CN104903288A - Method for producing polyfunctional (meth) acrylic acid ester - Google Patents
Method for producing polyfunctional (meth) acrylic acid ester Download PDFInfo
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- CN104903288A CN104903288A CN201380066990.2A CN201380066990A CN104903288A CN 104903288 A CN104903288 A CN 104903288A CN 201380066990 A CN201380066990 A CN 201380066990A CN 104903288 A CN104903288 A CN 104903288A
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/48—Separation; Purification; Stabilisation; Use of additives
- C07C67/58—Separation; Purification; Stabilisation; Use of additives by liquid-liquid treatment
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Abstract
The present invention provideS a method for producing a polyfunctional (meth)acrylic acid ester, which enables the final product to contain no aromatic hydrocarbon compound by not using an aromatic hydrocarbon compound, the environmental impact of which has been problematic, as an organic solvent. The present invention discloses a method for producing a polyfunctional (meth)acrylic acid ester by causing an esterification reaction of a (meth)acrylic acid and a polyhydric alcohol in the presence of an acid catalyst. In this method, the esterification reaction is carried out using, as a reaction solvent, an aliphatic hydrocarbon compound and/or alicyclic hydrocarbon compound having 6-12 carbon atoms and a boiling point of 160 DEG C or less at atmospheric pressure and neutralization and water washing of the thus-obtained reaction liquid is carried out using, as an organic solvent, a ketone compound and/or an ester compound, so that a polyfunctional (meth)acrylic acid ester which does not contain an aromatic hydrocarbon compound is produced.
Description
Technical field
The present invention relates to the manufacture method of multifunctional (methyl) acrylate.More particularly, the present invention relates to and not use aromatic hydrocarbon solvent in manufacturing process, under the prerequisite little to environmental influence, thus effectively manufacture the method for multifunctional (methyl) acrylate.The invention still further relates to the method manufacturing painted few multifunctional (methyl) acrylate.
Background technology
Usually, (methyl) acrylate utilizes (methyl) vinylformic acid and alcohol to carry out esterification to manufacture in the presence of acid catalyst.Simple function (methyl) acrylate is low due to boiling point, is thus easy to carry out purifying simple function (methyl) acrylate by distillation from the above-mentioned reaction solution be obtained by reacting.
On the other hand, the boiling point of multifunctional (methyl) acrylate is high, is thus difficult to carry out purifying by distillation as simple function (methyl) acrylate.Therefore, first with in alkali and esterification obtain, esterification liquid containing reaction solvent.Subsequently, (methyl) acrylate extracted from the corrective obtained is washed with water.By this washing operation, alkali composition, acid catalyst and unreacted (methyl) vinylformic acid (patent documentation 1) residual in (methyl) acrylate are removed.
In the manufacture of above-mentioned multifunctional (methyl) acrylate, need to use various organic solvent when esterification, neutralizing treatment and washing process.As these organic solvents, can enumerate (methyl) acrylate for multiple types is the arene compounds such as good solvent, toluene, dimethylbenzene and benzene.
But, in the assurance etc. of particular chemicals quantity discharged in the environment and in promoting the law (Japan PRTR method) that the improvement of management is relevant, arene compound as doubtful harmful material by control object.Therefore, manufacture the problem of the operating environment at scene for solution, because discharging the object of the problem of the topsoil caused, the problem in the room (sick house) that causes a disease etc. in air, a large amount of uses of arene compound are restricted gradually.
For the foregoing reasons, in the manufacture of multifunctional (methyl) acrylate, substitute the arene compound being in the past used as organic solvent, aliphatic hydrocarbon compound or alicyclic hydrocarbon compound obtain application (patent documentation 2).
But the intermiscibility of aliphatic hydrocarbon compound or alicyclic hydrocarbon compound and multifunctional (methyl) acrylate is poor.Therefore, often occur that aliphatic hydrocarbon compound etc. is difficult to the situation of the solvent being used as above-mentioned washing procedure.Mostly its result, be the arene compound such as toluene, dimethylbenzene and aliphatic hydrocarbon compound etc. at present and use (patent documentation 3).
On the other hand, the present inventor finds, when substituting the organic solvent of arene compound as washing procedure with ketone compound, can produce multifunctional (methyl) acrylate.But multifunctional (methyl) acrylate obtained by the method is easily painted.Therefore, with regard to multifunctional (methyl) acrylate manufactured by the method, the possibility that the purposes that there is use is restricted.
Prior art document
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 2001-48831 publication
Patent documentation 2: Japanese Unexamined Patent Publication 2007-182418 publication
Patent documentation 3: Japanese Unexamined Patent Publication 2-306938 publication
Summary of the invention
The problem that invention will solve
First object of the present invention is to provide a kind of manufacture method of multifunctional (methyl) acrylate, this manufacture method does not use becomes the arene compound of problem as organic solvent to the impact of environment, thus in the final product not containing arene compound.
Second object of the present invention is to provide a kind of manufacture method of painted few multifunctional (methyl) acrylate.
The method of dealing with problems
In order to solve the problem, what the present inventor carried out concentrating on studies found that, by selecting specific organic solvent shown below, multifunctional (methyl) acrylate not containing arene compound can be produced, thus complete the manufacture method (first aspect of the present invention) of multifunctional (methyl) acrylate.
And then the present inventor have developed before adding the organic solvent of ketone compound as washing procedure, to the method that part or all of acid catalyst neutralizes.According to the method, can produce not containing arene compound and painted few multifunctional (methyl) acrylate (second aspect of the present invention).
That is, first aspect of the present invention is the manufacture method of multifunctional (methyl) acrylate, and this manufacture method comprises following operation.
1) esterification operation, boiling point is that the aliphatic hydrocarbon compound of 40 ~ 160 DEG C and/or alicyclic hydrocarbon compound are as reaction solvent with carbonatoms 6 ~ 12 and under normal pressure, in the presence of acid catalyst, (methyl) vinylformic acid and polyvalent alcohol is made to carry out esterification, thus the reaction solution obtained containing multifunctional (methyl) acrylate
2) neutralizing treatment operation is diluted, carry out in the reaction solution obtained in esterification operation in any order or simultaneously, add the dilution process operation of the organic solvent be at least made up of ketone compound and/or ester cpds and add the neutralizing treatment operation of alkali aqueous solution, thus obtain dilution neutralizing treatment liquid
3) organic phase recovery process, is separated into aqueous phase and organic phase by the dilution neutralizing treatment liquid that dilution neutralizing treatment operation obtains, thus obtains organic phase,
4) washing step, carries out washing process to the organic phase reclaimed,
5) separation circuit of multifunctional (methyl) acrylate, organic solvent is distilled out from the organic phase of washing, thus isolate multifunctional (methyl) acrylate from organic solvent after, obtain multifunctional (methyl) acrylate.
Further, second aspect of the present invention is the manufacture method of multifunctional (methyl) acrylate, and this manufacture method comprises following operation.
1) esterification operation, boiling point is that the aliphatic hydrocarbon compound of 40 ~ 160 DEG C and/or alicyclic hydrocarbon compound are as reaction solvent with carbonatoms 6 ~ 12 and under normal pressure, in the presence of acid catalyst, (methyl) vinylformic acid and polyvalent alcohol is made to carry out esterification, thus the reaction solution obtained containing multifunctional (methyl) acrylate
6), in acid catalyst and operation, in the reaction solution obtained, add the alkali composition being at least 1/2 equivalent relative to input acid catalyst, thus obtain acid catalyst neutralization reaction liquid,
7) dilution in and operation, add while the solvent be made up of ketone compound carrys out dilute acid catalyzer neutralization reaction liquid in described acid catalyst neutralization reaction liquid, add buck and neutralize unreacted (methyl) vinylformic acid, thus obtain reaction mixture
8) organic phase recovery process, after the dilution neutralizing treatment liquid obtained is separated into organic phase and aqueous phase, reclaims organic phase in dilution with operation,
9) washing step, carries out washing process to the organic phase reclaimed,
10) separation circuit of multifunctional (methyl) acrylate, organic solvent is distilled out from the organic phase of washing, thus isolate multifunctional (methyl) acrylate from organic solvent after, obtain multifunctional (methyl) acrylate.
The effect of invention
As the manufacture method of first and second aspect of the present invention, in manufacturing process, do not use arene compound.For the foregoing reasons, the finished product obtained, i.e. multifunctional (methyl) acrylate are not containing arene compound.Therefore, on participate in multifunctional (methyl) acrylate manufacture personnel, use the health or minimum on the impact of environment of the personnel of multifunctional (methyl) acrylate.
And then, manufacture method according to a second aspect of the invention, the finished product painted few.Therefore, it is possible to the purposes of tackiness agent of the painted Clear coating, transparent film and the adhesive sheet that become problem that are applicable to product etc.
Embodiment
Below, the present invention is described in detail.In addition, in this specification sheets, (methyl) vinylformic acid refers to vinylformic acid and methacrylic acid.
(first aspect of the present invention)
First aspect of the present invention relates to the manufacture method of multifunctional (methyl) acrylate comprising following first operation (esterification operation (1)) and the second operation (diluting the separation circuit (5) of neutralizing treatment operation (2), organic phase recovery process (3), washing step (4) and multifunctional (methyl) acrylate).
First operation is in the presence of acid catalyst, carries out esterification, thus obtain the esterification operation of the reaction solution containing multifunctional (methyl) acrylate by stirring, mixing (methyl) vinylformic acid and polyvalent alcohol.
Second operation is added after organic solvent and alkali aqueous solution carry out neutralization reaction liquid in the reaction solution obtained in the first operation, the reaction solution of neutralization be separated into the two-phase of organic phase and aqueous phase and be separated organic phase, with the organic phase that after washing obtains, be finally separated the operation of multifunctional (methyl) acrylate.
With regard to multifunctional (methyl) acrylate manufactured by the manufacture method of first aspect of the present invention, as long as have the compound of (methyl) acryl of more than 2 in 1 molecule, just there is no particular limitation.
Specifically, (methyl) acrylate of tetramethylolmethane can be enumerated, (methyl) acrylate of Dipentaerythritol, (methyl) acrylate of tripentaerythritol, (methyl) acrylate of polyoxyethylene and/or polyoxypropylene bisphenol A ether, (methyl) acrylate of polyoxyethylene and/or polyoxypropylene bisphenol F ether, (methyl) acrylate of polyoxyethylene glycol, (methyl) acrylate of tricarbimide three (2-hydroxyethyl), (methyl) acrylate of the polyester be made up of polyprotonic acid and polyvalent alcohol, (methyl) acrylate of TriMethylolPropane(TMP), (methyl) acrylate of ditrimethylolpropane, (methyl) acrylate of polypropylene glycol, (methyl) acrylate of polyoxyethylene and/or polyoxypropylene TriMethylolPropane(TMP) ether, (methyl) acrylate etc. of polyoxyethylene and/or polyoxypropylene tetramethylolmethane ether.
In these multifunctional (methyl) acrylate, be preferably difficult to multifunctional (methyl) acrylate mixed with the solvent be made up of aliphatic hydrocarbon compound or alicyclic hydrocarbon compound.
As this multifunctional (methyl) acrylate, (methyl) acrylate of tetramethylolmethane can be enumerated, (methyl) acrylate of Dipentaerythritol, (methyl) acrylate of tripentaerythritol, (methyl) acrylate of polyoxyethylene and/or polyoxypropylene bisphenol A ether, (methyl) acrylate of polyoxyethylene and/or polyoxypropylene bisphenol F ether, (methyl) acrylate of polyoxyethylene glycol, (methyl) acrylate of tricarbimide three (2-hydroxyethyl), (methyl) acrylate etc. of the polyester be made up of polyprotonic acid and polyvalent alcohol.
First operation (esterification operation (1)) is in the presence of acid catalyst, after stirring, mixing (methyl) vinylformic acid and polyvalent alcohol promote esterification, obtain the esterification operation of the reaction solution containing (methyl) acrylate.
Esterification can conventionally be carried out.Usually, can enumerate in organic solvent, heating under the existence of acid catalyst, stir the method etc. of (methyl) vinylformic acid and polyvalent alcohol.
As polyvalent alcohol, the polyvalent alcohol that multifunctional with described (methyl) acrylate is corresponding can be used.OH radix in a part of polyvalent alcohol is preferably more than 2, is more preferably 2 ~ 10.
As the object lesson of polyvalent alcohol, the multi-ring alkyl glycol such as Tricyclodecane Dimethanol can be enumerated, the dibasic alcohol such as ethylene glycol, propylene glycol, pentanediol and hexylene glycol, the polyalkylene glycols such as glycol ether, triglycol, Tetraglycol 99, polyoxyethylene glycol, dipropylene glycol, tripropylene glycol and polypropylene glycol, the glycerol classes such as glycerol and two glycerol, the oxirane affixture of glycerol class, the bisphenols oxirane affixture such as bisphenol-A epoxy alkane affixture and Bisphenol F epoxy alkane affixture.
And then, the oxirane affixture of the polyvalent alcohols such as TriMethylolPropane(TMP), two TriMethylolPropane(TMP)s, tetramethylolmethane and Dipentaerythritol and these polyvalent alcohols can be enumerated, tricarbimide oxirane affixture, and polyester polyol etc.As the oxirane in oxirane affixture, oxyethane and propylene oxide etc. can be enumerated.Further, as the adduct number of oxirane, 1 ~ 20 is preferably.
With regard to (methyl) acrylic acid usage ratio, suitably can set according to object (methyl) acrylate.Usually, when the hydroxyl value that 1 molecular polylol has is set to n, relative to polyvalent alcohol 1 mole, be preferably 0.7n ~ 2.0n mole, be more preferably 0.9n ~ 1.5n mole.
As acid catalyst, the mineral acids such as hydrochloric acid, phosphoric acid, sulfuric acid can be enumerated, the sulfonic acid etc. such as tosic acid, methylsulfonic acid and trifluoromethanesulfonic acid.
As the usage ratio of acid catalyst, relative to the following total mass comprising the reaction solution of organic solvent, be preferably 0.1 ~ 10 quality %.
Esterification can conventionally be implemented.Temperature of reaction suitably can set according to the raw material used and object.For the reaction times shortening and prevent be polymerized viewpoint, temperature of reaction is preferably 65 ~ 140 DEG C, is more preferably 75 ~ 120 DEG C.By temperature of reaction is located at more than 65 DEG C, esterification speed can be improved, prevent the reduction of yield.On the other hand, by temperature of reaction is located at less than 140 DEG C, the thermopolymerization of (methyl) acrylate of (methyl) vinylformic acid or generation can be prevented.
As pressure during reaction, can be normal pressure or decompression.In order to prevent the thermopolymerization of (methyl) acrylate of (methyl) vinylformic acid or generation, for the object reducing temperature of reaction, preferably react at decompression state.
In esterification, generate water along with the carrying out of reaction.Preferably by with organic solvent azeotropic from react be remove the water of this generation, thus promote esterification.
The organic solvent used in esterification is carbonatoms 6 ~ 12, is preferably carbonatoms 6 ~ 10, and the boiling point under normal pressure is less than 160 DEG C, is preferably aliphatic hydrocarbon compound and/or the alicyclic hydrocarbon compound of 40 ~ 140 DEG C.
As the organic solvent used in esterification, normal hexane, normal heptane, octane, octane-iso, nonane, 2-methyloctane, 2 can be enumerated, the aliphatic hydrocarbon compounds such as 6-dimethyl octane, the alicyclic hydrocarbon etc. such as hexanaphthene, suberane, methylcyclohexane, cyclooctane and 1-methyl-4-ethylcyclohexane.Wherein, for the consideration of versatility aspect, preferred normal hexane, hexanaphthene, methylcyclohexane, normal heptane and octane-iso.
With regard to the usage quantity of described organic solvent, relative to described polyvalent alcohol and (methyl) acrylic acid total amount be 0.05 ~ 2.0 quality doubly, consider the factors such as the removal of the water in the carrying out smoothly of esterification, reaction solution, be more preferably 0.1 ~ 1.0 quality doubly.
In esterification, in order to prevent polymerization, preferably reacting in the presence of oxygen, for same object, preferably in reaction solution, adding stopper.
As stopper, organic compounds and metal-salt etc. can be there are.As organic compound, such as, benzoquinones, quinhydrones, catechol, diphenyl-benzoquinone, hydroquinone monomethyl ether, naphthoquinones, tert-butyl catechol, tert.-butyl phenol, dimethyl-tert-butyl phenol, tertiary butyl cresols, butylated hydroxytoluene, gallic acid, gallic acid ester and thiodiphenylamine etc. can be enumerated.
As metal-salt, the copper compound such as cupric chloride and copper sulfate can be enumerated, and the iron cpd etc. such as ferrous sulfate.
With regard to the addition of stopper, for benchmark, count 10 ~ 50,000ppm with quality standard using (methyl) the acrylic acid usage quantity as raw material, be preferably 100 ~ 10,000ppm.When addition is more than 10ppm, actual use is upper no problem, but when more than 100ppm, can give full play to polymerization inhibition effect.By controlling 10, below 000ppm by addition, the reduction of the polymerization-curable of painted, (methyl) acrylate of (methyl) acrylate generated can be prevented.
With regard to the degree of carrying out of esterification, can by monitoring the amount of the water generated by esterification (namely, dehydrating amount), or sour composition ((methyl) vinylformic acid and the acid catalyst) concentration in assaying reaction liquid, or analyze the content of resultant (methyl) acrylate and form to compare with target and judge.
As the reaction under existing at described oxygen, specifically, there is the reaction in the environment of oxygen-containing gas or import oxygen-containing gas in reaction solution while, carry out the method for reacting.Typical oxygen-containing gas is air.The industrial danger considering blast of igniting, the oxygen-containing gas of applicable is oxygen concn 3 ~ 15 volume %.As oxygen-containing gas, can by mixture of oxygen or air, prepare with rare gas element.As rare gas element, conventional is nitrogen or argon gas.
(the second operation)
After first operation terminates, carry out the second operation.Before carrying out the second operation, also can remove by the method such as distillation, reclaim reaction solution that the first operation obtains in organic solvent, carry out the second operation subsequently.
As the second operation, be in simple terms add in the reaction solution obtained in the first operation organic solvent and alkali aqueous solution carry out diluting and in and after, separatory is organic phase with the two-phase of aqueous phase and is separated organic phase, reclaims the operation of (methyl) acrylate subsequently.
Be two-phase by separatory after adding alkali aqueous solution in the reaction solution that obtains in the first operation, make sour composition such as unreacted (methyl) vinylformic acid and acid catalyst etc. move to aqueous phase, from reaction solution, remove these unreacted sour compositions.
And then, add organic solvent by the reaction solution that obtains in the first operation, effectively can be separated into two-phase.
Second operation is made up of the separation circuit diluting neutralizing treatment operation, organic phase recovery process, washing step and multifunctional (methyl) acrylate.
As the reaction solution that the first operation obtains, processed by the dilution neutralizing treatment operation (2) of the second operation subsequently.
Dilution neutralizing treatment operation (2) adds the dilution process operation of the organic solvent be at least made up of ketone compound and/or ester cpds in the reaction solution carrying out in any order or simultaneously obtaining in esterification operation and adds the neutralizing treatment operation of alkali aqueous solution, thus obtain the operation of diluting neutralizing treatment liquid.
Dilution neutralizing treatment operation is made up of dilution process operation and neutralizing treatment operation, and these each operation optionally first can carry out a side, or also can carry out simultaneously.
In the alkali aqueous solution that neutralizing treatment operation uses, as alkali composition, the alkali metal hydroxide such as sodium hydroxide and potassium hydroxide can be enumerated, and the alkaline-earth metal such as an alkali metal salt and the calcium hydroxide oxyhydroxide etc. such as sodium carbonate.In these, alkali metal hydroxide due to neutralization excellent, because of but preferably.
As the amount of the alkali composition in the alkali aqueous solution added in neutralizing treatment operation, relative to the sour composition of reaction solution, be preferably more than 1 times with molar ratio computing, be more preferably 1.0 ~ 1.6 times.The addition of alkali composition, when above-mentioned scope, can carry out the neutralization of sour composition fully.
The concentration of alkali aqueous solution is preferably 1 ~ 25 quality %, is more preferably 3 ~ 25 quality %, is particularly preferably 10 ~ 25 quality %.By the concentration of alkali aqueous solution is located at more than 1 quality %, the increase of the water displacement after neutralizing treatment can be prevented.By the concentration of alkali aqueous solution is located at below 25 quality %, the polymerization of multifunctional (methyl) acrylate can be prevented.
In addition, this neutralizing treatment also can be divided into and implementing several times.
The organic solvent used in dilution process operation in the dilution of the second operation and in operation (2) is ketone compound and/or ester cpds.
As ketone compound, acetone, methylethylketone, methyl iso-butyl ketone (MIBK), cyclopentanone and pimelinketone etc. can be enumerated.
As ester cpds, the acetic esters such as ritalin, vinyl acetic monomer, n-propyl acetate, Iso Butyl Acetate and N-BUTYL ACETATE can be enumerated, (methyl) acrylate such as (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) propyl acrylate, (methyl) isobutyl acrylate and (methyl) butyl acrylate.
In these, for the consideration of the removal efficiency aspect of sour composition, preferred carbonatoms 3 ~ 8 and under normal pressure boiling point be less than 160 DEG C, be preferably ketone compound and/or the ester cpds of 40 ~ 140 DEG C.
Specifically, methylethylketone, methyl iso-butyl ketone (MIBK), Iso Butyl Acetate, n-propyl acetate, N-BUTYL ACETATE, isobutyl acetate and tert-butyl acetate particularly preferably is.
These ketone compounds and/or ester cpds can be used alone or mix two or more use, use after can also mixing with other organic solvents beyond ketone compound and ester cpds.
With regard to the usage quantity of organic solvent be made up of ketone compound and/or ester cpds, be preferably 0.2 ~ 10 quality of the total mass of (methyl) vinylformic acid and polyvalent alcohol doubly, for the consideration of the removal effect aspect of sour composition, be more preferably 0.4 ~ 5.0 quality doubly.
In dilution neutralizing treatment operation, preferably reaction solution, organic solvent and alkali aqueous solution are supplied to slot-type device and stir and process, or use static mixer etc. to process.
In force with process before, the pre-washing that agent carries out reaction solution can be washed with water and process.
Particularly, when using the stopper of copper class in esterification operation, by washing process in advance, the stopper of copper class effectively can be removed.
As washing treatment process in advance, specifically, can be set forth in the reaction solution that esterification obtains and add rinsing agent, carry out the method etc. stirring and mix subsequently.
As rinsing agent, the aqueous solution of the inorganicss such as pure water, sodium chloride aqueous solution, ammonium sulfate solution can be used.With regard to the content of the inorganics in rinsing agent, the concentration below the solubleness of the inorganics preferably during service temperature.
With regard to the dilution neutralizing treatment liquid that reaction solution in dilution neutralizing treatment operation (2) obtains after treatment, subsequently, in organic phase recovery process (3), be separated into the two-phase of organic phase and aqueous phase, and isolate organic phase.As the separation method of organic phase, the method for lower floor, the i.e. aqueous phase extracting the two-phase be separated can be enumerated.
Isolated organic phase is washed in washing step (4).As washing the rinsing agent used, the rinsing agent used in described pre-washing treatment process can be used in, particularly preferably be water.
In the separation circuit (5) of multifunctional (methyl) acrylate, being separated after for the two-phase of described organic phase and aqueous phase, from isolated organic phase, distilling out organic solvent, thus isolate (methyl) acrylate.The distillation of organic solvent can according to ordinary method.Such as, the method etc. removing organic solvent with the desolventizing groove reduced pressure can be enumerated.As the vacuum tightness of desolventizing groove, suitably can set according to used raw material and object, preferably be set to 0.5 ~ 50kPa, and preferably progressively increase the method for degree of decompression according to the removal degree of organic solvent.
In the distillation of this organic solvent, in order to prevent the thermopolymerization of (methyl) acrylate, preferably under reduced pressure carrying out, the distillation temperature of solvent is maintained such as 20 ~ 80 DEG C for oxygen supply or while adding stopper.
As required, while removing organic solvent with desolventizing groove from organic phase, also can supply flocculating aids in desolventizing groove, and flocculating aids is accumulated on the strainer of the vertical horizontal filter board type be connected with desolventizing groove, thus carry out the filtration treatment of resultant of reaction.
As the aqueous phase be separated in described organic phase recovery process, washing process and washing water, can process as waste water by known method.
(second aspect of the present invention)
Below, second aspect of the present invention is described in detail.
Briefly, second aspect of the present invention relate to implement following first operation (esterification operation (5)) and the second operation (in acid catalyst and operation (6), dilute in operation (7), organic layer recovery process (8), washing step (9), be separated the operation (10) of multifunctional (methyl) acrylate) the manufacture method of multifunctional (methyl) acrylate.
First operation is in the presence of acid catalyst, carries out esterification, thus obtain the esterification operation of the reaction solution containing multifunctional (methyl) acrylate by stirring, mixing (methyl) vinylformic acid and polyvalent alcohol.
Second operation adds alkali composition with at least 1/2 of neutralizing acid catalyzer in the reaction solution obtained in the first operation, subsequently, to remove the ketone compound and the alkali aqueous solution that add organic solvent for the purpose of unreacted (methyl) vinylformic acid, acid catalyst etc., extract organic phase after being separated into the two-phase of organic phase and aqueous phase, thus reclaim the operation of multifunctional (methyl) acrylate.
With regard to multifunctional (methyl) acrylate obtained by the manufacture method of second aspect of the present invention, as long as have the compound of (methyl) acryl of more than 2, just there is no particular limitation.Specifically, identical with first aspect of the present invention.Further, as the esterification operation (1) of the first operation, identical with the esterification operation of first aspect of the present invention.
(the second operation)
After first operation terminates, carry out the second operation.In the second operation, first, add in the reaction solution obtained in the first operation alkali composition with at least 1/2 of neutralizing acid catalyzer (acid catalyst 1/2 ~ all) (in acid catalyst and operation (6)).Subsequently, to add for the purpose of unreacted (methyl) vinylformic acid, (methyl) acrylic acid polymkeric substance etc. as the ketone compound of organic solvent and alkali aqueous solution (in dilution and operation) to remove.
Order of addition for organic solvent and alkali aqueous solution does not limit, and optionally first can add one, and these also can add simultaneously.
Secondly, the two-phase be separated as organic phase and aqueous phase.Subsequently, extract the organic phase (organic layer recovery process (8)) be separated, wash the organic layer (washing step (9)) obtained, reclaim multifunctional (methyl) acrylate (being separated the operation (10) of multifunctional (methyl) acrylate).
In addition, in the second operation, before interpolation organic solvent, also can remove, be recovered in the reaction solvent (aliphatic hydrocarbon compound and/or alicyclic hydrocarbon compound) used in the first operation by methods such as distillations.
The alkali composition of neutralizing acid catalyzer can add before the ketone compound adding organic solvent, also or can add afterwards before removing, reclaiming the first operation reaction solvent used.
As in acid catalyst and the alkali composition of middle use, the alkali metal hydroxide such as sodium hydroxide and potassium hydroxide can be enumerated, and the alkaline-earth metal such as an alkali metal salt and the calcium hydroxide oxyhydroxide etc. such as sodium carbonate.
Do not limit with the form of the alkali composition of middle use in acid catalyst, but based on being easy to the viewpoint of adding, being easy to mixing, be preferably the form of the aqueous solution.As in acid catalyst and the addition of alkali composition of middle use, relative to the acid catalyst dropped into, be preferably 1/2 equivalent doubly more than, be more preferably 2/3 equivalent doubly more than.When the ratio of the acid catalyst be neutralized is less than 1/2 equivalent times relative to the catalyzer dropped into, be difficult to obtain painted few product (methyl) acrylate.
The organic solvent used in the dilution of the second operation and in operation (7) is ketone compound.Specifically, acetone, methylethylketone, methyl iso-butyl ketone (MIBK), cyclopentanone and pimelinketone etc. can be enumerated.
In these, for being easy to remove the viewpoint of organic solvent, particularly preferably carbonatoms 3 ~ 8 and under normal pressure boiling point be less than 160 DEG C, the preferably ketone compound of 40 ~ 140 DEG C, such as, preferred methylethylketone and methyl iso-butyl ketone (MIBK).
Ketone compound can separately or mix two or more, uses after also can mixing with other organic solvents beyond ketone compound.As other solvent this, normal hexane, normal heptane, octane, octane-iso, nonane, 2-methyloctane, 2 can be enumerated, the aliphatic hydrocarbon compounds such as 6-dimethyl octane, the alicyclic hydrocarbon etc. such as hexanaphthene, suberane, methylcyclohexane, cyclooctane and 1-methyl-4-ethylcyclohexane.
As the usage quantity of ketone compound, be preferably 0.2 ~ 10 quality of the total mass of (methyl) acrylic acid quality of blending and the quality of polyvalent alcohol in the remaining quality of the reaction solvent that the first operation uses, the first operation doubly, for the consideration of the removal effect aspect of organic solvent, be particularly preferably 0.4 ~ 5.0 quality doubly.
In dilution and in operation (7), as to remove the alkali composition added in reaction solution for the purpose of the sour compositions such as unreacted (methyl) vinylformic acid, the alkali metal hydroxide such as sodium hydroxide and potassium hydroxide can be enumerated, and the alkaline-earth metal such as an alkali metal salt and the calcium hydroxide oxyhydroxide etc. such as sodium carbonate.This alkali composition can with in acid catalyst with time the alkali composition that uses identical, also can be different.In these alkali compositions, alkali metal hydroxide due in and removal effect excellent, because of but preferably.
Alkali composition preferably adds in reaction solution with the state of the aqueous solution.With regard to the concentration of the alkali aqueous solution of use, be preferably 1 ~ 25 quality %, be more preferably 3 ~ 25 quality %, be particularly preferably 10 ~ 25 quality %.When the concentration of alkali aqueous solution is more than 1 quality %, can prevent the water displacement after neutralizing treatment from increasing.When the concentration of alkali aqueous solution is below 25 quality %, the polymerization of multifunctional (methyl) acrylate can be prevented.Neutralizing treatment also can be divided into repeatedly to be implemented.
As the addition to neutralize the alkali composition added in reaction solution for the purpose of the sour compositions such as unreacted (methyl) vinylformic acid, with the mole number of the sour compositions such as unreacted (methyl) vinylformic acid for benchmark, be preferably more than 1 times with molar ratio computing, be more preferably 1.0 ~ 1.6 times.By adding alkali composition in the scope of above-mentioned mol ratio, can neutralize fully, removing the sour compositions such as unreacted (methyl) vinylformic acid.
For by the reaction mixture obtained with the neutralizing treatment of operation (7) in dilution, preferably wash agent with water and carry out carrying out washing treatment.As rinsing agent, the aqueous solution of pure water and the inorganic salt such as sodium chloride aqueous solution, ammonium sulfate solution can be used.Washing process also can be implemented several times.
Although for there is no particular limitation with operation in dilution, as preferred mode, the method for carrying out while stirring by slot-type device can be enumerated, or the method using static mixer etc. to carry out.In diluting and after operation, by the two-phase be separated as organic phase and aqueous phase by the reaction mixture obtained with operation in dilution, extract organic phase, wash the organic layer obtained, the solvent of organic layer is removed in distillation, thus can reclaim multifunctional (methyl) acrylate.
In addition, in force with process before, reaction solution can be washed based on various object.Particularly, when using the stopper of copper class in esterification operation, by washing the reaction solution that the first operation obtains, effectively can remove the stopper of copper class.
As the method for washed reaction liquid, can conventionally, also can wash with processing identical method with the washing after described neutralizing treatment.As rinsing agent, the aqueous solution of pure water and the inorganics such as sodium chloride aqueous solution, ammonium sulfate solution can be used.
As the organic layer recovery process (8) of second aspect of the present invention, washing step (9) and the operation (10) being separated multifunctional (methyl) acrylate, can adopt and carry out with the organic layer recovery process (8) of first aspect of the present invention, washing step (9) and the operation that is separated the operation (5) of multifunctional (methyl) acrylate identical.
Embodiment
Below, embodiment and comparative example is enumerated to further illustrate first aspect of the present invention.In addition, " % " that below mention refers to quality %, and ppm is mg/kg.
Embodiment, the comparative example of first aspect of the present invention
Embodiment 1
Be provided with return line 3L with in the four-hole boiling flask of arm, drop into Dipentaerythritol 628.1g, vinylformic acid 1281.9g, tosic acid monohydrate (following, to be referred to as PTS) 112.0g, cupric chloride 3.0g, hexanaphthene 675.0g.While being injected in flask by oxygen-containing gas (oxygen 5 volume %, nitrogen 95 volume %), carry out heated and stirred reacting liquid temperature 75 ~ 80 DEG C.The water Dean-Stark tube drainage generated along with the carrying out of reaction to outside system, thus carries out the dehydration esterification reaction of 13 hours.
After reaction terminates, in reaction solution, add n-propyl acetate 2000.0g dilute, and then add distilled water 150g.After fully stirring and washing reaction solution, leave standstill and make it to be layered as aqueous phase (lower floor) and organic solvent phase (upper strata), the aqueous phase of removal lower floor.
Subsequently, organic solvent mutually in add 20% aqueous sodium hydroxide solution come in and organic solvent mutually in after the sour composition that contains, leave standstill and make it to be layered as aqueous phase (lower floor) and organic solvent phase (upper strata), after removing the aqueous phase of lower floor, reclaim organic solvent phase.The organic solvent reclaimed mutually in add after distilled water 450g washes again, leave standstill, remove the aqueous phase (lower floor) be separated, reclaim the organic solvent phase on upper strata.
At the organic solvent middle interpolation hydroquinone monomethyl ether 200ppm mutually of above-mentioned recovery, while injection air, be under reduced pressure heated to 80 DEG C distill removal solvent, thus obtain polyfunctional acrylic ester.
During the aromatic series kind solvent contained in the polyfunctional acrylic ester obtained with gas-chromatography (Monitoring lower-cut: 10ppm) analysis, be not detected (representing with N.D.).
Embodiment 2
Be provided with return line 3L with in the four-hole boiling flask of arm, drop into tetramethylolmethane 668.2g, vinylformic acid 1556.6g, PTS 67.5g, cupric chloride 2.7g, hexanaphthene 405.0g.While injecting the oxygen-containing gas identical with embodiment 1, carry out heated and stirred reacting liquid temperature 75 ~ 80 DEG C, the water of generation with Dean-Stark tube drainage to outside system, thus carry out 10 hours dehydration esterification reaction.
After reaction terminates, in reaction solution, add n-propyl acetate 1500.0g, hexanaphthene 1000.0g dilutes.Add distilled water 200g again and after fully stirring and washing, leave standstill and make it to be layered as aqueous phase (lower floor) and organic solvent phase (upper strata), the aqueous phase of removal lower floor.
Subsequently, organic solvent mutually in add 20% aqueous sodium hydroxide solution come in and organic solvent mutually in after the sour composition that contains, leave standstill and make it to be layered as aqueous phase (lower floor) and organic solvent phase (upper strata).Remove the aqueous phase of lower floor, reclaim organic solvent phase.The organic solvent reclaimed mutually in add after distilled water 500g washes again, leave standstill.Remove the aqueous phase (lower floor) be separated, reclaim the organic solvent phase on upper strata.
At the organic solvent reclaimed middle interpolation hydroquinone monomethyl ether 200ppm mutually, while injection air, be under reduced pressure heated to 80 DEG C distill removal solvent, thus obtain polyfunctional acrylic ester.
During the polyfunctional acrylic ester obtained with gas-chromatography (Monitoring lower-cut: 10ppm) analysis, aromatic series kind solvent is not detected.
Embodiment 3
Be provided with return line 3L with in the four-hole boiling flask of arm, drop into Dipentaerythritol 586.0, vinylformic acid 1196.0g, PTS 105.3g, cupric chloride 2.7g, normal heptane 810.0g.While injecting the oxygen-containing gas identical with embodiment 1, carry out heated and stirred reacting liquid temperature 95 ~ 100 DEG C.Generate water with Dean-Stark tube drainage to outside system, thus carry out 10 hours dehydration esterification reaction.
After reaction terminates, in reaction solution, add methylethylketone 1890.0g dilute, then add distilled water 150g and fully stir and wash reaction solution.Subsequently, leave standstill and make it to be layered as aqueous phase (lower floor) and organic solvent phase (upper strata), remove the aqueous phase of lower floor.
Subsequently, organic solvent mutually in add 20% aqueous sodium hydroxide solution come in and organic solvent mutually in the sour composition that contains.Leave standstill and make it to be layered as aqueous phase (lower floor) and organic solvent phase (upper strata), after removing the aqueous phase of lower floor, reclaim organic solvent phase.The organic solvent reclaimed mutually in, then add distilled water 450g and wash.Remove the aqueous phase (lower floor) be separated after leaving standstill, reclaim the organic solvent phase on upper strata.
At the organic solvent middle interpolation hydroquinone monomethyl ether 200ppm mutually of above-mentioned recovery, be under reduced pressure heated to 80 DEG C distill removal solvent while injecting air, thus obtain polyfunctional acrylic ester.
During the polyfunctional acrylic ester obtained with gas-chromatography (Monitoring lower-cut: 10ppm) analysis, aromatic series kind solvent is not detected.
Embodiment 4
Be provided with return line 3L with in the four-hole boiling flask of arm, drop into TriMethylolPropane(TMP) 688.0g, Tetra hydro Phthalic anhydride 380.2g, vinylformic acid 739.4g, PTS 81.0g, hydroquinone monomethyl ether 1.4g, hexanaphthene 810.0g.While injecting the oxygen-containing gas identical with embodiment 1, carry out heated and stirred reacting liquid temperature 75 ~ 80 DEG C.Generate water with Dean-Stark tube drainage to outside system, thus carry out 12 hours dehydration esterification reaction.
After reaction terminates, add after methylethylketone 1000.0g dilutes in reaction solution, then add 10% aqueous sodium hydroxide solution come in and organic solvent mutually in the sour composition that contains.Leave standstill and make it to be layered as aqueous phase (lower floor) and organic solvent phase (upper strata), after removing the aqueous phase of lower floor, reclaim organic solvent phase.
Subsequently, the organic solvent reclaimed mutually in add distilled water 350g and carry out leaving standstill after washing, remove the aqueous phase (lower floor) be separated, the organic solvent phase on recovery upper strata.While the organic solvent reclaimed mutually middle injection air, be under reduced pressure heated to 80 DEG C distill removal solvent, thus obtain polyfunctional acrylic ester.
During the polyfunctional acrylic ester obtained with gas-chromatography (Monitoring lower-cut: 10ppm) analysis, aromatic series kind solvent is not detected.
Embodiment 5
Be provided with return line 3L with in the four-hole boiling flask of arm, drop into Dipentaerythritol 518.4g, methacrylic acid 1263.6g, PTS 105.3g, cupric chloride 2.7g, normal heptane 810.0g.While injecting the oxygen-containing gas identical with embodiment 1, carry out heated and stirred reacting liquid temperature 95 ~ 100 DEG C.Generate water with Dean-Stark tube drainage to outside system, thus carry out 10 hours dehydration esterification reaction.
After reaction terminates, in reaction solution, add methylethylketone 1890.0g dilute, then add distilled water 150g and fully stir and wash reaction solution.Subsequently, leave standstill and make it to be layered as aqueous phase (lower floor) and organic solvent phase (upper strata), remove the aqueous phase of lower floor.
Subsequently, organic solvent mutually in add 20% aqueous sodium hydroxide solution come in and organic solvent mutually in the sour composition that contains.Leave standstill and make it to be layered as aqueous phase (lower floor) and organic solvent phase (upper strata), after removing the aqueous phase of lower floor, reclaim organic solvent phase.The organic solvent reclaimed mutually in, then add distilled water 450g and wash.Remove the aqueous phase (lower floor) be separated after leaving standstill, reclaim the organic solvent phase on upper strata.
At the organic solvent middle interpolation hydroquinone monomethyl ether 200ppm mutually of above-mentioned recovery, be under reduced pressure heated to 80 DEG C distill removal solvent while injecting air, thus obtain polyfunctional acrylic ester.
During the polyfunctional acrylic ester obtained with gas-chromatography (Monitoring lower-cut: 10ppm) analysis, aromatic series kind solvent is not detected.
The comparative example of first aspect of the present invention
Comparative example 1
Except changing to except toluene by the organic solvent used in the reaction process of embodiment 1 and washing procedure, obtain polyfunctional acrylic ester with the operation identical with embodiment 1.
During the polyfunctional acrylic ester obtained with gas-chromatography (Monitoring lower-cut: 10ppm) analysis, detect that toluene is 255ppm.
Comparative example 2
Except changing to except hexanaphthene by the solvent used in the washing procedure of embodiment 1, carry out the operation identical with embodiment 1.In this comparative example, polyfunctional acrylic ester and hexanaphthene occur that layer is separated, and fail to be separated and remove rinsing agent (aqueous phase), thus do not obtain polyfunctional acrylic ester in washing procedure.
Table 2
Embodiment, the comparative example of second aspect of the present invention
Below, embodiment and comparative example is enumerated to further illustrate second aspect of the present invention.In addition, " % " that below mention refers to quality %, and ppm is mg/kg.
Black once colourity is according to JIS K-0071-1-1998 [the colorimetric assay method of chemical products first: the measuring method (platinum-cobalt colour code) of black Zeng Danwei colourity] and is measured by visual.
Embodiment 6
Be provided with return line 3000mL with in the four-hole boiling flask of arm, drop into Dipentaerythritol 607.3g, vinylformic acid 1239.5g, 78% sulfuric acid 40.5g, hydroquinone monomethyl ether 2.7g, normal heptane 810.0g.While oxygen-containing gas (oxygen 5 volume %, nitrogen 95 volume %) is injected into four-hole boiling flask, in reacting liquid temperature 95 ~ 100 DEG C of heated and stirred, the water of generation with Dean-Stark tube drainage to outside system, thus carry out 8 hours dehydration esterification reaction.
After reaction terminates, in reaction solution, drop into the aqueous sodium hydroxide solution 122.5g of 20 quality % and stir, thus a part (0.92 equivalent doubly) for sulfuric acid input by neutralization.Subsequently, add after methylethylketone 1890.0g dilutes, add again relative to organic solvent mutually in the sour composition (vinylformic acid) that contains take molar ratio computing as 20% aqueous sodium hydroxide solution of 1.0 times, thus in and organic solvent mutually in the sour composition (vinylformic acid) that contains.Subsequently, leave standstill and make it to be layered as aqueous phase (lower floor) and organic phase (upper strata), remove the aqueous phase of lower floor.
Secondly, in organic phase, add 20% aqueous sodium hydroxide solution and stir.Leave standstill after making it to be layered as aqueous phase (lower floor) and organic phase (upper strata), remove the aqueous phase of lower floor, reclaim organic phase.In the organic phase reclaimed, then add distilled water 450g and wash.Remove the aqueous phase (lower floor) by standing separation, reclaim the organic phase on upper strata.
Add hydroquinone monomethyl ether 200ppm in the organic phase reclaimed, be under reduced pressure heated to 80 DEG C distill removal solvent while injecting air, thus obtain polyfunctional acrylic ester.
The black once colourity of the polyfunctional acrylic ester obtained is 60.Further, when analyzing polyfunctional acrylic ester by gas-chromatography (Monitoring lower-cut: 10ppm), aromatic series kind solvent is not detected.
Embodiment 7
Be provided with return line 3000mL with in the four-hole boiling flask of arm, drop into tetramethylolmethane 668.2g, vinylformic acid 1556.6g, tosic acid monohydrate (following, to be referred to as PTS) 67.5g, cupric chloride 2.7g, hexanaphthene 405.0g.While injecting the oxygen-containing gas identical with embodiment 6, carry out heated and stirred reacting liquid temperature 75 ~ 80 DEG C.The water Dean-Stark pipe simultaneously generated along with the carrying out of reaction is removed to outside system, thus carries out the dehydration esterification reaction of 10 hours.
After reaction terminates, drop in the reaction solution obtained 20 quality % aqueous sodium hydroxide solution 777.0g (relative to the tosic acid dropped into be 10.9 equivalents doubly) and stir and neutralize, add methylethylketone 1500.0g subsequently, hexanaphthene 1000.0g carry out dilute reaction solution.Leave standstill and make it to be layered as aqueous phase (lower floor) and organic phase (upper strata), remove the aqueous phase of lower floor.
Subsequently, in organic phase, add the aqueous sodium hydroxide solution 500g of 20 quality %, leave standstill after stirring.After being layered as aqueous phase (lower floor) and organic phase (upper strata), remove the aqueous phase of lower floor, reclaim organic phase.In the organic phase reclaimed, then add distilled water 500g and wash.Remove the aqueous phase (lower floor) be separated after leaving standstill, reclaim the organic phase on upper strata.
In the organic phase reclaimed, add hydroquinone monomethyl ether 200ppm, be under reduced pressure added to 80 DEG C to distill removal solvent while injecting air, thus obtain polyfunctional acrylic ester.
The black once colourity of the polyfunctional acrylic ester obtained is 40.During the polyfunctional acrylic ester obtained with gas-chromatography (Monitoring lower-cut: 10ppm) analysis, aromatic series kind solvent is not detected.
Embodiment 8
Except in embodiment 6, after reaction terminates, 20 quality % aqueous sodium hydroxide solution 92.1g are dropped into and in carrying out stirring and after a part (0.70 equivalent doubly) for input sulfuric acid in reaction solution, use methylethylketone dilute reaction solution, add subsequently beyond 20 quality % sodium hydroxide, obtain polyfunctional acrylic ester with the operation identical with embodiment 6.
The black once colourity of the polyfunctional acrylic ester obtained is 60.Further, during the polyfunctional acrylic ester obtained with gas-chromatography (Monitoring lower-cut: 10ppm) analysis, aromatic series kind solvent is not detected.
Comparative example 3
Except in embodiment 6, do not neutralize the sulfuric acid as acid catalyst in advance, but use methylethylketone dilute reaction solution, add subsequently beyond 20 quality % sodium hydroxide, obtain polyfunctional acrylic ester with the operation identical with embodiment 6.
The black once colourity of the polyfunctional acrylic ester obtained is 90.Further, with gas-chromatography (Monitoring lower-cut: 10ppm) analyze the polyfunctional acrylic ester obtained time, aromatic series kind solvent is not detected.
Comparative example 4
Except in embodiment 7, do not neutralize the sulfuric acid as acid catalyst in advance, but use methylethylketone dilute reaction solution, add beyond 20 quality % aqueous sodium hydroxide solutions subsequently, obtain polyfunctional acrylic ester with the operation identical with embodiment 7.
The black once colourity of the polyfunctional acrylic ester obtained is 150.Further, during the polyfunctional acrylic ester obtained with gas-chromatography (Monitoring lower-cut: 10ppm) analysis, aromatic series kind solvent is not detected.
Comparative example 5
Except in embodiment 6, after having reacted, 20 quality % aqueous sodium hydroxide solution 39.5g are dropped into and in carrying out stirring and after a part (0.30 equivalent doubly) for input sulfuric acid in reaction solution, use methylethylketone dilute reaction solution, add subsequently beyond 20 quality % sodium hydroxide, obtain polyfunctional acrylic ester with the operation identical with embodiment 6.
The black once colourity of the polyfunctional acrylic ester obtained is 80.Further, during the polyfunctional acrylic ester obtained with gas-chromatography (Monitoring lower-cut: 10ppm) analysis, aromatic series kind solvent is not detected.
Table 3
Table 4
Industrial applicibility
According to the manufacture method of (methyl) of the present invention acrylate, in esterification and washing procedure, do not use arene compound as organic solvent.Its result, can obtain causing because of arene compound, on personnel's impact of operator and (methyl) acrylate little on the impact of environment, and, painted few (methyl) acrylate can be obtained.
Claims (8)
1. the manufacture method of multifunctional (methyl) acrylate, this manufacture method comprises
1) esterification operation, boiling point is that the aliphatic hydrocarbon compound of 40 ~ 160 DEG C and/or alicyclic hydrocarbon compound are as reaction solvent with carbonatoms 6 ~ 12 and under normal pressure, in the presence of acid catalyst, (methyl) vinylformic acid and polyvalent alcohol is made to carry out esterification, thus the reaction solution obtained containing multifunctional (methyl) acrylate
2) neutralizing treatment operation is diluted, carry out in the reaction solution obtained in esterification operation in any order or simultaneously, add the dilution process operation of the organic solvent be at least made up of ketone compound and/or ester cpds and add the neutralizing treatment operation of alkali aqueous solution, thus obtain dilution neutralizing treatment liquid
3) organic phase recovery process, is separated into aqueous phase and organic phase by the dilution neutralizing treatment liquid that dilution neutralizing treatment operation obtains, thus obtains organic phase,
4) washing step, carries out washing process to the organic phase reclaimed, and
5) separation circuit of multifunctional (methyl) acrylate, organic solvent is distilled out from the organic phase of washing, thus isolate multifunctional (methyl) acrylate from organic solvent after, obtain multifunctional (methyl) acrylate.
2. the manufacture method of multifunctional (methyl) acrylate as claimed in claim 1, wherein, before neutralizing treatment operation, also there is the diluent that the dilution process operation that washes reaction solution that agent washing esterification operation obtains or dilution neutralizing treatment operation with water obtains, thus remove the pre-washing step of acid catalyst.
3. the manufacture method of multifunctional (methyl) acrylate as claimed in claim 1 or 2, wherein, aliphatic hydrocarbon compound and/or alicyclic hydrocarbon compound are more than one compounds being selected from normal hexane, hexanaphthene, methylcyclohexane, normal heptane and octane-iso.
4. as the manufacture method of multifunctional (methyl) acrylate in claims 1 to 3 as described in any one, wherein, ketone compound and/or ester cpds are carbonatoms 3 ~ 8 and under normal pressure, boiling point is the compound of 40 ~ 160 DEG C.
5. the manufacture method of multifunctional (methyl) acrylate, this manufacture method comprises
1) esterification operation, boiling point is that the aliphatic hydrocarbon compound of 40 ~ 160 DEG C and/or alicyclic hydrocarbon compound are as reaction solvent with carbonatoms 6 ~ 12 and under normal pressure, in the presence of acid catalyst, (methyl) vinylformic acid and polyvalent alcohol is made to carry out esterification, thus the reaction solution obtained containing multifunctional (methyl) acrylate
6), in acid catalyst and operation, in the reaction solution obtained, add the alkali composition being at least 1/2 equivalent relative to input acid catalyst, thus obtain acid catalyst neutralization reaction liquid,
7) dilution in and operation, add while the solvent be made up of ketone compound carrys out dilute acid catalyzer neutralization reaction liquid in described acid catalyst neutralization reaction liquid, add buck and neutralize unreacted (methyl) vinylformic acid, thus obtain reaction mixture
8) organic phase recovery process, after the dilution neutralizing treatment liquid obtained is separated into organic phase and aqueous phase, reclaims organic phase in dilution with operation,
9) washing step, carries out washing process to the organic phase reclaimed,
10) separation circuit of multifunctional (methyl) acrylate, organic solvent is distilled out from the organic phase of washing, thus isolate multifunctional (methyl) acrylate from organic solvent after, obtain multifunctional (methyl) acrylate.
6. the manufacture method of multifunctional (methyl) acrylate as claimed in claim 5, wherein, is carrying out in acid catalyst and before operation, is also having the pre-washing step washing agent washing reaction liquid with water.
7. the manufacture method of painted few multifunctional (methyl) acrylate as described in claim 5 or 6, wherein, carbonatoms 6 ~ 12 and under normal pressure, boiling point is the aliphatic hydrocarbon compound of 40 ~ 160 DEG C and/or alicyclic hydrocarbon compound is more than one compounds being selected from normal hexane, hexanaphthene, methylcyclohexane, normal heptane and octane-iso.
8. as the manufacture method of painted few multifunctional (methyl) acrylate in claim 5 ~ 7 as described in any one, wherein, ketone compound is carbonatoms 3 ~ 8 and under normal pressure, boiling point is the compound of 40 ~ 160 DEG C.
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| JP2012-284774 | 2012-12-27 | ||
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| JP2013007322 | 2013-01-18 | ||
| PCT/JP2013/082929 WO2014103676A1 (en) | 2012-12-27 | 2013-12-09 | Method for producing polyfunctional (meth)acrylic acid ester |
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| JPH03271252A (en) * | 1990-03-16 | 1991-12-03 | Arakawa Chem Ind Co Ltd | Production of pentaerythritol-based polyfunctional acrylate |
| JPH07267897A (en) * | 1994-03-30 | 1995-10-17 | Mitsubishi Rayon Co Ltd | Method for purifying hydroxyalkylmono(meth)-acrylate |
| JPH09169699A (en) * | 1995-12-21 | 1997-06-30 | Osaka Organic Chem Ind Ltd | New dibenzoylmethane derivative and its production |
| JP2007182418A (en) * | 2005-07-13 | 2007-07-19 | Koei Chem Co Ltd | Method for producing tripentaerythritol poly(meth)acrylate |
| CN101300221A (en) * | 2005-12-26 | 2008-11-05 | 东亚合成株式会社 | Process for producing (meth)acrylic ester |
| CN101443305A (en) * | 2006-05-10 | 2009-05-27 | 东亚合成株式会社 | Method for producing (meth)acrylate ester |
| CN102276461A (en) * | 2010-06-10 | 2011-12-14 | 湖南石油化学株式会社 | Method of preparing acrylic acid alkyl ester based on azeotropic esterification reaction |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| DE10156116A1 (en) * | 2001-11-15 | 2003-06-26 | Basf Ag | Process for the preparation of (meth) acrylic esters of polyhydric alcohols |
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2013
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- 2013-12-09 JP JP2014554283A patent/JP5900657B2/en not_active Expired - Fee Related
- 2013-12-09 TW TW102145121A patent/TWI582070B/en active
- 2013-12-09 WO PCT/JP2013/082929 patent/WO2014103676A1/en active Application Filing
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02306938A (en) * | 1989-04-19 | 1990-12-20 | Arakawa Chem Ind Co Ltd | Production of dipentaerythritol polyacrylate resistant to emulsification |
| JPH03271252A (en) * | 1990-03-16 | 1991-12-03 | Arakawa Chem Ind Co Ltd | Production of pentaerythritol-based polyfunctional acrylate |
| JPH07267897A (en) * | 1994-03-30 | 1995-10-17 | Mitsubishi Rayon Co Ltd | Method for purifying hydroxyalkylmono(meth)-acrylate |
| JPH09169699A (en) * | 1995-12-21 | 1997-06-30 | Osaka Organic Chem Ind Ltd | New dibenzoylmethane derivative and its production |
| JP2007182418A (en) * | 2005-07-13 | 2007-07-19 | Koei Chem Co Ltd | Method for producing tripentaerythritol poly(meth)acrylate |
| CN101300221A (en) * | 2005-12-26 | 2008-11-05 | 东亚合成株式会社 | Process for producing (meth)acrylic ester |
| CN101443305A (en) * | 2006-05-10 | 2009-05-27 | 东亚合成株式会社 | Method for producing (meth)acrylate ester |
| CN102276461A (en) * | 2010-06-10 | 2011-12-14 | 湖南石油化学株式会社 | Method of preparing acrylic acid alkyl ester based on azeotropic esterification reaction |
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| TW201437196A (en) | 2014-10-01 |
| TWI582070B (en) | 2017-05-11 |
| JP5900657B2 (en) | 2016-04-06 |
| WO2014103676A1 (en) | 2014-07-03 |
| JPWO2014103676A1 (en) | 2017-01-12 |
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