JP4381166B2 - Process for producing α-substituted acrylates - Google Patents

Description

  The present invention relates to a novel process for producing α-substituted acrylates. Specifically, dialkyl 2,2 '-[oxybis (methylene)] bisacrylate such as dimethyl 2,2'-[oxybis (methylene)] bisacrylate is reacted with an active hydrogen-containing compound such as alkyl alcohol. The present invention relates to a method for efficiently producing α-substituted acrylates such as α- (alkyloxymethyl) methyl acrylate.

α-substituted acrylates are useful as optical materials, paints, resin materials, reactive diluents, surfactant raw materials, intermediates for the production of pharmaceuticals and agricultural chemicals, monomer materials for resists, and their production methods are also known. ing.
For example, methyl α- (bromomethyl) acrylate and alkyl alcohol are reacted in the presence of triethylamine as a catalyst to give the corresponding methyl α- (alkyloxymethyl) acrylate, specifically methyl α- (ethoxymethyl) acrylate, Methods for producing methyl α- (propoxymethyl) acrylate and the like are known (see Non-Patent Document 1 and Non-Patent Document 2). Also disclosed is a method for synthesizing methyl α- (2,2,2-trifluoroethoxymethyl) acrylate from methyl α- (bromomethyl) acrylate and 2,2,2-trifluoroethyl alcohol (patent) Reference 1).

  Further, ethyl α- (hydroxymethyl) acrylate and alkyl alcohol are reacted in the presence of a protonic acid (for example, sulfuric acid) as a catalyst to give the corresponding ethyl α- (alkyloxymethyl) acrylate, specifically ethyl α A method for producing-(ethoxymethyl) acrylate and the like is described (see Non-Patent Document 3 and Patent Document 2).

  Further, ethyl α- (hydroxymethyl) acrylate and alkyl alcohol are reacted in the presence of a tertiary amine to give a corresponding ethyl α- (alkyloxymethyl) acrylate, specifically ethyl α- (methoxyethoxymethyl) acrylate. Is described (see Patent Document 3).

Macromol. Chem. , 192, 2713-2722 (1991) Polymer Preprints, Japan vol. 41, No. 6, 1707-1709 (1992) J. Polym. Sci. , A. , Vol. 1, pp. 1919–1926 (1963) JP-A-6-145108 JP-A-8-325200 Specification Japanese Patent Laid-Open No. 10-226669

  However, among the conventional production methods described above, the method using α-halomethyl acrylate as a raw material takes measures for preventing corrosion of the production equipment, for example, in the case of industrial production. In addition, there is a problem that the process for producing the obtained reaction product becomes complicated. Further, since hydrogen halide is generated as a by-product in the manufacturing process, there is a problem that discarding the hydrogen halide causes environmental destruction.

  In addition, the method described in Non-Patent Document 3 has a drawback of low selectivity and yield. In the case of this method, the polyesterification product (transesterification reaction product) produced by the side reaction increases the viscosity of the reaction solution, and further induces gelation, making separation and purification of the target product difficult. There are problems with industrial implementation.

  In Patent Documents 2 and 3 in which these problems are improved, it is a method that can be applied only to a reaction with a hydroxyl group-containing compound such as an alkyl alcohol, which is not preferable for the production of a wide range of compounds. A manufacturing method was desired.

  Therefore, the present invention aims to improve the above-mentioned problems of the prior art and to provide a new and industrially advantageous method to replace the above method in the production of α-substituted acrylates.

  As a result of intensive studies to provide a novel production method of α-substituted acrylates, the present inventors have dialkyl 2,2 ′-[oxybis (methylene)] bisacrylate as a starting material and an active hydrogen group For example, when a compound is reacted in the presence of a tertiary amine as a catalyst, for example, it has been found that the desired α-substituted acrylates can be obtained in a high yield with few side reactions. It came to complete.

  According to the method of the present invention, since hydrogen halide is not generated as a by-product in the production process of α-substituted acrylates, corrosion of production equipment and environmental destruction that are problems in conventional production methods are prevented. I thought that I could do it.

  Furthermore, since active hydrogen group-containing compounds other than hydroxyl group-containing compounds can be used, various active hydrogen group-containing compounds can be directly added to the α-position of acrylic acid, and when α-substituted acrylates are polymerized. Thus, a polymer having an active hydrogen group-containing compound in the side chain portion of the polymer is obtained. For this reason, the polymer which provided the new function can be obtained by selecting an active hydrogen group containing compound. For this reason, the molecular design of the polymer becomes easy, and there is a possibility of developing a new polymer.

  That is, the present invention provides the following general formula (1)

It is characterized in that a dialkyl 2,2 ′-[oxybis (methylene)] bisacrylate represented by the formula (wherein R ₁ represents an organic residue) is reacted with an active hydrogen-containing compound.

  Further, in the present invention, the active hydrogen group-containing compound is a hydroxyl group-containing compound, a phenolic hydroxyl group-containing compound, an amino group-containing compound, a carboxyl group-containing compound, a mercapto group-containing compound, a cyano group-containing compound, The present invention relates to a method for producing an α-substituted acrylate, which is a compound having at least one functional group selected from methylene biscarbonyl group-containing compounds.

  Furthermore, the present invention is characterized in that a tertiary amine catalyst is preferably used as the reaction catalyst. Furthermore, the present invention relates to a method for producing α-substituted acrylates characterized by allowing a polymerization inhibitor and / or molecular oxygen to coexist.

  Hereinafter, embodiments of the present invention will be described in detail. The following general formula (1) used as a raw material for the production method of α-substituted acrylates according to the present invention

The dialkyl 2,2 ′-[oxybis (methylene)] bisacrylates represented by the formula is not particularly limited, but is a compound in which the substituent represented by R ₁ is composed of an organic residue. . The organic residue represented by R ₁ is specifically a linear, branched, or cyclic alkyl group or aryl group having 1 to 18 carbon atoms.

  Specific examples of the dialkyl 2,2 ′-[oxybis (methylene)] bisacrylate represented by the general formula (1) include dimethyl 2,2 ′-[oxybis (methylene)] bisacrylate, Diethyl 2,2 '-[oxybis (methylene)] bisacrylate, dibutyl 2,2'-[oxybis (methylene)] bisacrylate, di-t-butyl 2,2 '-[oxybis (methylene)] bisacrylate, dicyclohexyl 2 , 2 '-[oxybis (methylene)] bisacrylate, diisobornyl 2,2'-[oxybis (methylene)] bisacrylate, di-t-butylcyclohexyl 2,2 '-[oxybis (methylene)] bisacrylate, ditricyclodeca Nyl 2,2 '-[oxybis (methylene)] bisac Rate, diadamantyl 2,2' [oxybis (methylene)] bis acrylate dialkyl 2,2' [oxybis (methylene)] bis acrylates and the like.

  These dialkyl 2,2 ′-[oxybis (methylene)] bisacrylates may be used alone or in a suitable mixture of two or more. Among the compounds exemplified above, dimethyl 2,2 '-[oxybis (methylene)] bisacrylate, diethyl 2,2'-[oxybis (methylene)] bisacrylate, dibutyl 2,2 '-[oxybis (methylene)] bis Acrylate, di-t-butyl 2,2 '-[oxybis (methylene)] bisacrylate, dicyclohexyl 2,2'-[oxybis (methylene)] bisacrylate, diisobornyl 2,2 '-[oxybis (methylene)] bisacrylate, Diadamantyl 2,2 ′-[oxybis (methylene)] bisacrylate is preferred because of its good reactivity with active hydrogen-containing compounds, polymerizability, and the like.

  The above-mentioned dialkyl 2,2 ′-[oxybis (methylene)] bisacrylates are conventionally known methods, for example, alkyl acrylates such as the method described in US Pat. No. 4,889,948, formaldehyde, 1,4-diazabicyclo [ It can be easily obtained by reaction with 2,2,2] octane, or reaction between alkyl α- (hydroxymethyl) acrylates and 1,4-diazabicyclo [2,2,2] octane.

  The active hydrogen group-containing compound used as a raw material in the method for producing an α-substituted acrylate according to the present invention is a hydrogen atom directly bonded to a hetero atom; a hydrogen atom bonded to the same carbon as the electron withdrawing group; Examples thereof include a hydrogen atom (α-hydrogen atom) bonded to adjacent carbon.

  More specifically, as the hydrogen atom directly bonded to the heteroatom, specifically, for example, a functional group such as —NH group, —CONH group, —OH group, —COOH group, —SH group, etc. The hydrogen atom which comprises is mentioned.

  Specific examples of the hydrogen atom bonded to the same carbon as the electron withdrawing group include hydrogen atoms such as a —CHO group and an HCN group. Examples of the hydrogen atom bonded to the carbon atom adjacent to the electron withdrawing group include the α-position hydrogen atom of the carbonyl compound and the α-position hydrogen atom of the nitrile compound. Furthermore, in the case of a compound in which a vinyl group is bonded to an electron withdrawing group such as an αβ unsaturated ketone or an αβ unsaturated nitrile, a hydrogen atom at the β position can be mentioned.

Therefore, the active hydrogen-containing compound according to the present invention refers to a compound having the active hydrogen.
Among the active hydrogen-containing compounds, hydroxyl group-containing compounds, phenolic hydroxyl group-containing compounds, amino group-containing compounds, carboxyl group-containing compounds, mercapto group-containing compounds, cyano group-containing compounds, methylene biscarbonyl group Containing compounds are preferred.

  Specific examples of hydroxyl group-containing compounds include alkyl alcohols such as methanol, ethanol, n-butanol, t-butanol and 2-ethylhexanol; cycloalkyl alcohols such as cyclopentanol and cyclohexanol, benzyl Aryl alcohols such as alcohol; unsaturated alcohols such as allyl alcohol and propaginol; amino alcohols such as dimethylaminoethanol and diethylaminoethanol; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4- Polymeric group-containing alcohols such as hydroxybutyl (meth) acrylate, methyl 2- (hydroxymethyl) acrylate, ethyl 2- (hydroxymethyl) acrylate, methyl cellosolve , Ethyl cellosolve, butyl cellosolve, carbitol, polyethylene glycol monomethoxy ether, polypropylene glycol monoethoxy ether, etc., alkylene glycol monoalkyl ethers, ethylene glycol, propylene glycol, diethylene glycol, polyethylene glycol, polypropylene glycol, etc. , Glycerin, trimethylolpropane, polyhydric alcohols such as pentaerythritol, saccharides such as glucose and mannose, and halogen-substituted products of these compounds.

  Examples of phenolic hydroxyl group-containing compounds include phenol, hydroquinone, catechol, bisphenol A, bisphenol F, and naphthol.

  Examples of amino group-containing compounds include mono- and dialkylamines such as ammonia, monomethylamine, dimethylamine, monoethylamine, diethylamine; cycloalkylamines such as cyclopentylamine, cyclohexylamine, 1,4-diaminocyclohexane; Examples include diamines such as 3-diaminopropane and ethylaminoethylamine; cyclic amines such as pyrrolidine, piperidine, morpholine, piperazine, succinimide, phthalimide, and carbazole.

  Examples of the carboxyl group-containing compounds include fatty acids such as formic acid, acetic acid and propionic acid, unsaturated acids such as acrylic acid, methacrylic acid and itaconic acid, succinic acid, maleic acid, phthalic acid, pyromellitic acid and malonic acid. Examples include basic acids.

  Examples of the mercapto group-containing compounds include alkyl mercaptans such as hydrogen sulfide, methyl mercaptan, ethyl mercaptan, and butyl mercaptan.

  Examples of the cyano group-containing compounds include hydrocyanic acid, acetonitrile, and dicyanomethylene.

  Examples of the methylenebiscarbonyl group-containing compound include malonic acid diesters such as dimethyl malonate and diethyl malonate, and acetoacetoxy compounds such as acetoacetoxyethyl methacrylate and acetoacetoxyethyl methacrylate.

  In addition, the said active hydrogen group containing compound may use only one type, and may mix and use two or more types suitably. The active hydrogen group-containing compound may contain a plurality of active hydrogens. Further, when the active hydrogen-containing compound contains a plurality of active hydrogens, these active hydrogens may be the same or different from each other.

  The α-substituted acrylate obtained in the method for producing an α-substituted acrylate according to the present invention is the following general formula (2).

(Wherein R ₁ represents an organic residue, and X represents a group to which active hydrogen of the active hydrogen-containing compound was bonded).

  More specifically, when the active hydrogen-containing compound is methyl alcohol, it is an alkyl 2- (methoxymethyl) acrylate, and when the active hydrogen-containing compound is phenol, it is an alkyl 2- (phenoxymethyl) acrylate and is active. If the hydrogen-containing compound is dimethylamine, it is alkyl 2- (dimethylaminomethyl) acrylate, if the active hydrogen-containing compound is cyanic acid, it is alkyl 2- (cyanomethyl) acrylate, and the active hydrogen-containing compound is acetic acid. For example, alkyl 2- (acetoxymethyl) acrylate.

  The amount of the active hydrogen group-containing compound added to the dialkyl 2,2 '-[oxybis (methylene)] bisacrylate depends on the type of dialkyl 2,2'-[oxybis (methylene)] bisacrylate used. The ratio of the dialkyl 2,2 ′-[oxybis (methylene)] bisacrylate to 1 mol may be in the range of 0.01 mol to 100 mol. Preferably the ratio with respect to 1 mol of dialkyl 2,2 '-[oxybis (methylene)] bisacrylates is in the range of 0.1 mol to 10 mol, more preferably in the range of 0.5 mol to 5 mol.

  A tertiary amine is preferable as a catalyst used as necessary in the method for producing an α-substituted acrylate according to the present invention.

  Specific examples of the tertiary amine catalyst include trimethylamine, triethylamine, tri n-butylamine, dimethylethylamine, dimethyl n-butylamine, triethylenediamine, tetramethylethylenediamine, tetramethylpropylenediamine, tetramethylbutylenediamine, Weak basic ion exchange resins such as DB-U, Diaion WA-10 manufactured by Mitsubishi Chemical Corporation, Dowex MWA-1 manufactured by Dow Chemical Company, and Amberlite IRA-68 manufactured by Rohm and Haas Although it can mention, it does not specifically limit. Only one kind of these catalysts may be used, or two or more kinds may be appropriately mixed.

  The amount of the catalyst added to the dialkyl 2,2 ′-[oxybis (methylene)] bisacrylate depends on the type of dialkyl 2,2 ′-[oxybis (methylene)] bisacrylate used, but for example, the dimethyl 2 , 2 '-[oxybis (methylene)] bisacrylates in a range of 0.001 mol% to 50 mol%, preferably 0.01 mol% to 20 mol%. Good. When the addition amount of the catalyst is less than 0.001 mol%, the catalytic activity is not sufficiently exhibited, the reaction time becomes too long, and the α-substituted acrylates cannot be efficiently produced, which is not preferable. Further, even if the amount of the catalyst added is more than 50 mol%, further improvement of the catalytic effect such as shortening of the reaction time in proportion to the increase of the catalyst amount cannot be expected, and a part of the added catalyst is wasted, Since it becomes economically disadvantageous, it is not preferable.

  The reaction conditions for carrying out the above reaction are not particularly limited, but the dialkyl 2,2 ′-[oxybis (methylene)] bisacrylates as raw materials and the α-substituted acrylates as products are Since the molecule contains a vinyl group or the like, it has a property of being easily polymerized. Accordingly, when the dialkyl 2,2 ′-[oxybis (methylene)] bisacrylate is reacted with an active hydrogen group-containing compound, the dialkyl 2,2 ′-[oxybis (methylene)] bisacrylate or α-position is used. In order to suppress the polymerization of the substituted acrylates, it is preferable to add a polymerization inhibitor (or polymerization inhibitor) or molecular oxygen to the reaction system.

  Examples of the polymerization inhibitor include hydroquinone, hydroquinone monomethyl ether, p-benzoquinone, t-butylcatechol, topanol, and phenothiazine, but are not particularly limited. These polymerization inhibitors may be used alone or in a suitable mixture of two or more. The amount of the polymerization inhibitor added is not particularly limited. For example, the ratio to the dialkyl 2,2 ′-[oxybis (methylene)] bisacrylate is 0.001 wt% to 5 wt%. It may be within the range. As molecular oxygen, for example, air can be used. In this case, air is dissolved in the reaction system, that is, dimethyl 2,2 '-[oxybis (methylene)] bisacrylate, or It may be blown (so-called bubbling). And in order to fully suppress the said superposition | polymerization, it is preferable to use a polymerization inhibitor and molecular oxygen together.

  In addition, the reaction can be performed without a solvent, but can also be performed in a solvent. Specific examples of the solvent include ketones such as methyl ethyl ketone, acetates such as ethyl acetate and butyl acetate, ethers such as dipropyl ether, and aromatics such as benzene, toluene, xylene, and chlorobenzene. Examples include hydrocarbons, aliphatic hydrocarbons such as hexane, heptane, cyclopentane, cyclohexane, and methylcyclohexane, but are not particularly limited as long as they do not inhibit the above reaction. Moreover, it is not specifically limited.

  The reaction temperature is not particularly limited, but is preferably in the range of 0 ° C to 150 ° C, particularly preferably in the range of 20 ° C to 120 ° C, in order to suppress the above-described polymerization. When the reaction temperature is lower than 0 ° C., the reaction time becomes too long, and it is not preferable because allyl ethers cannot be produced efficiently. And when reaction temperature is higher than 150 degreeC, since it becomes impossible to suppress above-described superposition | polymerization, it is unpreferable. The reaction time is the reaction temperature, dialkyl 2,2 ′-[oxybis (methylene)] bisacrylate, active hydrogen group-containing compound, solvent and catalyst, and the amount used so that the above reaction is completed. It may be set appropriately according to the above.

  The reaction pressure is not particularly limited, and may be any of normal pressure (atmospheric pressure), reduced pressure, and increased pressure.

  The reaction product, that is, the desired α-substituted acrylate can be obtained by purifying the reaction solution after completion of the reaction. Although the said refinement | purification means is not specifically limited, Specifically, for example, after extracting using a solvent, it can refine | purify by removing an extraction medium. In this case, examples of the solvent that can be used include aliphatic hydrocarbons such as hexane, cyclohexane, and methylcyclohexane; aromatic hydrocarbons such as benzene, toluene, and xylene, and the like. There is no particular limitation as long as it dissolves, dissolves the reaction product, and does not mutually dissolve with unreacted products other than the reaction product, by-products, catalysts and the like. Further, the extraction medium removal method includes distillation, evaporation and the like, but various methods can be used and are not particularly limited. Further, as another purification means, separation and purification can be performed by a distillation method, a crystallization method, a so-called column chromatography method, or the like.

  The α-substituted acrylates obtained by the above method can be easily polymerized to obtain a polymer. Polymerization conditions and the like are not particularly limited. For example, the α-substituted acrylates may be polymerized alone, or may be copolymerized with a copolymer copolymerizable with the α-substituted acrylates. The production method for obtaining the polymer by polymerizing the α-substituted acrylates is not particularly limited. For example, a polymerization method using a polymerization initiator such as a radical polymerization initiator; ionizing radiation, electron beam, etc. Various conventionally known methods such as a polymerization method of irradiating with radiation and ultraviolet rays; a polymerization method by heating, and the like can be employed.

  Accordingly, the α-substituted acrylates obtained by the production method of the present invention are excellent in polymerizability, and are optical materials, paints, various resin materials, resin-modified materials, reactive diluents, surfactant raw materials, medicines, and the like. It can be used for intermediates for producing agricultural chemicals, monomer materials for resists, antistatic agents, water repellents, cement dispersants and the like.

EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated concretely, the scope of the present invention is not limited only to these Examples. Unless otherwise specified, “%” indicates “mass%” and “part” indicates “mass part”.

Example 1
In a 100 ml glass flask equipped with a thermometer, a gas blowing tube and a stirrer, 30 g of dimethyl 2,2 ′-[oxybis (methylene)] bisacrylate, 30 g of methanol as an active hydrogen-containing compound, and 1,4- Diazabicyclo [2,2,2] octane 1.5 g dimethyl 2,2 ′-[oxybis (methylene)] bisacrylate was added in an amount of 5% by mass) and stirred. Next, air was blown into the reaction solution, and methanol was refluxed for 7 hours while maintaining the temperature in the reaction vessel at 80 ° C. to complete the reaction. After completion of the reaction, the reaction solution was washed twice with water using a separatory funnel, the washed liquid was transferred to a glass flask, and methanol and water were distilled off. In addition, the pressure was reduced to 30 mmHg, and 3.2 g of a reaction product was obtained at a distillation temperature of 68 ° C.

  The reaction product obtained as described above was analyzed by gas chromatography. As a result, 98% of methyl α- (methoxymethyl) acrylate was contained.

  According to the present invention, a target α-substituted acrylate can be obtained in a high yield in the reaction of a dialkyl 2,2 ′-[oxybis (methylene)] bisacrylate and an active hydrogen-containing compound. In addition, since hydrogen halide is not generated in the manufacturing process, corrosion of the manufacturing apparatus and environmental destruction that are problems in the conventional manufacturing method can be prevented.

  Furthermore, in the α-substituted acrylates obtained by the production method of the present invention, the active hydrogen group-containing compound is directly added to the α-position of acrylic acid, so that the α-substituted acrylate is polymerized on the side chain portion of the polymer. A polymer having an active hydrogen group-containing compound is obtained. For this reason, the polymer which provided the new function can be obtained by selecting an active hydrogen group containing compound. For this reason, the molecular design of the polymer becomes easy, and a new polymer can be developed.

The α-substituted acrylates obtained by the production method of the present invention are excellent in polymerizability, and are optical materials, paints, various resin materials, resin-modified materials, reactive diluents, surfactant raw materials, medical and agricultural chemical production. Intermediates, resist monomer materials, antistatic agents, water repellents, cement dispersants and the like.

Claims (2)

The following general formula (1)

Production of α-substituted acrylates by reacting dialkyl 2,2 ′-[oxybis (methylene)] bisacrylates represented by the formula (wherein R ₁ represents an organic residue) and an active hydrogen group-containing compound A method,
The α-substituted acrylates are α- (alkoxymethyl) acrylates,
The active hydrogen group-containing compound includes alkyl alcohol, cycloalkyl alcohol, aryl alcohol, unsaturated alcohol, amino alcohol, polymerizable group-containing alcohol, alkylene glycol monoalkyl ether, alkylene glycol, polyhydric alcohol, sugar, and these At least one hydroxyl group-containing compound selected from the group consisting of halogen-substituted compounds;
The method for producing an α-substituted acrylate, wherein the organic residue represented by R ₁ is a linear, branched or cyclic alkyl group or aryl group having 1 to 18 carbon atoms. The process according to claim 1 alpha-position substituted acrylates, wherein the use of tertiary amine catalyst.