JPH1072404A - (meth)acrylic acid ester of sorbitol and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a new (meth)acrylic acid ester of sorbitol useful as a compound cured by active energy rays by reacting sorbitol with a (meth)acrylic acid, etc. SOLUTION: The objective (meth)acrylic acid ester of sorbitol is represented by the formula [R<1> is H or methyl; (m) is a number having average value of 0.1-6.0 with the proviso that (m)+(n) is 6]. For example, the ester is preferably obtained by reacting (A) the sorbitol with (B) a (meth)acrylic acid, (C) a (meth) acrylic ester or (D) a (meth)acrylic halide [especially a (meth)acrylic chloride] and the component A is reacted with compound B in the presence of a catalyst such as p-toluenesulfonic acid at a temperature within a range of 20-200 deg.C for about 0.5-20hr.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a novel (meth) acrylate of sorbitol and a method for producing the same.

[0002]

2. Description of the Related Art (Meth) acrylates may be used alone or in combination with other polymerizable monomers, oligomers, polymers,
When mixed with dyes, pigments, inorganic fillers, etc., it is easily polymerized by radicals generated by thermal decomposition or decomposition by irradiation with active energy rays such as ultraviolet rays and radiation, and has mechanical properties, heat resistance, weather resistance, and oxidation resistance. It produces a polymer with excellent properties.

Further, (meth) acrylic acid esters can be easily copolymerized with various compounds having a carbon-carbon double bond, so that the physical properties of the polymer can be adjusted according to the intended use. Paints, inks, coatings,
It is used in a wide range of fields as a raw material for adhesives, adhesives, resins, rubbers, optical materials, and the like.

[0004]

However, conventionally known (meth) acrylic acid esters may not have sufficient performance depending on the use.

When used as a polymerizable monomer in a curable resin composition, for example, a monofunctional (meth) acrylate compound has a low viscosity and good adhesion,
It has the disadvantage of slow curing, and polyfunctional (meth) acrylate compounds have excellent curing speed but high viscosity, and have problems with adhesion,
In terms of curing speed, viscosity, adhesion and the like, no compound having satisfactory performance in a well-balanced manner has been found.

[0006] Further, from the viewpoint of environmental preservation, water-based paints and printing inks are being promoted.
(Meth) acrylic acid ester compounds which are excellent in adhesion and the like and which can be used for such an aqueous curable resin are not known.

[0007]

The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, the (meth) acrylic acid ester of sorbitol is a novel compound, which is an active energy ray-curable compound. It is useful, and since the (meth) acrylic acid ester of sorbitol can control the ratio of (meth) acryloyl group to hydroxyl group, it is well-balanced in terms of curing speed, viscosity, adhesion and the like. As an active energy ray-curable compound having satisfactory performance, and as an active energy ray-curable compound useful as an aqueous curable resin material,
They have found that they can be synthesized and used according to the purpose, and have completed the present invention.

That is, the present invention provides (1) a (meth) acrylate of sorbitol represented by the general formula (1):

[0009]

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(Wherein, R 1 represents a hydrogen atom or a methyl group, m is a number in the range of 0.1 to 6.0 on average, and m + n = 6)

(2) a method for producing (meth) acrylic acid ester of sorbitol, which comprises reacting sorbitol with (meth) acrylic acid, (meth) acrylic acid ester or (meth) acrylic acid halide;

(3) The process according to claim 2, wherein the (meth) acrylic halide is (meth) acrylic chloride.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION The (meth) acrylic acid ester of sorbitol in the present invention may be any one represented by the following general formula (1), and its production method is not limited.

[0014]

Embedded image

In the formula, R1 represents a hydrogen atom or a methyl group.

The (meth) acrylic acid ester of sorbitol of the present invention is a mixture of compounds having different m in an arbitrary ratio, wherein m is 0.1 to 6.0 on average in this mixture. The number in the range, preferably on average in the range from 1.0 to 5.5, and n in each compound in the mixture is chosen to be m + n = 6.

The ratio of m and n is not particularly limited, but can be adjusted and synthesized and used according to the purpose of use. For example, when a compound having an excellent curing rate or a compound having a low viscosity is desired, m is 3.0 on average.
A polyfunctional (meth) acrylate of from 5.5 to 5.5 is suitable, and for use as an aqueous cured resin material, m has an average water solubility of from 1.0 to 3.0. (Meth) acrylic acid esters are preferred.

The method for producing the (meth) acrylic acid ester of sorbitol according to the present invention is characterized in that sorbitol is converted to (meth) acrylic acid, (meth) acrylic acid ester or (meth) acrylic acid.
It reacts with acrylic acid halide.

More specifically, a dehydration esterification method (A) in which sorbitol reacts with (meth) acrylic acid in the presence of a catalyst, and a transesterification method in which sorbitol reacts with (meth) acrylic acid ester in the presence of a catalyst. (B) or an esterification method (C) involving dehydrohalogenation of sorbitol with (meth) acrylic halide.

The amount of (meth) acrylic acid used in the reaction of the dehydration esterification method (A) is usually in the range of 0.5 to 30 mol per 1 mol of sorbitol used. It is selected and used according to the number of substituents of the group, and is preferably selected and used in a range of 1.0 to 15 mol depending on the use.

The catalyst used in the dehydration esterification method (A) is preferably an acid compound, specifically, aromatic sulfonic acids such as p-toluenesulfonic acid, benzenesulfonic acid and cresolsulfonic acid; methanesulfonic acid And aliphatic sulfonic acids such as trifluoromethanesulfonic acid;
Mineral acids such as sulfuric acid, chlorosulfuric acid, fluorosulfuric acid, phosphoric acid and the like can be mentioned, and the amount of use is usually 0.1 to 10 parts by weight with respect to 100 parts by weight of the raw material sorbitol.

The reaction in the dehydration esterification method (A) can be carried out in a solvent or without a solvent.
In order to suppress the generation of sorbitol dehydrated product by the catalyst and to facilitate the progress of the reaction, it is particularly preferable to carry out the reaction in the presence of water.

The amount of the solvent used is usually 10 to 500 parts by weight based on 100 parts by weight of the raw material sorbitol as an amount necessary for completely azeotropically removing water produced by the reaction from the system. Parts by weight, preferably 30 to 100 parts by weight.

Further, in order to improve the final reaction rate, the reaction can be carried out while using a solvent capable of azeotropic distillation together with water while suppressing the amount of water in the system to a certain limit. in this case,
The solvent to be used is not particularly limited as long as it is a compound which can be azeotropic with water and can be phase-separated from water, and specific examples thereof include aromatic hydrocarbons such as benzene, toluene and xylene; hexane, heptane, cyclohexane and the like. And the like.

When the reaction is carried out in the presence of water, the amount of water in the system is usually 1 to 1000 parts by weight, preferably 10 to 100 parts by weight, based on 100 parts by weight of the raw material sorbitol. .

The reaction in the dehydration esterification method (A) is as follows:
Usually, it is carried out in the range of 20 to 200 ° C, preferably 50 to 140 ° C. The reaction time is usually 0.5 to 20 hours, and can be adjusted according to the reaction temperature and the desired number of substituted (meth) acryl groups.

The (meth) acrylic acid ester used as a raw material in the transesterification method (B) is not particularly limited, but alcohol produced by the transesterification reaction is distilled off to the outside of the system, and To facilitate the progress, the alcohol moiety has 1 to 1 carbon atoms.
The (meth) acrylate ester which is the alkyl group of No. 4 is preferred.

The amount of (meth) acrylic acid used in the reaction of the transesterification method (B) is usually in the range of 0.5 to 30 mol per 1 mol of sorbitol to be used. It is selected and used according to the number, and is preferably selected and used in the range of 1.0 to 15 mol depending on the use.

As the catalyst used for the reaction in the transesterification method (B), a known compound generally known as a transesterification reaction catalyst can be used. Specifically, dibutyltin oxide, tetraethyl titanate, tetrabutoxy Organometallic compounds such as cobalt complex salts of titanium and acetylacetonate; inorganic compounds such as lithium hydroxide, lithium carbonate, calcium chloride, potassium hydrogen phosphate and potassium phosphate; metal alcoholates such as sodium methylate and potassium methylate The amount is usually 0.1 to 10 parts by weight based on 100 parts by weight of the raw material sorbitol.

In the transesterification method (B), the reaction can be carried out in a solvent or without a solvent. When the reaction is carried out in a solvent, the solvent used is not particularly limited as long as it is inert to the reaction and the sorbitol as a raw material is soluble to some extent. Specifically, aprotic polar solvents such as dimethylformamide and sulfolane are preferred.

The reaction in the transesterification method (B) is carried out usually at a temperature of from 20 to 200 ° C., preferably from 50 to 140 ° C. The reaction time is usually 0.5 to 20 hours, and can be adjusted according to the reaction temperature and the desired number of substituted (meth) acryl groups.

In the esterification method (C) accompanied by dehydrohalogenation, the (meth) acrylic halide used includes, for example, (meth) acrylic chloride, (meth) acrylic bromide, (meth) acrylic bromide, Acrylic iodide and the like can be mentioned, and usually (meth) acrylic chloride is used.

The amount of the (meth) acrylic acid halide used in the reaction of the esterification method (C) is usually in the range of 0.5 to 20 mol per 1 mol of sorbitol, and the desired number of substitution of the (meth) acrylic group is usually within the range. Depending on the use, and preferably in the range of 1.0 to 12 mol.

In the esterification method (C), it is also possible to use a base as a reaction catalyst or a scavenger for generated hydrogen halide. The base to be used is not particularly limited, but specific examples include amine compounds such as triethylamine, pyridine, N, N-dimethylaminopyridine, and N, N-dimethylamine; hydroxylation of alkali metals such as sodium hydroxide and potassium hydroxide. And the like, among which N,
N-dimethylaminopyridine is preferably used.

The amount of the base used in the reaction of the esterification method (C) differs depending on whether it is used as a reaction catalyst or as a supplement for hydrogen halide. When used as a reaction catalyst, it is preferably used in an amount of 0.01 to 10 parts by weight, more preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the raw material sorbitol.

On the other hand, when it is used as a hydrogen halide scavenger, it is preferably used in an amount of 0.5 to 5.0 mol, more preferably 1.0 mol, per 1 mol of the (meth) acrylic halide used. Preferably, it is used in the range of 1.5 to 1.5 mol.

In order to exhibit both functions of the reaction catalyst and the hydrogen halide scavenger, an amount suitable for use as the hydrogen halide scavenger, that is, the (meth)
It is preferably used in the range of 0.5 to 5.0 mol per mol of the acrylic acid halide, and among them, 1.0 to 5.0 mol is preferable.
More preferably, it is used in the range of 1.5 mol.

The reaction in the esterification method (C) is usually carried out at a temperature in the range of -20 to 200 ° C, preferably 0 to 40 ° C. The reaction time is usually 0.5 to 20 hours, and can be adjusted according to the reaction temperature and the desired number of substituted (meth) acryl groups.

After the completion of the above-mentioned reactions (A) to (C), for example, the reaction solution is diluted with an organic solvent capable of phase-separating with water, if necessary, and then water, an alkaline aqueous solution or an inorganic neutral salt aqueous solution is added. After washing with water and removing the solvent, the desired (meth) acrylate of sorbitol can be obtained.

In the production of the sorbitol (meth) acrylate according to the present invention, regardless of the production method, it is preferable to carry out operations such as reaction and solvent removal in the presence of a polymerization inhibitor.

Examples of the type of polymerization inhibitor used include phenolic compounds such as hydroquinone, methylhydroquinone and tert-butylcatechol; amine compounds such as phenothiazine and diphenylamine; copper sulfate, copper acetate;
Copper compounds such as copper chloride; oxygen or a mixture of oxygen and an inert gas; and the like, and these compounds can be used alone or in combination.

According to the above-mentioned production method and the like, the (meth) acrylic acid ester of sorbitol of the present invention has the general formula (1)
Is usually obtained as a mixture of different compounds of m and n.

The desired ranges of m and n can be attained by adjusting the use ratio of the raw materials, the reaction temperature, the reaction time and the like as described above.

The novel sorbitol (meta) of the present invention
Acrylic esters are useful as active energy ray-curable compounds and are widely used in paints, inks, various coating materials, and the like.

The active energy ray-curable resin composition containing the (meth) acrylic acid ester of sorbitol of the present invention may optionally contain other polymerizable monomers and oligomers other than the (meth) acrylic acid ester. , Polymers, polymerization initiators and various additives.

Other polymerizable monomers include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isobornyl (meth) acrylate, Mono (meth) acrylic esters such as phenoxyethyl (meth) acrylate, cyclohexyl (meth) acrylate, and dimethylaminoethyl (meth) acrylate;

Neopentyl glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate Acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, bisphenol A
Di (meth) acrylic esters such as di (meth) acrylate;

Tri (meth) acrylic esters such as pentaerythritol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate and glycerin tri (meth) acrylate; pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate ) Tetra (meth) acrylic esters such as acrylates;

Dipentaerythritol hexa (penta)
Pentavalent or higher (meth) acrylic esters such as (meth) acrylate; and (meth) acrylic esters of derivatives in which the alcohol part of the above compound is modified with an alkylene oxide such as ethylene oxide or propylene oxide.

As oligomers, polyurethane (meth) acrylate of polyether polyol, polyurethane (meth) acrylate of carbonate polyol,
Polyurethane (meth) acrylates such as polyurethane (meth) acrylate of polyester polyol;

(Meth) of bisphenol A epoxy resin
Epoxy (meth) acrylates such as acrylate, (meth) acrylate of bisphenol F epoxy resin, and bisphenol A urethane-modified resin (meth) acrylate;

Ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol,
(Meth) acrylates of polyester diols comprising a diol compound such as 1,5-hexanediol and a dibasic acid such as succinic acid, adipic acid, phthalic acid and tetrahydrophthalic acid; and the like.

These polymerizable monomers and oligomers can be used singly or as a mixture of two or more kinds in an optional ratio, if necessary.

When polymers are used, examples of the polymers include phthalic anhydride, succinic anhydride,
Derivatives such as maleic anhydride, phthalic acid, terephthalic acid and the like are included.

The active energy rays used for curing include, for example, electron beams, X-rays, ultraviolet rays, visible rays, etc. Among them, it is particularly preferred to cure using ultraviolet rays.

In general, when curing a resin using ultraviolet rays, a photopolymerization initiator is usually used. Specifically, 1-
Acetophenone-based compounds such as hydroxycyclohexylphenyl ketone and 2-hydroxy-2-methyl-1-phenylpropan-1-one;

Benzoin compounds such as benzoiethyl ether, benzoin isopropyl ether and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone;

Benzophenone compounds such as benzophenone, o-benzoylbenzoic acid methyl ester, N, N-diethylaminobenzophenone; thioxanthone compounds such as 2,4-diethylthioxanthone and isopropylthioxanthone;

Benzyl, 2-ethylanthraquinone, p
And other compounds such as dimethylaminobenzyl aldehyde.

These photoinitiating polymerization agents can be used alone or in combination of two or more. Further, the amount used varies depending on the type, polymerization conditions and the like.

Further, if necessary, a photoinitiating auxiliary such as ethyl 4-dimethylaminobenzoate or isoamyl 4-dimethylaminobenzoate may be used in combination with the above photopolymerization initiator.

Various additives contained in the active energy ray-curable resin composition vary depending on the use of the active energy ray-curable resin composition, but if necessary, organic or inorganic pigments, plasticizers, surfactants, and the like. Agents, thermal polymerization inhibitors, antioxidants, ultraviolet absorbers and the like can also be added.

The active energy ray-curable resin composition thus produced is irradiated with a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a metal halide lamp or the like as a light source to polymerize and cure to obtain a polymer.

The obtained polymer includes coating materials such as paints, coating materials, fiber treatment agents, paper processing agents, inks, adhesives, sealing agents, optical materials, dental materials, hot resists, photographic materials, electrical insulating materials, It can be used as a raw material for molding resins.

[0065]

EXAMPLES The present invention will be specifically described below with reference to examples, but the contents of the present invention are not limited only to the examples. The parts and percentages in the examples are on a weight basis.

Example 1 80.1 g (0.44 g) of sorbitol was placed in a 3 L glass four-necked flask equipped with a reflux condenser, a thermometer and a stirrer.
Mol), 1.02 g of dimethylaminopyridine (1.3 parts per 100 parts of sorbitol) and 342 mg (772 ppm) of methylhydroquinone.

Next, 30 ml / air of air was introduced into the flask.
While blowing at a rate of 13 min, 132.0 g (1.46 mol) of acryloyl chloride was added dropwise over 3 hours while maintaining the internal temperature at 20 ° C. or lower. After completion of the dropwise addition, stirring and air blowing were continued at 20 ° C. or lower for another 6 hours.

After the completion of the reaction, 300 ml
After addition of 200 ml of water, two times with 200 ml of water, 200 ml of 10
The extract was washed twice with an aqueous solution of NaOH, dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure to obtain 123.8 g of acrylate of sorbitol.

The obtained acrylate of sorbitol had a viscosity of 560 cps (25 ° C.), and was a compound in which 3.3 mol of acrylic acid was added on average to 1 mol of sorbitol. The addition number of acrylic acid is
It was determined from 1H-NMR and FDMS spectrum. <1H-NMR spectrum> (δ value) 1.2 2.8 3.5 3.8 4.0 to 4.5
4.9-5.7 5.9 6.1 6.4 <FDMS spectrum> (Detected molecular weight) 344, 398, 290

Example 2 Instead of acryloyl chloride, methacroyl chloride 15
The experiment was carried out in the same manner as in Example 1, except that 2.4 g (1.46 mol) was used. As a result, 144.6 g of methacrylic acid ester of sorbitol was obtained. The resulting methacrylate of sorbitol has a viscosity of 540 cps
(25 ° C.), and the compound was obtained by adding 3.1 mol of methacrylic acid on average to 1 mol of sorbitol. <1H-NMR spectrum> (δ value) 1.2 1.4 2.8 3.5 3.9 4.0
-4.6 4.9-5.2 5.9 6.2 6.7 <FDMS spectrum> (Detected molecular weight) 318, 250, 386

Example 3 A 3L glass four-necked flask equipped with a reflux condenser, a thermometer and a stirrer was charged with 501.0 g (2.7) of sorbitol.
5 mol), 713.0 g (9.9 mol) of acrylic acid, 75 g of water, 26.0 g of o-cresolsulfonic acid, and 0.76 g of copper sulfate.

Next, 30 ml / air of air was introduced into the flask.
The mixture was stirred at 75 ° C. for 9 hours while blowing at a rate of min. After the completion of the reaction, water and unreacted acrylic acid were distilled off under reduced pressure, 1,000 ml of ethyl acetate was further added, and the mixture was washed twice with 200 ml of saturated saline. The extract was dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure to obtain 356.9 g of an acrylate of sorbitol.

The resulting acrylate of sorbitol had a viscosity of 4280 cps (25 ° C.), and was a compound in which 1.4 mol of acrylic acid was added on average to 1 mol of sorbitol. <1H-NMR spectrum> (δ value) 1.2 2.8 3.5 3.8 4.0 to 4.5
4.9-5.7 5.9 6.1 6.4 <FDMS spectrum> (Detected molecular weight) 290, 236

Example 4 An experiment was carried out in the same manner as in Example 1, except that 47.9 g (0.53 mol) of acryloyl chloride was added dropwise over 3 hours.
As a result, the resulting acrylate mixture of sorbitol had a viscosity of 4860 cps (25 ° C.), and was a compound in which 1.2 mol of acrylic acid was added on average to 1 mol of sorbitol.

Example 5 An experiment was conducted in the same manner as in Example 1 except that 262.6 g (2.90 mol) of acryloyl chloride was added dropwise over 6 hours. As a result, the obtained acrylate mixture of sorbitol had a viscosity of 86 cps (25 ° C.), and was a compound in which 5.8 mol of acrylic acid was added on average to 1 mol of sorbitol.

[0076]

The (meth) acrylic ester of sorbitol of the present invention is useful as an active energy ray-curable compound.

Claims (3)

[Claims] 1. A (meth) acrylic acid ester of sorbitol represented by the general formula (1). Embedded image (Wherein, R 1 represents a hydrogen atom or a methyl group, m is a number in the range of 0.1 to 6.0 on average, and m + n
= 6. ) 2. The method of claim 1, wherein the sorbitol is (meth) acrylic acid,
A method for producing (meth) acrylic acid ester of sorbitol, which is reacted with (meth) acrylic acid ester or (meth) acrylic acid halide. 3. The method of claim 1, wherein the (meth) acrylic halide is (meth) acrylic halide.
3. The process according to claim 2, wherein the process is acrylic acid chloride.