JP2611614B2 - Method for producing lactone-modified acrylate or methacrylate - Google Patents

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 a lactone-modified acrylate or methacrylate ester which can be cured at room temperature by irradiation with an active energy ray such as an electron beam or ultraviolet ray, or at room temperature or by heating. The compounds obtained by the present invention can be used in various industrial fields such as paints and printing inks. In the following, acrylates and / or methacrylates are referred to as (meth) acrylates, acryloyloxy groups or methacryloyloxy groups as (meth) acryloyloxy groups, and acrylic acid and / or methacrylic acid as (meth) acrylic. Expressed as acid.

[0002]

2. Description of the Related Art In recent years, the field of application of ultraviolet or electron beam curable resins has greatly expanded. These components of the ultraviolet or electron beam curable resin are composed of monomers and oligomers as basic components, and the ultraviolet curable resin is composed of these components and a photopolymerization initiator. In general, many oligomers have a high viscosity, and it is important to select an appropriate monomer as a diluent when using the oligomer. As the field of application has expanded, the development of monomers suitable for each application has been actively conducted, and characteristic monomers have been developed.

[0003] Among these monomers, (meth) acrylate monomers are frequently used as monomers satisfying various conditions, and some of them have strong odor and toxicity. For this reason, it is important to develop a (meth) acrylate monomer having low odor and no toxicity. The following two methods are known as improvement means for achieving these objects. 1. The molecular weight of the (meth) acrylate is increased by using a high molecular weight alcohol to which an alkylene oxide (eg, ethylene oxide, propylene oxide) is added. 2. A lactone (eg, caprolactone, valerolactone) and an alcohol are used to form a high molecular weight (meth) acrylate.

[0004] The compound obtained in the above 2 has a (meth) acryloyloxy group at one of the molecular terminals and the alcohol in the (meth) acrylate through the lactone ring-opened or ring-opened polymer. Derived from site (meta)
Lactone-modified (meth) having acrylate residue
The lactone-modified (meth) acrylate is low in odor and skin irritation (PII) and can lower the Tg of a cured product obtained by blending the composition with the lactone-modified (meth) acrylate. . As a method for producing the lactone-modified (meth) acrylic acid ester, conventionally, an alcohol is reacted with lactone at a high temperature in the presence of a catalyst to synthesize a lactone-modified alcohol, and then the lactone-modified alcohol and (meth) acrylic acid are mixed. An esterification reaction using a dehydrating solvent in the presence of an acidic catalyst, and a reaction between (meth) acrylic acid and a lactone to synthesize a lactone-modified (meth) acrylic acid, followed by esterification of the alcohol with the lactone-modified (meth) acrylic acid It is manufactured by a method of reacting.

[0005]

However, in the case of producing a lactone-modified (meth) acrylic acid ester by the above-mentioned production method, the reaction must be carried out in two steps, so that the process becomes complicated and any reaction is required. High temperature,
It has the disadvantage of requiring long-term conditions. The present inventors have conducted intensive studies in order to find a method that can produce lactone-modified (meth) acrylates in a simple manner at a low temperature and in a short time.

[0006]

DISCLOSURE OF THE INVENTION The present invention provides an alkyl group,
Wherein the reacting a carbon number of 1-12 and (meth) alkyl et <br/> ester and lactone acrylate in the presence of an acidic catalyst, has one to (meth) acryloyloxy groups at the molecular terminal , lactone-modified (meth) acrylic acid, a ring-opened form or the ring-opening polymerization of lactones having alkyl <br/> residues from the (meth) alkyl alcohol portion of the acrylic acid alkyl <br/> ester on the other The present invention relates to a method for producing an ester. Hereinafter, the present invention will be described in detail.

The alkyl group used in the present invention has 1 to 1 carbon atoms.
As the alkyl (meth) acrylate ester 12, an ordinary commercial product can be used. Representative specific examples of the alkyl (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, tertiary butyl (meth) acrylate,
Cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate and lauri (meth) acrylate
And the like .

It is preferable to use a lactone having a 6-membered ring or more because the ring-opening reaction proceeds smoothly, and specifically, δ-valerolactone, β-methyl-δ-
Examples include valerolactone, ε-caprolactone, and trimethylcaprolactone, and it is particularly preferable to use ε-caprolactone. (Meth) the amount of the lactone to acrylic acid alkyl e <br/> ester is an amount that is determined depending on the molecular weight and viscosity of the object, and the type and amount of catalyst,
Affected by the type and amount, etc. of the solvent, but 0.1 to (meth) acrylic acid alkyl ester le 1 mole
Mol, more preferably from 0.2 to 20 Ah in molar
You . When the amount of the lactone used per mole of the alkyl ( meth) acrylate exceeds 100 moles, the viscosity may be so high during the production that it may be difficult to continue the reaction.
You . Incidentally, the theoretical ratio of the reaction raw materials in the present invention, when the number of repeating units derived from lactone is, for example, 1
The amount of lactone is 1 mol per 1 mol of (meth) acryloyl group in the alkyl (meth) acrylate. However, even when the equimolar raw materials are used, in an actual reaction, for example, under the conditions as described in Examples described below, the number of repeating units derived from lactone is about 3 as an average value of lactone-modified (meth) acrylic acid. This produces an ester. In this case, the raw material alkyl (meth) acrylate that does not take part in the reaction with the lactone remains in the reaction system as an unreacted substance and functions as a solvent during the reaction, and the reaction product is used as a curable composition as it is. When used, it is used as a diluent. The same applies to the function and availability of an excessive amount of the raw material (meth) acrylic acid alkyl ester when the esterification reaction is carried out with the amount of the lactone used being less than the theoretical amount.

The acidic catalyst which can be used in the present invention includes a Lewis acid such as aluminum chloride and stannic chloride, sulfuric acid, p
-Toluenesulfonic acid, benzenesulfonic acid, Bronsted acid such as sulfonic acid type ion exchange resin, phosphomolybdic acid, phosphotungstate phosphomolybtotungstic acid, silicotungstic acid, heteropolyacid such as silicomolybdate, silica, alumina, A solid acid such as zeolite may be used, but a catalyst that dissolves in the reaction solution is preferable,
Preferred are toluenesulfonic acid, benzenesulfonic acid and heteropolyacid. The amount of acid catalyst may vary depending on the average degree of polymerization of the desired product, (meth) acrylic acid A
The amount is preferably 0.1 to 50 parts by weight, more preferably 1 to 20 parts by weight, based on 100 parts by weight of the total amount of the alkyl ester and the lactone. When a sulfonic acid type ion exchange resin is used, a large amount is required as compared with sulfuric acid, p-toluenesulfonic acid and the like.

In the present invention, it is preferable to carry out the reaction without a solvent because the reaction rate is increased, but a solvent can be used if necessary. Solvents that can be used are those that do not react with the alkyl (meth) acrylate, lactone and acidic catalyst, and specific examples include aromatic hydrocarbons such as benzene, toluene and xylene.

The method for producing the lactone-modified (meth) acrylate according to the present invention is specifically described below. The acid catalyst is used in an amount of 0.1 to 50 parts by weight based on 100 parts by weight of the total amount of the alkyl (meth) acrylate and the lactone. If necessary, for example, 0.01 to 0.5 parts by weight of a polymerization inhibitor such as hydroquinone, hydroquinone monomethyl ether, dibutylhydroxytoluene (BHT), and phenothiazine are added, and the reaction temperature is 40 to 150 ° C, preferably 60 to 11%.
At 0 ° C., lactones are added at once or continuously to react. When a solvent is used, the solvent can be used preferably in a concentration of 95% by weight or less in the reaction solution. After completion of the reaction, the reaction solution containing the lactone-modified (meth) acrylic acid ester is purified by removing the acidic catalyst from the reaction solution by a treatment such as neutralization and adsorption, and, if necessary, washing with water, distillation and the like. These operations, (meth) acrylic acid alkyl <br/> ester (meth) acryloyloxy group and the (meth) alkyl alcohol acrylic acid alkyl ester
The target product of the present invention can be obtained in which a ring-opened lactone or a ring-opened polymerized lactone is inserted between an alkyl residue derived from the moiety . The structure of the obtained lactone-modified (meth) acrylic acid ester can be identified and confirmed by NMR, elemental analysis, GPC, measurement of double bond and the like.

[0012] Lactone degeneration (meth) acrylic acid ester obtained by the present invention by irradiation of active energy rays such as electron rays or ultraviolet rays, or are those curable by ambient temperature or heating, either alone or in various compositions And can be used in various industrial fields such as paints and printing inks.

[0013]

The present invention will be described more specifically with reference to the following examples. In addition, the part in each example means a weight part,
The yield indicates the percentage of the weight of the product obtained relative to the total weight of the alkyl (meth) acrylate and the lactone. Example 1 In a glass flask equipped with a stirrer, a reflux condenser, and a thermometer, 42.52 parts of ethyl acrylate, 48.47 parts of ε-caprolactone, 0.02 part of hydroquinone monomethyl ether, and p-toluenesulfonic acid monohydrate 9 parts of salt was charged and reacted at 80 ° C. for 6 hours with stirring. Reaction solution is GP
As measured by C, the conversion of ε-caprolactone was almost 100%. After cooling the reaction solution, 100 parts of toluene was added and mixed well, and then 50 parts of water was added to the mixture.
Washed twice. Thereafter, toluene was distilled off at 80 ° C. under reduced pressure. The yield of the product obtained was 85%. GPC of the obtained product is shown in FIG. 1, an NMR chart is shown in FIG. 2, and an infrared absorption spectrum is shown in FIG. The bromine number is 35.1 g Br ₂
/ 100 g. Table 1 shows the measurement results of color tone, viscosity, and acid value. The chemical formula of the obtained product is as follows.

[0014]

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Comparative Example 1 In a glass flask similar to that in Example 1, acrylic acid 55.
76 parts, 35.22 parts of ε-caprolactone, 9 parts of p-toluenesulfonic acid monohydrate, and 0.02 part of hydroquinone monomethyl ether were charged and reacted at 80 ° C for 6 hours. 100 parts of toluene was added to the reaction solution, and a 10% aqueous solution of caustic soda was added four times by mole to the acid catalyst in the reaction solution to remove the catalyst. After separating the heavy liquid, 50 parts of water was added to the light liquid, and the liquid was washed twice. 9.36 parts of ethyl alcohol and 0.99 of p-toluenesulfonic acid monohydrate were added to this light liquid.
, 0.01 part of hydroquinone monomethyl ether and 0.05 part of cuprous chloride were charged, and an esterification reaction was carried out at 92 to 120 ° C. for 8 hours. After the reaction is completed, add 10%
An aqueous solution of caustic soda was added in a molar amount of 1.2 times the amount of the acidic catalyst in the reaction solution, and a neutralization treatment was performed to remove the catalyst in the reaction solution. After separating the heavy liquid, 50 parts of water was added to the light liquid, washed with water, and toluene in the light liquid was distilled off under reduced pressure. The yield of the product obtained was 85%. GPC of the product obtained
Is shown in FIG. 4, and the NMR chart is shown in FIG. The bromine number is 33.
9gBr was ₂ / 100g.

Example 2 44.39 parts of ethyl acrylate, ε-caprolactone 5
0.60 parts, hydroquinone monomethyl ether 0.0
The reaction was carried out under the same conditions as in Example 1 using 2 parts and 5 parts of phosphotungstic acid. When the reaction solution was measured by GPC, the reaction rate of ε-caprolactone was almost 100%. After the reaction solution was cooled, 100 parts of toluene was added and mixed, and then a 10% aqueous sodium hydroxide solution was added at 1.2 times the mol of the acidic catalyst in the reaction solution, neutralized, and the catalyst in the reaction solution was removed. did. After separating the heavy liquid, 33 parts of water was added to the light liquid, washed with water, and toluene in the light liquid was distilled off at 80 ° C. under reduced pressure. The yield of the product obtained was 66.7%. The GPC of the product obtained is shown in FIG. Table 1 shows the results of measuring the color tone, viscosity, and acid value. The chemical formula of the obtained product is as follows.

[0017]

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Example 3 42.52 parts of methyl methacrylate, 48.47 parts of ε-caprolactone, hydroquinone monomethyl ether 0.1%
Using 02 parts, 9 parts of p-toluenesulfonic acid monohydrate,
The reaction was carried out under the same conditions as in Example 1. When the reaction solution was measured by GPC, the reaction rate of ε-caprolactone was almost 1
00%. When the reaction solution was purified in the same manner as in Example 1, the yield of the obtained product was 93%. The GPC of the product obtained is shown in FIG. Table 1 shows the results of measuring the color tone, viscosity, and acid value. The chemical formula of the obtained product is as follows:
As shown in Chemical formula 3.

[0019]

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[0020]

[0021]

[0022]

[0023]

[Table 1]

[0024]

According to the method for producing a lactone-modified (meth) acrylic acid ester of the present invention, the desired product can be produced in a single step at a low temperature and in a short time without requiring a complicated process.

[Brief description of the drawings]

FIG. 1 is a gel permeation chromatogram of the product obtained in Example 1.

FIG. 2 is an NMR analysis chart of a product obtained in Example 1.

FIG. 3 is an infrared absorption spectrum of the product obtained in Example 1.

FIG. 4 is a gel permeation chromatogram of the product obtained in Comparative Example 1.

FIG. 5 is an NMR analysis chart of the product obtained in Comparative Example 1.

FIG. 6 is a gel permeation chromatogram of the product obtained in Example 2.

FIG. 7 is a gel permeation chromatogram of the product obtained in Example 3.

 ────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-57-185236 (JP, A) JP-A-59-190951 (JP, A) JP-A-61-112046 (JP, A)

Claims (1)

(57) [Claims] 1. A Accession <br/> acrylic acid alkyl ester having a carbon number of 1 to 12 alkyl groups and / or methacrylic acid alkyl
And wherein the reacting esters and lactones in the presence an acid catalyst, having acryloyloxy group or a methacryloyloxy group at one molecular end, the accession <br/> acrylic acid alkyl ester or alkyl methacrylate in the other A method for producing a lactone-modified acrylate or methacrylate which is a ring-opened or ring-opened polymer of a lactone having an alkyl residue derived from an alkyl alcohol moiety of an ester.