of complex esters such as polyol bisalkylambate, 1 ster of O fatty acid 2, such as alkyd paints and modified ester paints.
It is useful as a catalyst for various esterification and transesterification reactions, such as esterification and transesterification of basic acids and fatty acids with polyols.

Hereinafter, the present invention will be explained in more detail based on examples, but the present invention is not limited to these examples in any way unless it deviates from the technical idea thereof.

〔Example〕

<Example 1> Tetrabutoxyditane 349 (0.1 mol, 0.4 molar equivalent) was dissolved in butanol 709, and while stirring,
7 containing 3.6y (0.2 mol, 0.4 molar equivalent) of water
0 g of the butanol mixture was mixed dropwise at a reduced temperature. The liquid becomes cloudy upon the first drop, but when the drop is stopped, it mixes and dissolves. When added for 1 hour, an oily substance or a precipitate will form at the end. Raising the temperature by 1 degree while stirring and refluxing will result in 4
After some time, some of the solids precipitate out. The butanol is then distilled to a mostly solid precipitate. Be careful while preventing bumping. [When the pressure is reduced to 1 temperature, butanol will be distilled out, and the final temperature will be 180-190°C/20 mmfl (J). After heating for 3 hours, no butanol will come out. ¥8: Confirmed and further heated under reduced pressure for 15 minutes using 1ml and 1g.

Then, 3.6!7 water dissolved in 20 g of butanol was added, heated for 1 hour), the constant was collected by filtration, washed with butanol, and dried under reduced pressure to obtain 8.4 g of polytitanic acid solid catalyst. Ta.

0.50309 in a mixture of 146 g (1 mol) of Adipine M and 325 g (2.5 mol) of 2-ethylhexanol.
Add the polytitanic acid solid catalyst prepared as described above,
The dehydration esterification reaction was carried out at 180-200°C in the presence of a small amount of toluene. In 30 minutes! - Half of the water of 1Rm was distilled out, and the distillation was almost completed after 80 minutes. 12
The acid value after 0 minutes is 0.13.The acid value after 240 minutes is 0.02
I failed.

Control Example> 3.49 g of rhabdoxytitanium was dissolved in 53 g of butanol and added to a mixed solution of 20 g of water and 50 g of butanol under reflux. A colorless precipitate was deposited, and after 6 hours, the precipitate was collected by filtration, washed, and left to dry overnight at 80°C in a vacuum dryer. h as the reaction product Ti(OH)4
Adipine M 14G was calculated using 0.70059 as a weight that matched 0.5g of polytitanic acid in Example 1.
7 (1 mol) and 2-ethylhexanol 3259 (
2.5 mol) to carry out a dehydration and esterification reaction. The water in the dehydration esterification reaction is quickly distilled out after 45 minutes? After 90 minutes, an amount of about δl was distilled out. The measured acid value of the dehydrated esterification reaction product was 6.6n after 3 hours.
II2/'j, 4 after 7 hours, 2 and 2 after 15 hours, and it was determined that the value did not fall below 1 even after long-term heating. The rate at which water is produced in the dehydration reaction increases when the surface of the solid catalyst is hydrated, or conversely, the acid value of the esterification reaction product does not decrease.

<Example 2> To a butanol 209 solution of 9.7 g of tetrabutoxytitanium tetramer (Tokyo Kasei Co., Ltd. product), 1.359 g of water was added 2
The solution was dissolved in 0 g of butanol and kneaded (while heating).

Tetrabutoxytitanium tetramer is presumed to be polytitanic acid represented by the N'SW formula of O.

Adipine following Example 1! 0.5005 g of the above catalyst was added to a mixture of 146 g (1 mol) and 2-ethylhexanol 3259 (2.5 mol), and the IJR water esterification reaction was carried out at 180-200°C in the presence of a small amount of toluene. I did it. Half of the amount of water was distilled out after 30 minutes, and the calculated amount of water was distilled out after 2 hours, and the acid value was already 0.05 after 4 hours, and 0.02 after 5 hours.

<Example 3, 4> Buburgitane - 1 to 17 g (0.05 sill, 0.2
Dissolve 103 parts of butanol and 1 part of water. ag
(0,L pill, 0.2'Ele award) and butanol 2
09) While adding the kneaded mixture little by little, raise the temperature to 100~
The mixture was heated to 120°C and the reaction was carried out for 1 hour. In this case too, an oil was first deposited and then a solid was precipitated. After heating for an additional 3 hours, the produced butanol was removed by distillation, and the mixture was heated under reduced pressure at 180-190°C for 3 hours, and then heated under reduced pressure of 1Mn for 15 minutes. The product was dissolved in water 0.809 (0,
088-E) and 20 g of butanol and further heated for 1 hour, the solvent and the produced butanol were completely distilled under reduced pressure to obtain a solid catalyst of 5.29.

0.50077 of the above solid catalyst was added to a mixture of Adipine W 146s (1 mol) and 2-ethylhexanol 32'+9 (2,5-El), and dehydrated and esterified in the presence of a small amount of toluene at 180-200°C. The reaction was carried out.

As a result, half of the amount of water was distilled out after 35 minutes, a false amount of water was distilled out after 105 minutes, and the acid value of the esterification reaction product after 2 hours was 0.0.
The acid value became 0.03 after 8.3 hours and 0.04.4 hours.

For the same solid catalyst, phthalic acid 1489 (1 mol)
In the same manner, 0.50109 catalyst was added to a mixture of 3259 and 2-ethylhexanol (2.5 mol), and 180
The dehydration esterification reaction was carried out at ~205°C in the presence of a small amount of toluene. Half of the amount of water was distilled out after 40 minutes, and the maximum amount of water was distilled out after 4 hours, and the acid value at that time was 3.35, 0.15 after 8 hours, and 0.02 after 12 hours.

In this way, it is possible to achieve a low acid value in any case, but it can be seen that the rate of esterification varies by as much as 11 J depending on the type of acid value.

<Example 5> 28.4 g of tetraisopropyl titanate (0,1'E
2-ethylhexanol 52
When 9 (0.4 mol) is added and heated to 160-180°C, isopropanol is distilled out after about 30 minutes and finally becomes a volatile liquid at 180'C/20% Hg.
An approximately quantitative amount of 1 q of product was obtained. This product is a liquid thought to be tetra-2-ethylhexyloxyditane, which is mixed with 1.80209 mol of water (0.1 mol) while cooling.

An isopropanol solution containing 0.2 molar equivalent) was added under cold conditions, and then the partially precipitated white cloud was heated to completely dissolve it and form a titanate oligomer. Remaining under cooling again 1.79619 (0.1 mol, 0.2
Add 1000 ml of water dissolved in isopronol, stir and raise the temperature. At about 80'C, a colorless precipitate begins to precipitate and 1q of a white cloudy liquid is obtained. After refluxing, the isopronol was distilled off and the volatile components were removed under reduced pressure to obtain a highly viscous oil containing solids.
It solidifies when heated to 0'C. This solid substance was reconverted to 2-ethylhexylline-1~ and 180~190'
After heating at C for 8 hours, concentrating and heating under reduced pressure again for 30 minutes, 50 U of butanol containing 3.6 U of water was added.
The mixture was stirred at 30°C for 20 minutes, and the resulting precipitate was filtered and dried under reduced pressure to remove the solid catalyst of 869 and 157. This is roughly 1
The production amount was close to the planned amount for 02.

Next, 14 JJ (1 mole) of anhydrous phthalic acid and 325 g (2.5 moles) of octatool were added with 0.50 g of the above solid catalyst.
When 30g was added and a dehydration esterification reaction was carried out, 3
Approximately half of the amount of water was distilled out after 0 minutes, approximately the calculated amount of water was distilled out after 70 minutes, and the acid value of the esterification reaction product after 90 minutes was 0.14.
The value was 0.08 after 2 hours, and 0.04 after 4 hours.

<Example 6> 26 g (0.2 mol) of 2-ethylhexanol was added to butyl titanate 349 (0.1 mol 0.4' mol equivalent), heated to 160-180'C, and then produced under reduced pressure. 14 g of butanol was recovered while removing the butanol.

This resulted in a titanium compound in which half of the alkogides were replaced with 2-ethylhexanol.

To this, butanol 209 and sorbitol 39 (0,01
6 moles, 0.1 molar equivalent) and 3.6025 g of water (0
, 2 mol, 0.4 mol equivalent) were added and refluxed for 3 hours, and then the produced butanol and 2
- Distill ethylhexanol under reduced pressure and further 180'
Polyditane oxidation reaction was performed by heating with 1 g of C20 mm for 6 hours and 1 mm of 1 l (] for 33 minutes.Next, it was heated with butanol containing 3.6 g of water for 30 minutes, and the solvent was removed by heating under reduced pressure. The solid catalyst of i was removed.It should be noted that, considering the theoretical amount, this solid catalyst still had an alkyl terminal.

Next, 0.8027'j of the solid catalyst was added to a mixture of 1 $749 (0.5 mol) of anhydrous phthal and 163 g (1.25 mol) of octatool to carry out a dehydration esterification reaction. After 65 minutes, 81 calculations of water was distilled out, and the acid value after 2 and a half hours was 0.13.5 hours (IThio, 04).

<Example 7> Tetraisopropoxytitanium 28.47 (0.1 mol).

0.4 molar equivalents) was added with 1.80089 molar equivalents of water (0.4 molar equivalents) under cooling.
, 1 mol, 0. Add the isopropanol solution of FE Ru), heat and dissolve the partially formed white turbidity,
After heating for 30 minutes, it was cooled again and the remaining 1.78207 water (0.1 mol, 0.1 mol equivalent ♀) was added. At first, it was in a solution state, but as the temperature rose, a precipitate precipitated out, and the temperature reached 40°
At C, a gel-like precipitate is deposited. Then, after concentrating the isopropanol, butanol was added and the mixture was refluxed for 8 hours. When the solvent was completely evaporated, a solid remained. Add 3 parts water to butanol again
．． A solution in which 09 was dissolved was heated for 30 minutes to avoid a hydration reaction, and then filtered φυ repeatedly. Using the solid catalyst thus prepared, transesterification reactions were carried out, including the esterification of adipic acid, diols, and monoalcohols as described below.

A mixture of adipine iV 1469 (1 mol), 36 g (0.4 mol) of 1.4-butanediol, and 104 g (0.8 mol) of 2-ethylhexanol was added with 0.0 ml of the solid catalyst.
50049 was added to perform a dehydration esterification reaction.

After 25 minutes, 15 d of water was distilled out and 40% of the calculated amount reacted.

From this point the remaining 2-ethylhexanol 1049
(0.8 mol) was added dropwise, and the addition was completed by 60 minutes after 80% reaction. Meanwhile, the dehydration esterification reaction is 190
The process proceeded smoothly at ~200'C, and after 1.5 hours, an almost quantitative amount of water 3.6d was distilled out, and the acid value of the esterification reaction product after 2.5 hours was 0.25.4 hours later. The acid value of is 0.06
．． After 5 hours, it became 0.03. The composition of the low acid value ester mixture after the esterification reaction is theoretically based on the above reaction molar ratio: 0.6 mol of DOA and 0.4 mol of ester alcohol (octyl on one side, 1.3 butanediol on the other). ester). This mixture of ester alcohol and diester was mixed under reduced pressure for 20 hours (]~
When heated to 180-190°C with 1 mm 1 liter (l), 1
51 g of 2-ethylhexanol was recovered, ie, almost quantitatively, and it was found that the dehydration esterification catalyst functioned as the esterification catalyst. The product had an acid number of 0.04 and was distilled after decatalyst to remove 8 DOA. The main component of the resulting complex ester was 1,3-butanediol bis-2-ethylhexyl adipate, which was a mixture with a few oligomers. When this is used as a plasticizer for vinyl chloride resin, DO
A plasticized polyvinyl chloride sheet with approximately the same plasticity as P and excellent heat resistance with almost no heat loss even after long-term heating (heated at 100°C for 280 minutes) was produced.

<Example 8> 28, lI'J (0,1[-le)'s te 1 ~ rightsb]
42 g (0.4 mol) of 2-ethyl quinanol was added to 1 pyruditanate and heated to 160-180°C, and the produced isopropyl alcohol was distilled off to synthesize tetraoctyl titanate. Add 20 g of Chromo Soap W (Diatomaceous raw material carrier manufactured by Gascro Kogyo Co., Ltd.) to this reaction product solution.
After adding 1.7952 ml of water, it was cooled while stirring, and 1.7952 ml of water was added to it.
50 g of isopropanol containing ff was added, warmed, and flowed rapidly for 1 hour, and then the isopropanol was concentrated. Next, cool it again, add 50 g of isopropatool containing 1.80089 water in exactly the same way, then gradually raise the temperature, and finally after distilling the isopropatool, add 20 g of 2-■ dirheginanol. , 7J at 160-180°C for 16 hours
It was hot. After washing the product by one stroke, butanol 1007 containing 3.6 g of water was added, heated for 30 minutes, filtered and washed, and then dried under reduced pressure to obtain 29.5 g of I-port catalyst.

Said carrier F$, anhydrous phthalic acid as a catalyst 1
48g (1 mol) and 2739 2-ethylhexanol
A dehydration esterification reaction was carried out in addition to a mixture of (2.1 mol). ? After () minutes, half (n) of water was distilled out after 55 minutes, and the acid value after 1 and a half hours was 0.16. After 2 hours, it was 0.
．． After 0.8.3 hours, the acid value was 0.0.1, and the reaction solution was completely transparent. , filtration has become extremely easy.

〔Effect of the invention〕

The catalyst for esterification and transesterification reactions comprising solid highly crosslinked polytitanic acid according to the present invention can make the acid value of the reaction product extremely low. The industrial significance of this is extremely large; the catalyst residue (solid) can be removed by a simple filtration operation, and the reaction products of esterification and transesterification produced in the presence of the catalyst of the present invention have extremely high acid values. Since the reaction product is low, the step of washing the reaction product can be omitted.

Patent applicant: New Technology Development Corporation Agent: Patent attorney Yoshio Mizuno Procedure Neyama iE book (voluntary) 2nd day of month g, 1986

Claims (6)

[Claims] (1) A catalyst for esterification reactions and transesterification reactions consisting of polymerized and highly crosslinked polytitanic acid. (2) A method for producing a catalyst for esterification and transesterification reactions comprising polymerized and highly crosslinked polytitanic acid, which is characterized by subjecting a reaction product of alkoxytitanium and water to dealcoholization treatment. (3) Polymerization according to claim 2, characterized in that water is calculated as a divalent equivalent to the alkoxy equivalent of alkoxy titanium, and both components are reacted in a ratio of 1:1 to 2 equivalents. , and a method for producing a catalyst for esterification reaction and transesterification reaction comprising highly crosslinked polytitanic acid. (4) The polymer according to claim 2 or 3, characterized in that alkoxy titanium and water are reacted in the presence of a carrier such as silica, alumina, zeolite, diatomaceous earth, molecular sieve, or activated carbon. A method for producing a catalyst for esterification reaction and transesterification reaction consisting of molecularized and highly crosslinked polytitanic acid. (5) Claims 2, 3, or 4 are characterized in that the alkoxy titanium is made by reacting a lower alcohol alkoxy titanium with a higher alcohol to form a higher alcohol alkoxy titanium. A method for producing a catalyst for esterification reaction and transesterification reaction comprising the polymerized and highly crosslinked polytitanic acid described above. (6) The polymer according to claim 2, 3, 4, or 5, characterized in that the polymerized and highly crosslinked polytitanic acid is made into a hydrate by water treatment. A method for producing a catalyst for esterification reaction and transesterification reaction consisting of molecularized and highly crosslinked polytitanic acid.