JPH04316536A - Production of alicyclic diester compound - Google Patents

Abstract

PURPOSE:To produce an alicyclic diester compound useful for manufacturing a new acrylate-based polymer having excellent physical and chemical characteristics in high conversion and in high selectivity. CONSTITUTION:An alicyclic diolefin is reacted with acrylic acid by using a dehydrated heteropoly-acid or an acidic salt thereof as an acid catalyst to produce an alicyclic diester compound shown by the formula (R is hydrogen or methyl group and R' is alicyclic olefin residue).

Description

[Detailed description of the invention]

0001

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing an alicyclic diester compound by reacting an alicyclic diolefin with acrylic acid or methacrylic acid.

[0002] The alicyclic compound diacrylate or dimethacrylate (hereinafter abbreviated as di(meth)acrylate) obtained by the present invention has physical properties such as transparency, heat resistance, thermal stability, solvent resistance, and dielectric properties. , is an extremely useful chemical substance used to produce new acrylate polymers with excellent chemical properties.

[0003] Specific applications include the modification of photocurable resins, thermosetting resins, acrylic paints, and acrylic adhesives.

0004

[Prior Art] A method for producing an ester from a carboxylic acid and an olefin by an acid addition reaction in the presence of an acid catalyst is as follows:
It has been known for a long time. For example, Chemical Abstracts, pages 63-9055 (1966) discloses a method for producing a carboxylic acid ester of dicyclopentadiene using an ether complex of boron trifluoride as a catalyst. In addition, JP-A-56-59736 and JP-A-63-8355 disclose a method for producing (meth)acrylate of octahydrodimethanonaphthalene and its derivatives, in which concentrated sulfuric acid or an ion exchange resin is used as a catalyst. A method is disclosed. However, these methods have the problems of equipment corrosion, the need for an excessive amount of methacrylic acid or acrylic acid (hereinafter abbreviated as (meth)acrylic acid) relative to the olefin, and the need for a large amount of catalyst. There is. Therefore, it cannot be said to be an effective method.

On the other hand, Japanese Patent Application Laid-Open No. 56-406445
JP-A-56-59735 discloses a method for producing dicyclopentadiene (meth)acrylate using a tungsten heteropolyacid as an acid catalyst. Although this method solves the problem of equipment corrosion, the yield of (meth)acrylate is not sufficient.

JP-A No. 63-280043 discloses that di(meth)acrylate is prepared from norbornadiene and (meth)acrylate.
A method for making acrylates is disclosed. However, sufficient yields have not been achieved due to intermolecular and intramolecular reactions of the double bonds of norbornadiene.

[0007]

[Problems to be Solved by the Invention] According to the studies of the present inventors, in general, when the olefin is a compound with a norbornene skeleton or when methacrylic acid is used as the carboxylic acid, The yield of the target product tends to be low due to the polymerization of the ester.

Therefore, the object of the present invention is to produce esters in high yield even when a heteropolyacid is used as an acid catalyst, a monocyclic or polycyclic aliphatic hydrocarbon is used as an olefin, and acrylic acid or methacrylic acid is used as a carboxylic acid. The goal is to provide a method for manufacturing.

[0009]

[Means for Solving the Problems] The present invention provides a compound having the general formula (I) by reacting an alicyclic diolefin with acrylic acid.

0
010]

In the method for producing an alicyclic diester compound represented by [Formula 2] (wherein R represents hydrogen or a methyl group, and R' is an alicyclic diolefin residue), dehydration treatment is performed as an acid catalyst. The present invention relates to a method for producing an alicyclic diester compound, characterized by using a heteropolyacid or an acid salt thereof.

The present invention will be explained in detail below.

In the method of the present invention, the diolefin used as a reaction raw material is an alicyclic diolefin. Specifically, it has a structure represented by the following general formula (II) or (III).

[0013]

[Image Omitted] (In the formula, R1 to R8 are hydrogen atoms, hydrocarbon groups, or halogen atoms, and may be the same or different. n and m are positive integers, R5-R8
When repeated multiple times, these may be the same or different. )

[0014]

[Formula 4] (In the formula, R9 to R22 are hydrogen atoms, hydrocarbon groups, or halogen atoms, and each may be the same or different. n, m, and l are 0 or a positive integer. (If R9 to R18 are repeated multiple times, they may be the same or different.) R1 to R22 in the general formulas (II) and (III) are, for example, hydrogen atoms. , a hydrocarbon group, and a halogen atom. The hydrocarbon group is preferably an aliphatic hydrocarbon group or an alicyclic hydrocarbon group having 1 to 30 carbon atoms, and specifically, a methyl group, an ethyl group, a propyl group, an isopropyl group,
Butyl group, isobutyl group, hexyl group, stearyl group,
Examples include a cyclohexyl group and a cyclooctyl group. In addition, halogen atoms include fluorine, chlorine,
Examples include bromine. These may be different from each other, may be partially different, or may be entirely the same.

Specific examples of the alicyclic olefin represented by the general formula (II) or (III) are shown below.

[0016]

[Image Omitted] Note that the alicyclic diolefin represented by the above general formula (III) can be easily produced by subjecting cyclopentadiene and the corresponding olefin or alicyclic olefin to a Diels-Alder reaction. can do.

In the present invention, an alicyclic diester compound represented by the general formula (I) is produced by acid-adding acrylic acid or methacrylic acid to an alicyclic diolefin. Therefore, R' in the general formula (I) is a residue in which a carboxyl group of acrylic acid or methacrylic acid and its hydrogen are bonded to a pair of unsaturated carbon atoms of the alicyclic diolefin. A specific example is shown below.

[0018]

embedded image The heteropolyacid used in the present invention is generally known, and its structure is not particularly limited, but Keggin structure type or Dawson type heteropolyacids are preferred from the viewpoint of high activity. There are no particular limitations on the polyatoms constituting the heteropolyacid, but a heteropolyacid in which at least some of the polyatoms are tungstic acid is preferred from the viewpoint of high acid strength and high activity.

Specifically, H3PW12O40, H4S
iW12O40, H3PW12-pMopO40, H4
Examples include SiW12-pMopO40 (an integer of 12>p>1).

[0020] Furthermore, the heteropolyacid may be a salt,
Particularly in the synthesis of methacrylates, heteropolyacid salts are particularly preferred. Heteropolyacids include metal salts and onium salts. Metal salts are particularly preferred, and since they need to have activity as acid catalysts, they need to be acidic salts. Acidic salts, for example, have the composition formula
It can be expressed as Mx/qH3-x[PW12O40] (where M represents a metal atom, q represents a valence of the metal atom, and x is a number greater than 0 and less than or equal to 2). Particularly preferred metals for forming the salt are copper, chromium, manganese and sodium.

Specific examples of acidic salts include NaH2PW1
2O40, Na2HPW12O40, CuHPW12O
40, CuH2[PW12O40]2, CrH6[PW
12O40]3, Mn4[PW12O40]2, and the like.

The metal acid salt of phosphotungstic acid can be obtained by reacting it with a metal halide, carbonate, acetate, sulfate, etc. in an aqueous solution, followed by precipitation or evaporation to dryness.

[0023] The heteropolyacid or its acid salt used as a catalyst in the present invention has at least no physically adsorbed water. Heteropolyacids have deliquescent properties and generally have a large amount of physically adsorbed water. From monocyclic or polycyclic polycyclic unsaturated aliphatic hydrocarbons and (meth)acrylic acid (
When producing meth)acrylates, by using a heteropolyacid or its acid salt from which this physically adsorbed water has been removed, (meth)acrylates can be produced in high yield. For example, the physically adsorbed water of phosphotungstic acid can be removed by heating to 80° C. or higher at normal pressure. This temperature varies depending on the type of heteropolyacid or its acid salt, but can be easily determined by thermogravimetric analysis.

[0024] Heteropolyacids also have a large amount of water of crystallization. For example, H3PW12O40 has 29 molecules of water of crystallization per unit. Depending on the heat treatment conditions, crystallization water is also released next to physically adsorbed water. Conversion rate of olefin and (meth)acrylic acid and (meth)
Considering the selectivity to acrylate, the number of crystallization water is 1 to 20 molecules per heteropolyacid unit, and 3 to 1
It is particularly preferable that the number of molecules is 0. The relationship between the amount of crystallization water and the heat treatment conditions can be determined by thermogravimetric analysis. For example, in the case of H3PW12O40,
Approximately 150-300℃ at normal pressure, preferably 200-300℃
H3PW12O40 having a desired amount of water of crystallization can be obtained by heat treatment at °C.

[0025] The above heat treatment can also be carried out under reduced pressure; however, the heating temperature can be lower than that under normal pressure, depending on the degree of reduced pressure.

The amount of catalyst used is 1 of the alicyclic olefins.
0.1g to 10g is preferable, and 1 to 5g based on mole
is particularly preferred. If used in an amount exceeding this usage range, cationic polymerization of alicyclic olefins may be accelerated, which is not preferable.

[0027] The reaction temperature is preferably in the range of 40°C to 90°C, preferably 60 to 80°C. If the temperature is lower than 40°C, it will take a long time for the reaction to proceed sufficiently. Further, if the temperature exceeds 90°C, the polymerization of olefin and the polymerization of the produced (meth)acrylate may be accelerated, which may be undesirable.

[0028] The reaction time is usually suitably in the range of 2 to 10 hours.

In the method of the present invention, a solvent is required to dissolve the heteropolyacid or its acid salt in the production of dimethacrylate from an alicyclic diolefin and methacrylic acid. Examples include ketones, esters, and ethers. Specifically, examples of ketones include methyl ethyl ketone, diethyl ketone, and methyl isobutyl ketone, examples of esters include ethyl acetate, isopropyl acetate, and the like, and examples of ethers include dipropyl ether, dibutyl ether, and dioxane.

The amount of solvent to be used is preferably 20 to 200 parts by weight per 100 parts by weight of olefin from the viewpoint of dissolving the heteropolyacid or its acid salt and allowing the reaction to proceed.

Further, in the production of diacrylate from alicyclic diolefin and acrylic acid, no particular solvent is required, but the above-mentioned solvents may be used.

[0032] The amounts of alicyclic olefin and (meth)acrylic acid used are preferably substantially equal. For example, it is appropriate to use 2.0 to 3.0 equivalents of acrylic acid or methacrylic acid per equivalent of olefin.

Since the alicyclic olefin, (meth)acrylic acid, and the produced (meth)acrylate are thermally unstable substances, it is preferable to carry out the reaction by adding a polymerization inhibitor. Examples of polymerization inhibitors include quinones, naphthols, catechols, phenothiazines, and nitroso compounds. The amount used is preferably 50 to 500 ppm based on the total weight of the reaction substrates. 500pp
If the amount exceeds 50 ppm, it may be undesirable because the reaction solution will be colored and the catalyst activity will be significantly reduced.
Addition of less than m may not be effective.

[0034] Furthermore, an oxygen-containing gas may be blown into the reaction solution, and the amount thereof is not particularly limited. In this case, among the above polymerization inhibitors, it is preferable to use an alcohol-based inhibitor in combination.

The reaction can be carried out in a batch, semi-batch or continuous manner. However, batch type and semi-batch type are preferred. In the case of a batch method, a method of supplying the olefin to an acrylic acid solution in which a catalyst is dissolved or a mixed solution of a solvent and methacrylic acid is preferable from the viewpoint of suppressing the polymerization of alicyclic olefin, but the method is limited to this method. It's not a thing.

The reaction can be carried out under normal pressure or under pressure in an autoclave.

After the reaction is completed, the product can be recovered, for example, as follows. 5 for the reaction solution volume
It is poured into ~10 times the amount of normal hexane, and the polymer is precipitated and filtered. The collected filtrate is 5% by weight after washing with pure water.
Cleaning with alkaline aqueous solution such as sodium bicarbonate aqueous solution,
After further washing with pure water, low-boiling components are removed under reduced pressure to recover a high-purity crude product at a high yield.

Furthermore, if necessary, a product of even higher purity can be recovered by distillation under reduced pressure.

Since the obtained di(meth)acrylate has high polymerizability, it is preferable to carry out distillation in as short a time as possible, and it is preferable to carry out a method such as thin film distillation. At this time, it is preferable to add a polymerization inhibitor.

Examples of the polymerization inhibitor include tertiary butylcatechol, N-nitrosophenylamine, N-nitrosohydroxylamine salt, phenothiazine, di-β-naphthol, N,N-β-naphthyl-P-phenylenediamine, etc. These may be used alone or in combination of two or more.

[0041]

[Effects of the invention]) According to the present invention, alicyclic di(meth)acrylate can be produced with high conversion rate and high selectivity,
Its industrial value is high.

[0042]

[Examples] The present invention will be specifically explained with reference to Examples below, but the present invention is not limited thereto.

Reference Example In a 100 ml glass flask equipped with a stirrer and a thermometer, commercially available phosphotungstic acid (H3PW12
5.0 g of O40) was dissolved in 25 ml of pure water. Add 72 m of copper acetate (Cu(CH3COO)2.H2O) to this solution.
10 ml of an aqueous solution in which g was dissolved was added dropwise. After the proper procedure is completed,
Stirred at room temperature for 2 hours, then heated at 120°C and evaporated to dryness to remove water and acetic acid.

[0044] Further, after heat treatment in air at 300°C for 12 hours, it was allowed to cool to room temperature, and the composition formula CuH2 was quantitatively determined.
A heteropolyacid represented by [PW12O40]2·nH2O was obtained.

Example 1 48 g (0.66 mol) of acrylic acid, 0.06 g of hydroquinone, and H3PW12O4 as a catalyst were placed in a 200 ml four-necked flask equipped with a cooling device, a stirrer, and a thermometer.
After heating 01.5g in air for 2 hours, add 6
Dimethanooctahydronaphthalene 53.3g (0
．． 33 mol) was added dropwise over 1 hour. After the dropwise addition was completed, the reaction was further carried out at 70°C for 2 hours.

After cooling, the reaction crude liquid was poured into n-hexane, and the polymer was precipitated and filtered. The filtrate was collected and washed once with a 5% by weight sodium carbonate N aqueous solution and twice with pure water.
Normal hexane and low-boiling fractions were removed under reduced pressure to recover a crude product.

After the completion of the reaction, the reaction crude liquid and crude product were analyzed by gas chromatography to determine the yield, conversion rate, and selectivity. The results are shown in Table 1.

Example 2 57.6 g (0.66 mol) of methacrylic acid was placed in a 200 ml four-necked flask equipped with a cooling device, a stirrer, and a thermometer.
), diethyl ketone 40ml, methoxyphenol 0.
06 g, and 2.0 g of the copper acid salt of phosphotungstic acid prepared in Reference Example as a catalyst were added and stirred to form a homogeneous solution.

In an oil bath at 70° C., 53.3 g (0.3
3 mol) was added dropwise over 2 hours. After completion of dripping, 80
The reaction was continued for an additional 5 hours at °C.

After cooling, diethyl ketone and unreacted substances were removed under reduced pressure. This was poured into n-hexane, and the polymer was precipitated and filtered. The filtrate was collected and washed with a 5% by weight aqueous sodium carbonate solution and pure water, and then normal hexane and low-boiling fractions were removed under reduced pressure to collect a crude product. The results are shown in Table 1.

Example 3 The same method as in Example 1 was used, except that 31.3 g (0.33 mol) of norbornadiene was used instead of dimethanohexahydronaphthalene.

The results are shown in Table 1.

Example 4 Except that 31.3 g (0.33 mol) of norbornadiene was used instead of dimethanohexahydronaphthalene.
A method similar to Example 2 was used.

The results are shown in Table 1.

Example 5 Cyclohexadiene 26 instead of norbornadiene
．． The same method as in Example 1 was used except that 4 g (0.33 mol) was used.

The results are shown in Table 1.

Example 6 Cyclohexadiene 26 instead of norbornadiene
．． The same method as in Example 1 was used except that 4 g (0.33 mol) was used.

Comparative Example 1 As a catalyst, H3PW12O40·nH2O (n>29
) was used in the same manner as in Example 1.

The results are shown in Table 1.

Comparative Example 2 H3PW12O40·nH2O (n>29) as a catalyst
The same procedure as in Example 2 was used, except that no solvent was used.

The results are shown in Table 1.

Comparative Example 3 The same procedure as in Example 1 was carried out except that 4.0 g of concentrated sulfuric acid was used as the catalyst. The results are shown in Table 1.

Comparative Example 4 The same method as in Example 2 was carried out except that 4.0 g of concentrated sulfuric acid was used as the catalyst. The results are shown in Table 1.

[0064]

[Table 1]

Claims (1)

[Claims] Claim 1: An alicyclic diolefin and acrylic acid are reacted to form a compound of the general formula (I) [Chemical 1] (wherein, R represents hydrogen or a methyl group, and R' is an alicyclic olefin residue). A method for producing an alicyclic diester compound represented by (a), characterized in that a dehydrated heteropolyacid or an acid salt thereof is used as an acid catalyst.