JP2636636B2 - Method for producing (meth) acrylate - 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 (meth) acrylate. More specifically, the present invention relates to a method for producing a tertiary amine catalyst and / or pyridine and an analog thereof in an aqueous solution of an alkali metal hydroxide by mixing (meth) acrylic acid halide and an organic compound having an acidic hydroxyl group. The present invention relates to a method for producing a (meth) acrylate ester which is reacted in the presence.

[0002] The (meth) acrylate provided by the present invention is polymerized by itself or by copolymerization with other polymerizable vinyl monomers such as methyl methacrylate to provide heat resistance, water resistance and optical resistance. It is a polymer with improved physical properties, flame retardancy, water repellency, lubricity, etc., and is expected to have a wide range of application fields.

[0003]

2. Description of the Related Art A method of synthesizing a (meth) acrylic ester by reacting a (meth) acrylic halide with an organic compound having an acidic hydroxyl group is conventionally known.

For example, as a method for synthesizing phenyl or substituted phenyl esters, a method using only sodium hydroxide as a reaction aid in the reaction of phenol or substituted phenol with (meth) acrylic acid halide (G. Sumrell) et al., J. Am. Chem. Soc., Vol. 81, page 4310 (19
59)), methods using organic bases such as triethylamine and pyridine (BIBudzan et al., Zhur. Obshchei.Khim.),
Vol. 26, Page 1127 (1956), French Patent No. 1,547,223 (1968), Japanese Patent Publication No. 50-23
No. 019), a method using a molecular sieve (A
ARBanks et al., J. Org. Chem., Vol. 42, page 3965 (197).
7)), heating method (PLMogani (PLMog)
anini) et al., Gazz. Chim. Ital.
6, page 1035 (1966), U.S. Pat.
No. 29,685) and a method using an alkali metal hydroxide in the presence of a phase transfer catalyst such as a quaternary ammonium salt (Japanese Patent Publication No. 1-50689).

As a method for synthesizing naphthyl or a substituted naphthyl ester, a method using only sodium hydroxide as a reaction aid in the reaction of naphthol or substituted naphthol with (meth) acrylic acid halide (Espattai (S. Patai) et al., J. Am Chem Sos (JA)
m. Chem. Soc.), Vol. 74, page 845 (195)
2)), a method using an organic base such as triethylamine or pyridine (H. Kaemmerer et al.,
Macromol. Chem., 164, page 25 (1973), Y. Kodama et al., J. Polym. Sci., 13, page 7
07 (1975)), a method by heating (N.Kh. Maksudov et al., Uzb.Khim.
Zh.) Vol. 19, page 34 (1975)), a method using an alkali metal hydroxide in the presence of a phase transfer catalyst such as a quaternary ammonium salt (Japanese Patent Publication No. 1-50689) and the like are known. .

As a method for synthesizing a quinolyl or substituted quinolyl ester, a reaction between a quinolinol or a substituted quinolinol and a (meth) acrylic halide is carried out.
A method using an organic base such as triethylamine as a reaction aid (see Pitman Jr. (CUP
ittman.Jr.) et al., J.Coat.Te
chnol.), Vol. 50, page 49 (1978)), vol.
Method using an alkali metal hydroxide in the presence of a phase transfer catalyst such as a quaternary ammonium salt (Japanese Patent Publication No. 1-50689)
Etc. are known.

As a method for synthesizing a diacrylate or dimethacrylate of a bisphenol compound or a dihydroxybiphenyl compound, in the reaction of a bisphenol compound or a dihydroxybiphenyl compound with a (meth) acrylic halide, only an aqueous alkali solution is used as a reaction aid. (US Pat. No. 759,504, JP-A-55-33424) and a method using an organic base such as pyridine and tributylamine (JP-A-48-18264).
No. 4,068,082), a method of using an alkali metal hydroxide in a system substantially free of water in the presence of a quaternary ammonium halide or the like (Japanese Patent Laid-Open No. 55-0855).
No. 33429) and a method in which hydrogen chloride is used as a reaction aid in the reaction of a bisphenol compound with methacrylic acid (JP-A-48-48453), alkali metal hydroxide in the presence of a phase transfer catalyst such as a quaternary ammonium salt. A method using a product (Japanese Patent Publication No. 1-50689) and the like are known.

Further, as a method of synthesizing a fluorinated alkyl ester, a method of dehydrating a fluorinated alcohol with (meth) acrylic acid in the presence of concentrated sulfuric acid or fuming sulfuric acid (US Pat. No. 2,628,958) 1953), JP-A-57-118535 and JP-A-59-181239.
No., etc.), a method in which hexafluoroacetic anhydride and acrylic acid or methacrylic acid are passed through acrylic acid or methacrylic acid and trifluoroacetic acid anhydride (asymmetric acid anhydride), and then reacted with a fluorinated alcohol (US Patent No. 3,719,698 (1973)), a method of reacting acrylic acid or methacrylic acid chloride with a fluorinated alcohol in the presence of barium chloride or in the presence of quinoline-nitrobenzene (DW Codding et al., J. Pol
Sci.), vol. 15, page 515 (1955), U.S. Pat. No. 2,642,416 (1952)), and a method of reacting in the presence of an organic base such as triethylamine (Japanese Patent Laid-Open No. 59-117503). No., JP-A-59-1175
No. 04), a method using an alkali metal hydroxide in the presence of a phase transfer catalyst such as a quaternary ammonium salt (Japanese Patent Publication No.
No. 50689) is known.

However, in the above-mentioned method for synthesizing a (meth) acrylic ester, the method described in the above-mentioned literature using only sodium hydroxide generally has a low yield.
Unreacted starting materials remain, and after completion of the reaction, complicated separation and purification steps are required, which is economically disadvantageous.

Further, the method described in the above-mentioned literature using an organic base such as trialkylamine, pyridine or quinoline requires a complicated step of recovering an expensive organic base, which is economically disadvantageous.

Further, in the method described in the above-mentioned document using a molecular sieve or the method described in the above-mentioned document by heating, the generated hydrogen halide is not completely adsorbed or removed, and the corrosion of the apparatus and the treatment of the hydrogen halide are not performed. There is a disadvantage that a problem occurs.

Further, in the method described in JP-A-55-33429, water produced as a by-product during the production of bisphenolate of an alkali metal by the reaction of a bisphenol type compound and an alkali metal hydroxide is removed by azeotropic distillation. And
Furthermore, a dehydrating agent such as anhydrous sodium sulfate or anhydrous magnesium sulfate is added to carry out the reaction in a system in which substantially no free water is present. However, such a method is not only complicated in the reaction operation but also economically. Is also disadvantageous.

In the method for synthesizing a fluorinated alkyl ester, the method described in the above-mentioned literature by a dehydration reaction with (meth) acrylic acid in the presence of concentrated sulfuric acid or fuming sulfuric acid is
When a catalytic amount of sulfuric acid is used, the yield is low. To increase the yield, an excessive amount of concentrated sulfuric acid or fuming sulfuric acid and an excessive amount of (meth) acrylic acid must be used. Complicated operations such as neutralization of acid and recovery of excess (meth) acrylic acid are required.

Further, the method described in the above-mentioned literature via an acid anhydride of (meth) acrylic acid and trifluoroacetic acid not only involves a two-step synthesis method but also requires the use of an expensive and special reagent called hexafluoroacetic anhydride. It is economically disadvantageous to use.

Further, in the method described in Japanese Patent Publication No. 1-50689, since the amount of water used is large, not only does the load on wastewater increase, but also the yield of esters is insufficient. There is a disadvantage that there is. Furthermore, tetra- used as a phase transfer catalyst in the above invention
Since n-butylammonium bromide (TBAB) is highly toxic, it cannot be flown into wastewater and must be recovered. However, there is a problem that an efficient recovery method is not known.

[0016]

SUMMARY OF THE INVENTION Therefore, the present invention
Is an industrially inexpensive acrylic metal hydroxide,
Simultaneous with obtaining (meth) acrylic ester in high yield
ToThe use of highly safe catalysts with low toxicity
The medium recovery step can be omitted, further reducing the amount of water used
This can reduce the load on wastewater
To provide a method for producing a (meth) acrylate ester
It is intended for.

[0017]

The above objects are attained by reacting a (meth) acrylic acid halide represented by the following general formula (i) with an organic compound having an acidic hydroxyl group in an aqueous solution of an alkali metal hydroxide. To produce a (meth) acrylic acid ester, the organic compound having an acidic hydroxyl group
Is any of the following general formulas I, II, III, IV, V or VI
And a tertiary amine catalyst and / or a pyridine catalyst or picoline or pyrida.
Gin, pyrimidine, pyrazine, 1,3,5-triazi
Quinoline, isoquinoline, cinnoline, quinazoli
, Quinoxaline, phthalazine, 1,8-naphthyridi
, Pteridine, phenazine, phenanthridine, 1,
10-phenanthroline, 2,2'-bipyridyl, 3,
Group consisting of 3'-bipyridyl and 4,4'-bipyridyl
A pyridine analog catalyst selected from the group consisting of an organic compound having an acidic hydroxyl group and a hydroxyl group is used in an amount of 0.
This is achieved by a method for producing a (meth) acrylic ester, wherein the reaction is carried out using a usage amount of 01 to 10%.

[0018]

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[0019]

[0020]

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[0021]

[0022]

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[0023]

[0024]

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[0025]

[0026]

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[0027]

[0028]

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[0029]

[0030]

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[0031]

The present inventors have conducted intensive studies in order to solve the above-mentioned problems, and as a result, the (meta) represented by the following general formula (i )
In manufacturing by reacting (meth) acrylic acid ester and an organic compound in an aqueous solution of an alkali metal hydroxide having a hydroxyl group of an acrylic acid halide and acid, in general
Represented by any formula of formula I, II, III, IV, V or VI
Used as an organic compound having an acidic hydroxyl group.
And further reacting the above reaction with a tertiary amine catalyst and / or
Is a pyridine catalyst or picoline, pyridazine, pirimi
Gin, pyrazine, 1,3,5-triazine, quinoline,
Isoquinoline, cinnoline, quinazoline, quinoxali
Phthalazine, 1,8-naphthyridine, pteridine,
Phenazine, phenanthridine, 1,10-phenanthate
Lorin, 2,2'-bipyridyl, 3,3'-bipyridyl
And pyri selected from the group consisting of 4,4'-bipyridyl
Gin analog catalyst can be used to convert the organic compound having an acidic hydroxyl group
Use 0.01 to 10% based on gram atom equivalent of hydroxyl group.
By carried out using a dose, high yield (meth) simultaneously obtain the acrylic acid ester, by suppressing the amount of water used
Reduces the burden on wastewater, further reduces toxicity and increases safety
By using a high catalyst, the catalyst recovery process can be omitted.
Onsets saw that that has led to the completion of the present invention.

[0032]

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As the organic compound having an acidic hydroxyl group used in the present invention, a compound represented by the following general formula I is preferable.

[0034]

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Specific examples of these include phenol, o
-Cresol, m-cresol, p-cresol, o-
Propylphenols such as ethylphenol, m-ethylphenol, p-ethylphenol and pn-propylphenol; butylphenols such as pn-butylphenol; pentylphenols such as pn-pentylphenol; pn -Hexylphenols such as hexylphenol; nonylphenols such as pn-nonylphenol; 2,4-dimethylphenol, 2,6-
Dialkylphenols such as dimethylphenol, 2,4-di-tert-butylphenol and 2,6-di-tert-butylphenol; 2,6-di-tert-butyl-p-cresol, 4,6-di-tert- Trialkylphenols such as butyl-m-cresol; monofluorophenols such as 2-fluorophenol and 4-fluorophenol; difluorophenols such as 2,4-difluorophenol and 3,5-difluorophenol;
Trifluorophenols such as 6-trifluorophenol and 2,3,5-trifluorophenol;
Tetrafluorophenols such as 5,6-tetrafluorophenol; monochlorophenols such as pentafluorophenol, 2-chlorophenol and 4-chlorophenol; dichlorophenol such as 2,4-dichlorophenol and 3,5-dichlorophenol Kind; 2, 4, 6
Trichlorophenols such as trichlorophenol and 2,3,5-trichlorophenol; 2,3,5,6-
Tetrachlorophenols such as tetrachlorophenol; pentachlorophenol, 2-bromophenol,
Monobromophenols such as 4-bromophenol;
Dibromophenols such as 2,4-dibromophenol and 3,5-dibromophenol; tribromophenols such as 2,4,6-tribromophenol and 2,3,5-tribromophenol; 2,3,5 Tetrabromophenols such as 2,6-tetrabromophenol; pentabromophenol, 2-iodophenol, 4-iodophenol, 2,4-diiodophenol, 3,5-diiodophenol, 2,4,6-triphenol Iodophenols such as iodophenol; 2-fluoro-4-chlorophenol, 2-fluoro-4-bromophenol, 2-chloro-4-fluorophenol, 2-chloro-4-bromophenol, 2-bromo-4- Fluorophenol,
2-bromo-4-chlorophenol, 2-iodo-4-
Mixed halogen-substituted phenols such as chlorophenol, 2,6-difluoro-3,5-dichlorophenol, 2,6-dichloro-3,5-dibromophenol; 3-methyl-4-chlorophenol, 3-methyl-4 Alkyl-halogen mixed substituted phenols such as -bromophenol; arylphenols such as 4-phenylphenol and 4- (4-methoxyphenyl) phenol; carboxyl-substituted phenols such as 2-hydroxybenzoic acid and 4-hydroxybenzoic acid; Ester-substituted phenols such as methyl 2-hydroxybenzoate and methyl 4-hydroxybenzoate; 4-hydroxyphenyl methyl ketone,
Alkylcarbonyl-substituted phenols such as -hydroxyphenylethylketone; alkenylcarbonyl-substituted phenols such as 4-hydroxyphenylvinylketone;
Arylcarbonyl-substituted phenols such as -hydroxyphenylphenyl ketone; fluoroalkylphenols such as 4-trifluoromethylphenol; alkoxyphenols such as 4-methoxyphenol and 3-methoxyphenol; 4-phenoxyphenol, 3-phenoxyphenol and the like Aryloxyphenols; trialkylsilylphenols such as 4-trimethylsilylphenol; cyanophenols such as 4-cyanophenol and 3-cyanophenol; 4-nitrophenol;
Nitrophenols such as -nitrophenol; dialkylaminophenols such as 4-dimethylaminophenol and 2-dimethylaminophenol; sulfonic acid-substituted phenols such as 4-hydroxybenzenesulfonic acid and 3-hydroxybenzenesulfonic acid; hydroquinone; Examples include polyhydroxy-substituted benzenes such as catechol, resorcinol, and 1,2,4-benzenetriol.

As the organic compound having an acidic hydroxyl group used in the present invention, a compound represented by the following general formula II is also suitable.

[0037]

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Specific examples thereof include 1-naphthol, 2-naphthol, 2-methyl-1-naphthol,
Alkyl naphthols such as -isopropyl-2-naphthol; 3-fluoro-2-naphthol, 4-fluoro-
Fluoronaphthols such as 1-naphthol; chloronaphthols such as 4-chloro-1-naphthol and 2,4-dichloro-1-naphthol; 1-bromo-2-naphthol, 6-bromo-2-naphthol; 6-dibromo-
Bromonaphthols such as 2-naphthol and 2,4-dibromo-1-naphthol; iodonaphthols such as 1-iodo-2-naphthol; 2-chloro-4-fluoro-1
Mixed halogenated naphthols such as naphthol; aryl naphthols such as 4-phenyl-1-naphthol;
Carboxyl-substituted naphthols such as -hydroxynaphthalene-1-carboxylic acid; 4-hydroxynaphthalene-1
-Ester-substituted naphthols such as carboxylic acid methyl ester; alkylcarbonyl-substituted naphthols such as 4-hydroxy-1-naphthyl methyl ketone; alkenylcarbonyl-substituted naphthols such as 4-hydroxy-1-naphthyl vinyl ketone; 4-hydroxy- Arylcarbonyl-substituted naphthols such as 1-naphthyl phenyl ketone;
Fluoroalkylnaphthols such as 4-trifluoromethyl-1-naphthol; alkoxynaphthols such as 4-methoxy-1-naphthol, 4-ethoxy-1-naphthol and 4-benzyloxy-1-naphthol; 4-
Aryloxynaphthols such as phenoxy-1-naphthol; trialkylsilylnaphthols such as 4-trimethylsilyl-1-naphthol; cyanonaphthols such as 4-cyano-1-naphthol; 1-nitro-2-naphthol; Nitronaphthols such as 4-dinitro-1-naphthol; dialkylaminonaphthols such as 4-dimethylamino-1-naphthol; sulfonic acid-substituted naphthols such as 4-hydroxynaphthalene-1-sulfonic acid; 1,4-dihydroxy Examples thereof include polyhydroxynaphthalenes such as naphthalene and 1,5-dihydroxynaphthalene.

As the organic compound having an acidic hydroxyl group used in the present invention, a compound represented by the following general formula III is also suitable.

[0040]

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Specific examples thereof include quinolinols such as 2-quinolinol, 4-quinolinol and 8-quinolinol; alkylquinolinols such as 2-methyl-8-hydroxyquinoline; 5-fluoro-8-hydroxyquinoline; Halogenated quinolinols such as -chloro-8-hydroxyquinoline and 5-bromo-8-hydroxyquinoline; arylquinolinols such as 5-pheninyl-8-hydroxyquinoline; 8-hydroxyquinoline-5
Carboxyl-substituted quinolinols such as carboxylic acids; 8
Ester-substituted quinolinols such as -hydroxyquinoline-5-carboxylic acid methyl ester; 8-hydroxy-5
Alkyl- or alkenyl- or arylcarbonyl-substituted quinolinols such as -quinolylmethylketone, 8-hydroxy-5-quinolylvinylketone, and 8-hydroxy-5-quinolylphenylketone; 5-trifluoromethyl-8-hydroxyquinoline and the like Fluoromethoxyquinolinols; 5-methoxy-8-hydroxyquinoline,
Alkoxy or aryloxyquinolinols such as 5-phenoxy-8-hydroxyquinoline; trialkylsilylquinolinols such as 5-trimethylsilyl-8-hydroxyquinoline; cyanoquinolinols such as 5-cyano-8-hydroxyquinoline; 5-nitro Nitroquinolinols such as -8-hydroxyquinoline; dialkylaminoquinolinols such as 5-dimethylamino-8-hydroxyquinoline; and sulfonic acid-substituted quinolinols such as 8-hydroxyquinoline-5-sulfonic acid.

As the organic compound having an acidic hydroxyl group used in the present invention, a compound represented by the following general formula IV is also suitable.

[0043]

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Specific examples thereof include 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxydiphenyl ketone, 2,2'-dihydroxydiphenyl ketone, 4,4'-dihydroxydiphenylmethane,
1,1-bis (4-hydroxyphenyl) ethane, 2,
2-bis (4-hydroxyphenyl) propane, 1,
1,1,3,3,3-hexafluoro-2,2-bis (4-hydroxyphenyl) propane, 4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxydiphenyl sulfone, 4,4'-dihydroxy −3,
3 ', 5,5'-tetrabromodiphenylmethane, 2,
2-bis (4-hydroxy-3,5-dichlorophenyl) propane, 2,2-bis (4-hydroxy-3,5
-Dibromophenyl) propane, 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, 4,
4'-dihydroxy-3,3 ', 5,5'-tetrabromodiphenylsulfone, 4,4'-dihydroxy-3,
3 ', 5,5'-tetrabromodiphenyl ketone, 4,
4'-dihydroxy-3,3 ', 5,5'-tetrachlorodiphenylmethane, 2,2-bis (4-hydroxy-
3,5-diiodophenyl) propane, N- (4-hydroxyphenyl) -4-hydroxybenzoylamide and the like can be mentioned.

As the organic compound having an acidic hydroxyl group used in the present invention, a compound represented by the following general formula V is also suitable.

[0046]

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Specific examples of these are 4,4'-dihydroxydiphenyl, 2,2'-dihydroxydiphenyl, 4,4'-dihydroxy-3,3 ', 5,5'-tetrachlorodiphenyl, 4,4 '-Dihydroxy-3,
3 ', 5,5'-tetrabromodiphenyl, 4,4'-
Dihydroxy-3,3 ', 5,5'-tetraiododiphenyl and the like can be mentioned.

Further, as the organic compound having an acidic hydroxyl group used in the present invention, a compound represented by the following general formula VI is also suitable.

[0049]

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Specific examples thereof include 2-fluoroethanol, 2,2-difluoroethanol, 2,2,2
Trifluoroethanol, 2,2,3,3-tetrafluoropropanol, 2,2,3,3,3-pentafluoropropanol, 1H, 1H, 4H-hexafluorobutanol, 1H, 1H-heptafluorobutanol,
β, β, β-trifluoroisopropanol, 1H, 1
H, 5H-octafluoropentanol, 1H, 1H-
Nonafluoropentanol, 1H-heptafluoro-1
-Methylbutanol, 1-ethyl-1H-heptafluorobutanol, 1,1-bis (trifluoromethyl)-
2,2,2-trifluoroethanol, 1H, 1H-undecafluorohexanol, 1H, 1H-tridecafluoroheptanol, 1H, 1H, 7H-dodecafluoroheptanol, 1H, 1H-pentadecafluorooctanol, 1H , 1H, 2H, 2H-heptadecafluorodecanol and the like. Further, these organic compounds having an acidic hydroxyl group represented by the general formulas I to VI can be used alone or in a mixture of two or more.

Examples of the (meth) acrylic halide represented by the following general formula used in the present invention include acrylic chloride, acrylic bromide, methacrylic chloride, and methacrylic bromide.

[0052]

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Further, the (meth) acrylic halide is reacted with an organic compound having an acidic hydroxyl group, preferably a compound represented by the above general formulas I to VI to esterify it.
The reaction conditions for producing the corresponding (meth) acrylic acid ester include, for example, the amount of the (meth) acrylic acid halide used, the amount of the hydroxyl group of the organic compound having an acidic hydroxyl group used in the present invention. The gram atomic equivalent ratio is 0.6 to 4.0, preferably 1.0 to 2.0, in terms of gram atomic equivalent. 0.1 in gram atomic equivalent ratio.
If the amount is less than 6, the conversion is remarkably reduced, and if the gram atomic equivalent ratio is more than 4.0, not only is it economically disadvantageous, but also the treatment after the reaction becomes complicated.

The alkali metal hydroxide used in the present invention includes, for example, sodium hydroxide, potassium hydroxide, lithium hydroxide and the like. The amount of the alkali metal hydroxide to be used is 0.6 to 4.0, preferably 1 in terms of a gram atomic equivalent ratio to the gram atomic equivalent of the hydroxyl group of the organic compound having an acidic hydroxyl group used in the present invention. 0.0 to 2.5. At gram atomic equivalent ratios less than 0.6, the yield of product is significantly reduced, and at gram atomic equivalent ratios greater than 4.0, it is only economically disadvantageous. Further, the concentration of the aqueous solution of the alkali metal hydroxide used in the present invention is not particularly limited, but it is preferable in terms of operation that the alkali metal hydroxide is substantially dissolved in water.

The tertiary amine catalyst used in the present invention includes, for example, tri-n-butylamine, triisobutylamine, trisec-butylamine, tri-n-propylamine, triisopropylamine, triethylamine, trimethylamine, tripentylamine , Triethanolamine, triisopropanolamine, N-
Methylmorpholine, quinuclidine, hexamethylenetetramine, 1,5-diazabicyclo [5.4.0] unde-5-ene, and the like.

The pyridine and analogs thereof used in the present invention include, for example, pyridine, picoline, pyridazine, pyrimidine, pyrazine, 1,3,5
-Triazine, quinoline, isoquinoline, cinnoline,
Quinazoline, quinoxaline, phthalazine, 1,8-naphthyridine, pteridine, phenazine, phenanthridine, 1,10-phenanthroline, 2,2′-bipyridyl, 3,3′-bipyridyl, 4,4′-bipyridyl and the like. .

Of these, triethylamine, tripropylamine, tributylamine and pyridine are preferred.

The amount of the tertiary amine catalyst and / or pyridine and its analog catalyst is 0.01 to gram atom equivalent of the hydroxyl group of the organic compound having an acidic hydroxyl group used in the present invention. -10%, preferably 0.1%.
It can be selected from the range of 1 to 5.0%. The effect is small when the amount is less than 0.01%, and when the amount is more than 10%, it is economically disadvantageous with respect to the gram atomic equivalent of the hydroxyl group of the organic compound having an acidic hydroxyl group used in the present invention. It is just.

In the present invention, the solvent used in the reaction between the (meth) acrylic halide and the organic compound having an acidic hydroxyl group includes, for example, aromatic solvents such as toluene, xylene, benzene, ethylbenzene, chlorobenzene and dichlorobenzene. Hydrocarbons; aliphatic hydrocarbons such as pentane, hexane, heptane and octane; and halogen compounds such as carbon tetrachloride, chloroform and dichloromethane. The organic solvents can be used alone or in a mixture of two or more.

In the present invention, the reaction temperature is from 0 to
The temperature is 60 ° C, preferably 0 to 40 ° C. If the temperature is lower than 0 ° C., the reaction rate is low. If the temperature is higher than 60 ° C., side reactions such as hydrolysis and polymerization tend to occur, which is not preferable. In the present invention, the presence of a polymerization inhibitor in the reaction system is not necessarily essential, but cuprous chloride, phenothiazine, hydroquinone, methoxynone, etc., which are generally known as polymerization inhibitors, are added to the reaction system. It is also possible to use it.

The (meth) acrylic acid ester obtained in the present invention can be separated and purified by a method such as distillation or crystallization.

[0062]

EXAMPLES Hereinafter, the present invention will be described in more detail and specifically with reference to examples, but the present invention is not limited to these examples.

Example 1 500 m equipped with a stirrer, thermometer and dropping funnel
16.6 g (0.05 mol) of 2,4,6-tribromophenol (2,4,6-TBP) in a four-neck flask
A solution of 3.1 g (0.08 mol) in 20 ml of water, 80 ml of dichloromethane, and triethylamine (TEA)
0.15 g (1.5 mmol, 3 mol%) was charged and, while stirring at 0 to 6 ° C., 7.6 g (0.07 mol) of methacrylic chloride.
Was added dropwise over 1 hour. After completion of the dropwise addition, 0 to 0 hour
The mixture was stirred at 6 ° C., and the conversion was measured by HPLC. As a result, no peak other than tribromophenyl methacrylic acid (TBPM) was present. Thus, the conversion of TBPM was 100%.

After the HPLC analysis, the layers were separated, the organic layer was concentrated under reduced pressure, and dichloromethane was distilled off. After distillation, 60 ml of methanol and 40 ml of water were added, and the mixture was cooled to 0 ° C., filtered and dried to obtain 19.5 g (0.049 mol) of TBPM.

The TBPM thus obtained is converted to an HPL
As a result of analysis by C (internal standard method), the purity was 97.1%. Therefore, the crude yield based on the charged 2,4,6-TBP was 97.7%, and the net yield was 94.8%.

The HPLC analysis conditions for measuring the conversion were as follows.

Model used Pump Shimazu LC-9A Detector Shimazu SPD-6A Chromatopack Shimazu C-R5A Column oven Shimazu CTO-6A Analytical conditions Column μ-Bondasphere 5μ phenyl. 9 mm × 150 mm mobile phase methanol: water = 6: 4 flow rate 1 ml / min UV 230 nm column temperature 40 ° C. Further, after the reaction is completed, vigorously stirring two layers after the reaction is completed, sampling about 0.5 ml, and TBP And TB
The HPLC area of PM was measured and calculated based on the following equation.

[0068]

(Equation 1)

Examples 2 to 5 and Comparative Examples 1 to 3 Instead of triethylamine (TEA) (1.5 mmol, 3 mol%), TEA (1 mol%) (Example 2), tributylamine (TBA) (10 mol%) ( Example 3), TBA (3 mol%) Example 4), tripropylamine (TPA) (3 mol%) (Example 5), tetra-n-butylammonium bromide (TBAB) (6 mol%) (Comparative Example 1) , TBAB (3 mol%)
(Comparative Example 2) An experiment was performed in the same manner as in Example 1, except that TBAB (1 mol%) (Comparative Example 3) was used.

Table 1 shows the conversion and crude yield of the obtained TBPM.

[0071]

[Table 1]

As shown in Table 1, the tertiary amine catalyst
Is equivalent to T which is conventionally used as a phase transfer catalyst.
Has a catalytic effect comparable to or better than BAB,
High yields, and toxicity, which has been a problem in the past.
Problem can also be avoided. For this reason, the tertiary class according to the present invention is
High catalytic effect and yield by using Min catalyst
No need for processes such as catalyst quantification and recovery while maintaining
Because wastewater is available and uses less water,
Load is reduced.

Comparative Examples 3 to 6 500 m equipped with a stirrer, thermometer and dropping funnel
33.1 g (0.1 mol) of 2,4,6-tribromophenol (2,4,6-TBP) in a four-neck flask
A solution of 6.1 g (0.15 mol) in 40 ml of water, 160 ml of dichloromethane and 2.0 g (6 mmol, 6 mol%) of tetrabutylammonium bromide (TBAB) (Comparative Example 3) were charged, and the mixture was stirred at 0 to 6 ° C. Then, 15.2 g (0.14 mol) of methacrylic acid chloride was added dropwise over 1 hour. After completion of the dropwise addition, the mixture was further stirred at 0 to 6 ° C. for 1 hour, and the conversion was measured by HPLC. As a result, the conversion rate of TBPM is
It was 99.7% with respect to 2,4,6-TBP. H
After PLC analysis, liquid separation was performed, and dichloromethane was distilled off from the organic layer under reduced pressure. After distillation, 120 ml of methanol and 80 ml of water were added, and the mixture was cooled to 0 ° C., filtered, dried and tribromophenylmethacrylic acid (TBPM) 38.8.
g (0.097 mol) were obtained.

Instead of TBAB, benzyltriethylammonium chloride (6 mol%) (Comparative Example 4), benzyltrimethylammonium chloride (6 mol%) (Comparative Example 5), and tetraethylammonium chloride (6 mol%) (Comparative Example 6) were used. Except for using it as a catalyst, the same operation as above is performed,
BPM synthesis was performed.

Table 2 shows the conversion and the crude yield of the obtained TBPM.

[0076]

[Table 2]

Examples 6 to 10 500 m equipped with a stirrer, thermometer and dropping funnel
16.6 g (0.05 mol) of 2,4,6-tribromophenol (2,4,6-TBP) in a four-neck flask
A solution of 3.1 g (0.08 mol) in 20 ml of water, 80 ml of toluene, and 0.5 g (5 mmol,
7.6 g (0.07 mol) of methacrylic acid chloride was added dropwise over 1 hour while stirring at 0 to 6 ° C. After completion of the dropwise addition, the mixture was further stirred at 0 to 6 ° C for 1 hour,
The conversion was measured by PLC. As a result, the conversion rate of TBPM was 2,4,6-tribromophenol,
92.2%. After HPLC analysis, liquid separation was performed, and dichloromethane was distilled off from the organic layer under reduced pressure. After distillation, 60 ml of methanol and 40 ml of water were added, and the mixture was cooled to 0 ° C., filtered and dried to obtain 18.4 g (0.046 mol) of TBPM.

Further, the amount of triethylamine was 3 mol
%, 6 mol% (Examples 7 and 8), or using monochlorobenzene as a solvent instead of toluene, and adjusting the amount of triethylamine to 6 mol%, 10 mol
Except for 1% (Examples 9 and 10), the same operation as above was performed to synthesize TBPM.

Table 3 shows the conversion and crude yield of the obtained TBPM.

[0080]

[Table 3]

As shown in Table 3, even when toluene is used as a solvent, the yield is as good as 92.2% when 10 mol% of triethylamine is used as a catalyst. in this way,
When a tertiary amine is used as a catalyst, the selectivity of the solvent is lost, and the need to use a halogenated hydrocarbon such as dichloromethane or chloroform as the solvent can be eliminated.

Comparative Examples 7-11 500 m equipped with a stirrer, thermometer and dropping funnel
33.1 g (0.1 mol) of 2,4,6-tribromophenol (2,4,6-TBP) in a four-neck flask
12. A solution prepared by dissolving 6.1 g (0.15 mol) in 120 ml of water, 120 ml of dichloromethane and 2.0 g (6.0 mmol, 6 mol%) of tetrabutylammonium bromide are charged, and methacrylic acid chloride is stirred at 0 to 6 ° C. 8g (0.1
3 mol) was added dropwise over 1 hour. After completion of the dropwise addition, the mixture was further stirred at 0 to 6 ° C. for 1 hour. After completion of the reaction, liquid separation was performed, the organic layer was concentrated under reduced pressure, and dichloromethane was distilled off. After distillation, 140 ml of methanol and 60 ml of water were added,
℃, filtered, dried and 38.5g of TBPM
(0.096 mol) was obtained.

The TBPM thus obtained was analyzed by HPLC (internal standard method). As a result, the purity was 97.0%.
Met. Therefore, the crude yield based on the charged 2,4,6-TBP was 96.4%, and the net yield was 93.5%.

Also, instead of using dichloromethane,
TBPM was synthesized by performing the same operation as above except that chloroform (Comparative Example 8), chlorobenzene (Comparative Example 9), isopropyl ether (Comparative Example 10), and toluene (Comparative Example 11) were used as solvents. .

Table 4 shows the crude yield, purity and pure yield of the obtained TBPM.

[0086]

[Table 4]

As shown in Table 4, a sufficient yield cannot be obtained unless a halogenated hydrocarbon such as dichloromethane or chloroform is used as a solvent.

Examples 11 to 15 300 m equipped with a stirrer, thermometer and dropping funnel
16.6 g (0.05 mol) of 2,4,6-tribromophenol (2,4,6-TBP) in a four-neck flask
A solution of 3.1 g (0.08 mol) in 20 ml of water, 80 ml of dichloromethane and 0.12 g of pyridine (1.5 mmol,
7.6 g (0.07 mol) of methacrylic acid chloride was added dropwise over 1 hour while stirring at 0 to 6 ° C.
After completion of the dropwise addition, the mixture was further stirred at 0 to 6 ° C. for 1 hour,
The conversion was measured at C. As a result, no peak other than tribromophenyl methacrylic acid (TBPM) was present. Thus, the conversion of TBPM was 100%.
After HPLC analysis, the layers were separated, and the organic layer was concentrated under reduced pressure.
After distilling off dichloromethane, 60 ml of methanol and 40 ml of water were added, cooled to 0 ° C., filtered and dried to obtain 18.9 g (0.047 mol) of TBPM.

Also, instead of using pyridine (3 mol%), γ-picoline (3 mol%) (Example 12), quinoline (3 mol%)
mol%) (Example 13), 2,2′-bipyridyl (3 mol%)
(Example 14) and 1,5-diazabicyclo [5.
4.0] Unde-5-ene (DBU) (3 mol%) (Example 15)
PM synthesis was performed.

Table 5 shows the conversion and crude yield of the obtained TBPM.

[0091]

[Table 5]

Example 16 500 m equipped with a stirrer, thermometer and dropping funnel
1 4-g flask with 2-naphthol 14.4g (0.10mo
l), a solution of 6.2 g (0.16 mol) of sodium hydroxide dissolved in 40 ml of water, 160 ml of dichloromethane and 0.30 g (3.0 mmol, 3 mol%) of triethylamine were charged.
While stirring at 6 ° C., methacrylic acid chloride 15.2
g (0.14 mol) was added dropwise over 1 hour. After completion of the dropwise addition, the mixture was further stirred at 0 to 6 ° C. for 1 hour, and the conversion was measured by HPLC. As a result, no peak other than 2-naphthyl methacrylate was present. Therefore, the conversion of 2-naphthyl methacrylate was 100%. After HPLC analysis
The layers were separated, and the organic layer was concentrated under reduced pressure. After distilling off dichloromethane, 60 ml of ethanol was added, the mixture was cooled to 0 ° C., filtered and dried to give 2-naphthyl methacrylate.
4 g (0.098 mol) were obtained. Therefore, the yield based on the charged 2-naphthol was 91.5%. The filtrate at this time was evaporated to dryness to obtain 1.5 g (0.007 mol) of crude 2-naphthyl methacrylate. The yield when including the obtained crude product was 98.5%.

Example 17 500 m equipped with a stirrer, thermometer and dropping funnel
1-Quinolinol 14.5g (0.10mo
l), a solution of 6.2 g (0.16 mol) of sodium hydroxide in 40 ml of water, 160 ml of dichloromethane and 0.43 g (3.0 mmol, 3 mol%) of tripropylamine were charged.
14. While stirring at ク ロ 6 ° C., methacrylic acid chloride
2 g (0.14 mol) were added dropwise over one hour. After completion of the dropwise addition, the mixture was further stirred at 0 to 6 ° C. for 1 hour, and the conversion was measured by HPLC. As a result, no peak other than 8-quinolyl methacrylate was present. Therefore, methacrylic acid-8-
The conversion of quinolyl was 100%. After HPLC analysis, the layers were separated, and the organic layer was concentrated under reduced pressure. After distilling off dichloromethane, 60 ml of methanol was added, and the mixture was cooled to 0 ° C., filtered and dried to give 8-quinolyl methacrylate.
8.9 g (0.089 mol) were obtained. Therefore, 8-
The yield based on quinolinol was 88.7%. The filtrate at this time was evaporated to dryness to give crude methacrylic acid-
1.9 g (0.009 mol) of 8-quinolyl were obtained. The yield when including the obtained crude product was 97.7%.

Example 18 500 m equipped with a stirrer, thermometer and dropping funnel
22.8 g (0.10 mol) of 2,2-bis (4-hydroxyphenyl) propane and sodium hydroxide
A solution of 6.2 g (0.16 mol) in 40 ml of water, 160 ml of dichloromethane and 0.56 g of tributylamine
(3.0 mmol, 3 mol%), and stirring at 0 to 6 ° C.
15.2 g (0.14 mol) of methacrylic chloride was added dropwise over 1 hour. After completion of the dropwise addition, the mixture was further stirred at 0 to 6 ° C. for 1 hour, and the conversion was measured by HPLC. As a result,
There was no peak other than 2-bis (4-methacryloyloxyphenyl) propane. Therefore, the conversion of 2,2-bis (4-methacryloyloxyphenyl) propane was 100%. After HPLC analysis, liquid separation was performed, and dichloromethane in the organic layer was distilled off under reduced pressure, and then 2,2-bis (4-methacryloyloxyphenyl) propane 3
6.0 g (0.099 mol) were obtained. Therefore, the charged 2,
The yield based on 2-bis (4-hydroxyphenyl) propane was 99.0%.

Example 19 500 m equipped with a stirrer, thermometer and dropping funnel
l, 4′-dihydroxydiphenyl 18.6 g (0.10 mol), sodium hydroxide 6.2 g (0.16 mol)
Dissolved in 40 ml of water, dichloromethane 160
ml and tripropylamine 0.43 g (3.0 mmol, 3m
ol), and 15.2 g (0.14 mol) of methacrylic chloride was added dropwise over 1 hour while stirring at 0 to 6 ° C.
After completion of the dropwise addition, the mixture was further stirred at 0 to 6 ° C. for 1 hour,
The conversion was measured at C. As a result, there was no peak other than 4,4′-dimethacryloyloxydiphenyl. Therefore, the conversion of 4,4'-dimethacryloyloxydiphenyl was 100%. After HPLC analysis, liquid separation was performed, and dichloromethane in the organic layer was distilled off under reduced pressure, and then 4,4′-dimethacryloyloxydiphenyl 3
1.6 g (0.098 mol) were obtained. Therefore, the charged 4,
The yield based on 4'-dihydroxydiphenyl is 98.0.
%Met.

Example 20 300 m equipped with a stirrer, thermometer and dropping funnel
11.6 g (0.05 mol) of 1H, 1H, 5H-octafluoropentanol in a four-neck flask
A solution of 3.1 g (0.08 mol) in 20 ml of water, 80 ml of dichloromethane and 0.22 g of tripropylamine
(1.5 mmol, 3 mol%) and stirring at 0 to 6 ° C.
7.6 g (0.07 mol) of methacrylic chloride was added dropwise over 1 hour. After completion of the dropwise addition, the mixture was further stirred at 0 to 6 ° C. for 1 hour. After completion of the reaction, liquid separation was performed, and the organic layer was dried over anhydrous sodium sulfate. The anhydrous sodium sulfate was removed by filtration. Acid-1H,
14.3 g of 1H, 5H-octafluoropentyl (0.048
mol). Therefore, the charged 1H, 1H, 5H-
95.5% yield based on octafluoropentanol
Met.

[0097]

As described above, according to the present invention, a (meth) acrylic acid halide represented by the following general formula (i) and an organic compound having an acidic hydroxyl group are prepared in an aqueous solution of an alkali metal hydroxide. When producing (meth) acrylic acid ester by the reaction, the organic compound having the acidic hydroxyl group is used.
The compound of any of the general formulas I, II, III, IV, V or VI
A tertiary amine catalyst and / or a pyridine catalyst or picoline, pyridazi
, Pyrimidine, pyrazine, 1,3,5-triazine,
Quinoline, isoquinoline, cinnoline, quinazoline, quinoline
Noxaline, phthalazine, 1,8-naphthyridine, pute
Lysine, phenazine, phenanthridine, 1,10-phenyl
Enanthroline, 2,2'-bipyridyl, 3,3'-bi
Selected from the group consisting of pyridyl and 4,4'-bipyridyl
The pyridine analog catalyst is used in an amount of 0.01 to 1 with respect to the gram atom equivalent of the hydroxyl group of the organic compound having an acidic hydroxyl group.
A method for producing a (meth) acrylic ester, wherein the reaction is carried out using 0% of the used amount.

[0098]

Embedded image

[0099] According to the method of the present invention, can be maintained even higher indicates vital yields the tertiary amine catalysts and / or pyridine or the pyridine analogs catalyst is high catalytic effect,
The amount of water used can be reduced, and the load on wastewater can be reduced. Further, according to the method of the present invention, the selectivity of the solvent to be used is lost, and the need to use a halogenated hydrocarbon is eliminated. Further, according to the method of the present invention,
Although it has a high catalytic effect, it is highly toxic and poses a problem in terms of safety.
A catalyst with low toxicity and high safety instead of TBAB
High catalytic effect and yield
Further, steps such as quantification and recovery of the used catalyst can be omitted.

[0100] Thus, the method of the present invention, can have use industrially inexpensive raw materials of an aqueous solution of an alkali metal hydroxide, in high yield (meth) when obtained acrylic acid ester simultaneously, using The amount of water is also reduced , and the touch
Determination and collection like the process of medium is unnecessary der Ru (meth) acrylic acid ester.

[0101]

Continuation of the front page (56) References JP-A-62-63541 (JP, A) JP-A-2-110115 (JP, A) JP-A-1-68338 (JP, A) JP-A-63-130563 (JP) JP-A-62-192340 (JP, A) JP-A-59-84845 (JP, A) European Patent Application Publication 455533 (EP, A)

Claims (1)

(57) [Claims] 1. A (meth) acrylic acid ester represented by the following general formula (i) is reacted with an organic compound having an acidic hydroxyl group in an aqueous solution of an alkali metal hydroxide to form a (meth) acrylic acid ester. In the production, the acidic
Organic compounds having a hydroxyl group are represented by the following general formulas I, II, III,
A compound of formula IV, V or VI
Tertiary amine catalyst and / or pyridine catalyst
Or picoline, pyridazine, pyrimidine, pyrazine
, 1,3,5-triazine, quinoline, isoquinolin
, Cinnoline, quinazoline, quinoxaline, phthalazine
1,8-naphthyridine, pteridine, phenazine,
Phenanthridine, 1,10-phenanthroline, 2,
2'-bipyridyl, 3,3'-bipyridyl and 4,4 '
The reaction is carried out using a pyridine analog catalyst selected from the group consisting of -bipyridyl in an amount of 0.01 to 10% based on gram atomic equivalent of the hydroxyl group of the organic compound having an acidic hydroxyl group. A method for producing a (meth) acrylate. Embedded image Embedded image Embedded image Embedded image Embedded image Embedded image Embedded image