CN102227400B - Method for producing hydroxyalkyl(meth)acrylic acid ester - Google Patents
Method for producing hydroxyalkyl(meth)acrylic acid ester Download PDFInfo
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- CN102227400B CN102227400B CN200980148132.6A CN200980148132A CN102227400B CN 102227400 B CN102227400 B CN 102227400B CN 200980148132 A CN200980148132 A CN 200980148132A CN 102227400 B CN102227400 B CN 102227400B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/03—Preparation of carboxylic acid esters by reacting an ester group with a hydroxy group
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/28—Preparation of carboxylic acid esters by modifying the hydroxylic moiety of the ester, such modification not being an introduction of an ester group
- C07C67/29—Preparation of carboxylic acid esters by modifying the hydroxylic moiety of the ester, such modification not being an introduction of an ester group by introduction of oxygen-containing functional groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
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- C07C2601/14—The ring being saturated
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Abstract
Provided is a method whereby a hydroxyalkyl(meth)acrylic acid ester can be efficiently produced without requiring any troublesome purification step. A method for producing a hydroxyalkyl(meth)acrylic acid ester is characterized by comprising (meth)acrylating a vinyl ether-containing alcohol by the ester exchange method to give a vinyl ether-containing (meth)acrylic acid ester and then conducting a devinylation reaction in the presence of an acid catalyst together with water.
Description
Technical field
The present invention relates to alcohol that a kind of use contains vinyl ether and manufacture the method for (methyl) acrylic acid hydroxy alkyl ester.
Background technology
As the manufacture method of (methyl) acrylic acid hydroxy alkyl ester, common main stream approach is to be obtained, after glycol, monoesters and diester mixture, only monoesters body being extracted to separated method by esterification by alkanediol.Concrete discloses, and for example, under strong acid exists, method (, with reference to patent documentation 1) that vinylformic acid and alkanediol are reacted, still, the method has and produces secondary resultant, reduces the disadvantageous aspects such as yield because of strong acid.As the method addressing this problem, relevant for the various report (for example,, with reference to patent documentation 2～4) of the transesterification reaction of alkanediol and (methyl) acrylate.In addition, for 4-hydroxybutyl (methyl) acrylate, disclose and effectively extracted and the method (for example,, with reference to patent documentation 5～6) of purifying etc.But for the ester-interchange method from alkanediol, because resulting resultant is mixture, therefore, the amount of the extraction solvent needing is excessive for separated monoesters only, inefficent.
As obtain the method for (methyl) acrylic acid hydroxy alkyl ester with 2 stages, disclose the alcohol that contains vinyl ether is carried out after transesterify, under acid catalyst and alcohol existence, take off the method (for example,, with reference to patent documentation 7) of vinylation.But the method, owing to generating acetal compound when the reaction of de-vinylation, therefore need to be removed acetal compound, but the operation that the acetal compound in reaction is removed being not easy.In addition, must remove to discard by washing the alcohol of excessive use when this reaction, and inefficent.
Patent documentation 1: No. 15118572 communique of German Patent
Patent documentation 2: Japanese kokai publication hei 10-298143 communique
Patent documentation 3: Japanese kokai publication hei 11-43466 communique
Patent documentation 4: TOHKEMY 2000-159727 communique
Patent documentation 5: Japanese kokai publication hei 8-53392 communique
Patent documentation 6: TOHKEMY 2005-194201 communique
Patent documentation 7: Japanese kokai publication hei 10-18255 communique
Summary of the invention
The problem that invention will solve
Problem of the present invention is, providing a kind of does not need complicated purification procedures just can effectively manufacture the manufacture method of (methyl) acrylic acid hydroxy alkyl ester.
The means of dealing with problems
The present inventors carry out found that of all discussion, by the alcohol that contains vinyl ether being carried out to (methyl) acroleic acid esterification, generate after (methyl) acrylate that contains vinyl ether, the de-vinylation method that under acid catalyst exists, water is coexisted, can obtain highly purified (methyl) acrylic acid hydroxy alkyl ester with high yield, and the water layer of separated recovery after de-vinylation can recycle.
That is, the present invention is following invention.
(1) manufacture method of (methyl) acrylic acid hydroxy alkyl ester, it is characterized in that, by ester-interchange method, the alcohol that contains vinyl ether being carried out to (methyl) acroleic acid esterification generates after (methyl) acrylate that contains vinyl ether, while taking off vinylation reaction under acid catalyst exists, water is coexisted.
(2), according to the manufacture method of (methyl) acrylic acid hydroxy alkyl ester aforementioned (1) Suo Shu, wherein, temperature of reaction during de-vinylation reaction is below 60 ℃.
(3), according to the manufacture method of (methyl) acrylic acid hydroxy alkyl ester aforementioned (1) or (2) Suo Shu, wherein, the alcohol that contains vinyl ether represents with following general formula (I) or (II).
[changing 1]
(in general formula (I), n represents 3～11 integer.)
[changing 2]
(in general formula (II), A represents cyclopentylidene or cyclohexylidene.)
, Patent 2008-306256 (December 1 2008 applying date) and the application of having advocated right of priority enrolled the content in these specification sheetss in the application in order to reference the application is the Japanese patent application based on formerly being proposed by same applicant.
Invention effect
According to the present invention, can be without the purification procedures of the complexity such as distillation and effectively obtain (methyl) acrylic acid hydroxy alkyl ester, further can recycle the water using in de-vinylation operation, therefore the method for manufacture (methyl) acrylic acid hydroxy alkyl ester of a kind of casual labourer's order and economy can be provided.
Embodiment
Below explain the embodiment of relevant (methyl) of the present invention acrylic acid hydroxy alkyl ester manufacture method.
The manufacture method of (methyl) of the present invention acrylic acid hydroxy alkyl ester, it is characterized in that, by ester-interchange method, the alcohol that contains vinyl ether being carried out to (methyl) acroleic acid esterification generates after (methyl) acrylate that contains vinyl ether, while taking off vinylation reaction under acid catalyst exists, water is coexisted.
In the present invention, first, the hydroxyl of the alcohol that contains vinyl ether is carried out to esterification, obtain (methyl) acrylate that contains vinyl ether.Method as esterification mainly can be enumerated, use the carboxylic acid halides method of (methyl) acrylic acid dehydration esterification process, the ester-interchange method that uses rudimentary (methyl) acrylate, use (methyl) acrylate chloride, wherein, for dehydration esterification process owing to using acid catalyst, thereby produce de-vinylation simultaneously, therefore inapplicable.In addition, carboxylic acid halides method is owing to sloughing halogen by reaction, and remains in system, therefore needs the purification process such as washing, absorption or distillation.And on the other hand, ester-interchange method, because impurity is few, does not need purification process, so the present invention adopts ester-interchange method.
As the alcohol that contains vinyl ether using in the present invention, for example can enumerate, the compound that 4-hydroxy butyl vinyl ether, 6-hydroxyl hexyl vinyl ether, 9-hydroxyl nonyl vinyl ether, 10-hydroxy decyl vinyl ether, 12-hydroxyl dodecyl vinyl etc. represent with following general formula (I), the compound that cyclohexanedimethanol mono vinyl ether etc. represent with following general formula (II), phenyl dimethanol mono vinyl ether etc.
[changing 3]
(in general formula (I), n represents 3～11 integer.)
[changing 4]
(in general formula (II), A represents cyclopentylidene or cyclohexylidene.)
As rudimentary (methyl) acrylate using, specifically can enumerate (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) propyl acrylate, (methyl) butyl acrylate etc. in ester-interchange method., in the application, said rudimentary (methyl) acrylate refers to that having carbonatoms is that alkyl below 4 is as the substituent ester of ester.
When transesterification reaction, short from the reaction times, ester turnover ratio is high, the viewpoint of reacted aftertreatment, with respect to the alkylol cpd that contains vinyl ether, use rudimentary (methyl) acrylate in preferably from equivalent to excessive scope.Particularly, the 1 mole of hydroxyl having with respect to the alkylol cpd that contains vinyl ether is preferably used rudimentary (methyl) acrylate conventionally in the scope of 1.0～20 moles.With respect to 1 mole of hydroxyl of the alkylol cpd that contains vinyl ether, rudimentary (methyl) if the usage quantity of acrylate less than 1.0 moles, react deficiently, in addition, if surpass 20 moles, reacted enrichment process needs for a long time, productivity variation.
As the catalyzer using in ester-interchange method, can enumerate: the alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide; The alkaline carbonates such as Quilonum Retard, sodium carbonate, salt of wormwood; The basic metal alkoxy compounds such as lithium methoxide, sodium methylate, sodium ethylate, potassium tert.-butoxide; The alkali amides such as Lithamide, sodium amide, potassium amide; The titanium metal alkoxides such as metatitanic acid tetramethyl ester, tetraethyl titanate, metatitanic acid orthocarbonate, titanium isopropylate, tetrabutyl titanate; Other as aluminium alkoxide; Alkanol tin etc.Wherein, from the viewpoint that can suppress side reaction, can easily remove catalyzer by adding water reaction finishes, more preferably titanium metal alkoxide or aluminium alkoxide as far as possible.
In addition, the usage quantity of catalyzer is the total amount with the alkylol cpd that contains vinyl ether with respect to rudimentary (methyl) acrylate, is conventionally preferably the scope of 0.01～5.0 quality %.Even if what impact catalytic amount, for more than needing, does not have to speed of response yet, on the contrary, only can when removing, catalyzer need a large amount of water etc. to become uneconomical.
In transesterification reaction in the present invention, can add, also use known stopper.As stopper such as enumerating: the phenols such as quinhydrones, hydroquinone monomethyl ether (also referred to as " p methoxy phenol "); The sulphur compound such as thiodiphenylamine, ethylene thiourea; The mantoquitas such as copper dibutyldithiocarbamate; The manganese salt such as manganese acetate; The compound oxygen radical of nitrogen such as nitro-compound, nitroso compound, Tempol free radical etc.The addition of stopper, with respect to generating ester, is preferably below 0.1 quality %.If surpass 0.1 quality %, have and painted situation occurs because of additive.
When transesterification reaction, be preferably blown into for preventing a small amount of molecular oxygen of the reaction solution polymerization of reaction.As molecular oxygen, preferably under the state of dilution, use, it is suitable using air.In addition, being blown into preferably to evaporate as steam of molecular oxygen exists, or also can be blown in the polymerization of condensing (methyl) esters of acrylic acid such as the still wall on top in order to prevent.
Molecular oxygen refers to the triplet oxygen molecule (O of the ground state of making by 2 Sauerstoffatoms
2), can when reaction, with original state, participate in reaction directly, also can be transformed into after the states such as singlet oxygen molecule or Sauerstoffatom, super-oxide, superoxide by the interaction of catalyzer or reaction reagent, participate in the oxygen molecule of reaction.
As the import volume of molecular oxygen, by the shape of reaction machine or stir power and exert an influence, but with respect to 1 mole of the alcohol that contains vinyl ether as raw material, the 5～500ml/ of can usining divides the speed of (25～2500ml/ divides as air) to be blown into.If the import volume of molecular oxygen is less than 5ml/ timesharing, the effect that inhibition is closed is insufficient, if surpass 500ml/, divide, rudimentary (methyl) acrylate is extruded to the effect grow outside system, cause the loss as rudimentary (methyl) acrylate of raw material.
Transesterification reaction of the present invention is preferably under normal pressure or decompression, carry out at 60～120 ℃.If temperature is less than 60 ℃, speed of response reacts slack-off terrifically, if surpass 120 ℃, is easily created in the polymerization of (methyl) acrylate that contains vinyl ether obtaining in transesterification reaction, also easily causes painted.
As the form of transesterification reaction, can carry out with the method known to those skilled in the art of general manufactured (methyl) acrylate.When transesterification reaction, need to the raw lower alcohol of pair be carried out to component distillation with rudimentary (methyl) acrylate and/or solvent and remove.Therefore, as reaction unit, for example use the intermittent reaction groove of subsidiary rectifying tower.
After transesterification reaction finishes, by water, make catalyst deactivation, with concentrating unit distillation, remove excessive low boiling point component.Low boiling point component is removed by concentrating unit distillation, preferably on one side under normal pressure or decompression, liquid temperature remains on below 90 ℃, Yi Bian carry out, more preferably in the scope of 50～70 ℃.If liquid temperature surpasses 90 ℃, the possibility that produces the painted or polymerization of (methyl) acrylate that contains vinyl ether uprises.
Complete (methyl) acrylate that contains vinyl ether that the distillation of low boiling point component removes and can, by filtering, remove the remaining insoluble compositions such as decaying catalyst.In order effectively to remove insoluble composition, during filtration, preferably use the filtration adjuvants such as diatomite.
Next, to the de-vinylation reaction of (methyl) acrylate that contains vinyl ether, the method that obtains (methyl) acrylic acid hydroxy alkyl ester is illustrated.
In the present invention, under existing, acid catalyst takes off vinylation reaction, as operable acid catalyst, conventionally can enumerate: sulfuric acid, sodium pyrosulfate, tosic acid, Phenylsulfonic acid, methylsulfonic acid, solid acid (zeolite, An Bailaite, Amberlyst, Nafion etc.).In addition, the catalytic amount of use, with respect to (methyl) acrylate that contains vinyl ether reacting, is preferably 0.01 quality %～10 quality %, more preferably 0.1 quality %～5 quality %.If during less than 0.01 quality %, having, the catalytic amount using reduces significantly the situation that reactive, de-vinylation reaction becomes slow terrifically.In addition, if while surpassing 10 quality %, on almost not impact of speed of response, but then, likely produce impurity.
The de-vinylation reaction the present invention relates to is characterised in that, water is coexisted and carry out.By water is coexisted, react, can easily remove secondary raw aldehyde when de-vinylation reaction.Usage quantity as water, so long as take (methyl) acrylate of containing vinyl ether as benchmark is more than waiting mole, just be not particularly limited, preferably by use take that (methyl) acrylate of containing vinyl ether is benchmark more than 2 times moles, make to carry out with being swift in response.If with when waiting mole few ratio to make water, reaction stops halfway.
The de-vinylation reaction the present invention relates to is thermopositive reaction.At this moment, by temperature of reaction being controlled at below 60 ℃, be preferably controlled at 0 ℃～40 ℃, can obtain highly purified (methyl) acrylic acid hydroxy alkyl ester.As the method for controlling temperature of reaction, can enumerate cooling reactor, or in aqueous catalyst solution, add at leisure the method for (methyl) acrylate that contains vinyl ether.In addition, secondary during reaction have acetaldehyde, but by reducing pressure in system, can promptly remove acetaldehyde, promotes reaction.
After de-vinylation reaction finishes, from reaction residue, water layer is removed in separation.Now, in order to improve separating power, can be used singly or two or more kinds in combination as toluene or dimethylbenzene equal solvent.The water of the water layer that carries out separation to remove and obtain can the manufacture after next time in, as the water coexisting in de-vinylation reaction, recycle.
Separated organic layer is owing to containing catalyzer, therefore with alkali, neutralizes and separation is removed.As alkali, such as enumerating: oxyhydroxide or the salt of the basic metal such as potassium hydroxide, sodium hydroxide, salt of wormwood, sodium carbonate, saleratus, sodium bicarbonate, alkaline-earth metal.Preferably they are used with the form of the aqueous solution, after neutralization, carry out that separation is removed and the method used.
After neutralization, water or the excessive alkali of neutral salt aqueous cleaning and after removing, remove excessive water distillation by concentrated, or while using solvent distillation except desolventizing.Concentrated preferably on one side under normal pressure or decompression, to keep liquid temperature be below 90 ℃, Yi Bian carry out, in the scope of more preferably 50 ℃～80 ℃.If liquid temperature surpasses 90 ℃, the possibility that produces the painted or polymerization of (methyl) acrylic acid hydroxy alkyl ester becomes large.
After concentrated, can be by filtering to remove the remaining insoluble compositions such as neutralized salt.In order effectively to remove insoluble composition, during filtration, preferably use the filtration adjuvants such as diatomite.
The manufacture method of (methyl) of the present invention acrylic acid hydroxy alkyl ester, owing to making water when de-vinylation reacts, can obtain highly purified (methyl) acrylic acid hydroxy alkyl ester, does not therefore need the purification procedures such as distillation.
Embodiment
Below, enumerate embodiment and further specifically describe the present invention, but the present invention is not limited in these embodiment.
Embodiment 1
Synthesizing of methacrylic acid vinyloxy group butyl ester
In the detachable flask of four-hole round bottom of 4L, put into 4-hydroxy butyl vinyl ether (ball is apt to petroleum chemistry HBVE processed) 1000g, methyl methacrylate 3000g, p methoxy phenol 0.65g, rectifying tower (15 layers), stirrer, air leading-in conduit and thermometer are set.Under agitation, on one side with 100ml part, import dry air, start heating on one side, regulating pressure is that about 40kPa, the liquid temperature in the flask while making to reflux is 75 ℃, removes the moisture in system.Moisture in confirmation system be 300ppm following after, put into the tetraisopropoxy titanium 8.6g as catalyzer, the mode that the temperature of reaction of take is 95 ± 5 ℃ controls flask internal pressure for about 60kPa.If monitor the temperature (tower top temperature) of rectifier when reflux, owing to approaching the methyl alcohol of generation and the azeotropic temperature of methyl methacrylate, therefore regulating reflux ratio to make tower top temperature is 60 ℃ of left and right, on one side using methyl alcohol as distilling and remove with the azeotrope of methyl methacrylate, Yi Bian react.
Due to from reaction is during through 4 hours, tower top temperature starts to raise, and therefore increases at leisure reflux ratio, and sustained reaction.With the gc analysis reaction reaction solution of the 5th hour, consequently ester turnover ratio is 99.2%, so termination reaction.Cooling reaction solution, when liquid temperature is 75 ℃, adds the salt solution 250g of 17 quality %, hydrolyst.After standing 15 minutes, by decant, organic layer is fetched in eggplant type flask, uses Rotary Evaporators, under reduced pressure distillation is removed after excessive methyl methacrylate, by suction filtration, the liquid in eggplant type flask is filtered, obtain the methacrylic acid vinyloxy group butyl ester 1522g as object.
Synthesizing of methacrylic acid 4-hydroxyl butyl ester
In the detachable flask of four-hole of 1L, pack tosic acid 16g, pure water 200g into, stirrer, thermometer, air leading-in conduit are set and with the vacuum pump of cooling clip.In flask, slowly add above-mentioned synthetic methacrylic acid vinyloxy group butyl ester 500g.System internal pressure is made as to 20kPa, under agitation, on one side from removing the acetaldehyde of generation in system, advance reaction on one side.At this moment, on one side flask uses frozen water cooling, Yi Bian temperature of reaction is remained on to 15～30 ℃.React after 3 hours, utilize vapor-phase chromatography analysis, reaction conversion rate is almost 100%, therefore finishes reaction.The salt solution 50g that adds toluene 100g, 17 quality % in the liquid finishing in reaction, carries out oily water separation, only takes out organic layer (water layer is used in embodiment 4).Use separating funnel to clean after organic layer with the sodium bicarbonate aqueous solution 70g of 5 quality %, with the salt solution 70g of 17 quality %, clean.Organic layer is fetched in eggplant type flask, uses Rotary Evaporators, under reduced pressure distillation is removed after excessive toluene, by suction filtration, filters, and obtains the methacrylic acid 4-hydroxyl butyl ester 395g (yield 92.2%, purity 99.1%) as object.
Embodiment 2
Synthesizing of vinylformic acid vinyloxy group butyl ester
In the detachable flask of four-hole round bottom of 4L, put into 4-hydroxy butyl vinyl ether (ball is apt to petroleum chemistry HBVE processed) 1000g, ethyl propenoate 3000g, p methoxy phenol 0.65g, rectifying tower (15 layers), stirrer, air leading-in conduit and thermometer are set.With 100ml/, divide importing dry air under agitation, on one side, start heating on one side, regulating pressure is that about 40kPa, the liquid temperature in the flask while making to reflux is 75 ℃, removes the moisture in system.Moisture in confirmation system be 300ppm following after, put into the tetraisopropoxy titanium 8.6g as catalyzer, the mode that the temperature of reaction of take is 95 ± 5 ℃ controls flask internal pressure for about 60kPa.If monitor the temperature (tower top temperature) of rectifier when reflux, owing to approaching the ethanol of generation and the azeotropic temperature of ethyl propenoate, therefore regulating reflux ratio to make tower top temperature is 70 ℃ of left and right, on one side using ethanol as distilling and remove with the azeotrope of ethyl propenoate, Yi Bian react.
Due to from reaction is during through 4 hours, tower top temperature starts to raise, and therefore increases at leisure reflux ratio, and sustained reaction.With the gc analysis reaction reaction solution of the 5th hour, consequently ester turnover ratio is 99.0%, so reaction terminating.Cooling reaction solution, when liquid temperature is 75 ℃, adds the salt solution 250g of 17 quality %, hydrolyst.After standing 15 minutes, by decant, organic layer is fetched in eggplant type flask, uses Rotary Evaporators, under reduced pressure distillation is removed after excessive ethyl propenoate, by suction filtration, the liquid in eggplant type flask is filtered, obtain the vinylformic acid vinyloxy group butyl ester 1376g as object.
Synthesizing of vinylformic acid 4-hydroxyl butyl ester
In the detachable flask of four-hole of 1L, pack tosic acid 16g, pure water 200g into, stirrer, thermometer, air leading-in conduit are set and with the vacuum pump of cooling clip.In flask, slowly add above-mentioned synthetic vinylformic acid vinyloxy group butyl ester 500g.System internal pressure is made as to 20kPa, under agitation, on one side from removing the acetaldehyde of generation in system, advance reaction on one side.At this moment, on one side flask uses frozen water cooling, Yi Bian temperature of reaction is remained on to 15～30 ℃.React after 3 hours, by vapor-phase chromatography, analyze, reaction conversion rate is 99.9%, therefore finishes reaction.The salt solution 50g that adds toluene 200g, 17 quality % in the liquid finishing in reaction, carries out oily water separation, only takes out organic layer.Use separating funnel to clean after organic layer with the sodium bicarbonate aqueous solution 70g of 5 quality %, with the salt solution 70g of 17 quality %, clean.Organic layer is fetched in eggplant type flask, uses Rotary Evaporators, under reduced pressure distillation is removed after excessive toluene, by suction filtration, filters, and obtains the vinylformic acid 4-hydroxyl butyl ester 389g (yield 92.0%, purity 99.0%) as object.
Embodiment 3
Synthesizing of cyclohexanedimethanol vinyl ether methacrylic ester
In the four-hole round-bottomed flask of 1L, put into cyclohexanedimethanol mono vinyl ether (ball is apt to petroleum chemistry CHMVE processed) 300g, methyl methacrylate 600g, p methoxy phenol 0.20g, rectifying tower (15 layers), stirrer, air leading-in conduit and thermometer are set.With 100ml/, divide importing dry air under agitation, on one side, start heating on one side, regulating pressure is that about 40kPa, the liquid temperature in the flask while making to reflux is 75 ℃, removes the moisture in system.Moisture in confirmation system be 300ppm following after, put into the tetraisopropoxy titanium 2.6g as catalyzer, the mode that the temperature of reaction of take is 95 ± 5 ℃ controls flask internal pressure for about 60kPa.If monitor the temperature (tower top temperature) of rectifier when reflux, owing to approaching the methyl alcohol of generation and the azeotropic temperature of methyl methacrylate, therefore regulating reflux ratio to make tower top temperature is 60 ℃ of left and right, on one side using methyl alcohol as distilling and remove with the azeotrope of methyl methacrylate, Yi Bian react.
Due to from reaction is during through 2 hours, tower top temperature starts to raise, and therefore increases at leisure reflux ratio, and sustained reaction.With the gc analysis reaction reaction solution of the 3rd hour, consequently ester turnover ratio is 99.4%, so reaction terminating.Cooling reaction solution, when liquid temperature is 75 ℃, adds the salt solution 100g of 17 quality %, hydrolyst.After standing 15 minutes, by decant, organic layer is fetched in eggplant type flask, use Rotary Evaporators, under reduced pressure distillation is removed after excessive methyl methacrylate, by suction filtration, the liquid in eggplant type flask is filtered, obtain the cyclohexanedimethanol vinyl ether methacrylic ester 385g as object.
Synthesizing of cyclohexanedimethanol monomethacrylates
In the detachable flask of four-hole of 500mL, pack tosic acid 6.4g, pure water 80g into, stirrer, thermometer, air leading-in conduit are set and with the vacuum pump of cooling clip.In flask, slowly add above-mentioned synthetic cyclohexanedimethanol vinyl ether methacrylic ester 200g.System internal pressure is made as to 20kPa, under agitation, on one side from removing the acetaldehyde of generation in system, advance reaction on one side.At this moment, on one side flask uses frozen water cooling, Yi Bian temperature of reaction is remained on to 15～30 ℃.React after 2 hours, by vapor-phase chromatography, analyze, reaction conversion rate is 99.9%, therefore finishes reaction.The salt solution 30g that adds toluene 80g, 17 quality % in the liquid finishing in reaction, carries out oily water separation, only takes out organic layer.Use separating funnel to clean after organic layer with the sodium bicarbonate aqueous solution 20g of 5 quality %, with the salt solution 30g of 17 quality %, clean.Organic layer is fetched in eggplant type flask, use Rotary Evaporators, under reduced pressure distillation is removed after excessive toluene, by suction filtration, filters, and obtains the cyclohexanedimethanol monomethacrylates 163g (yield 91.5%, purity 99.4%) as object.
Embodiment 4
The manufacture method of the methacrylic acid 4-hydroxyl butyl ester based on water recycling
Be enclosed in embodiment 1 in the detachable flask of four-hole of 1L in, after reaction, carry out separated water layer (all wts), stirrer, thermometer, air leading-in conduit are set and with the vacuum pump of cooling clip.In flask, slowly add synthetic methacrylic acid vinyloxy group butyl ester 500g in embodiment 1.System internal pressure is made as to 20kPa, under agitation, on one side from removing the acetaldehyde of generation in system, advance reaction on one side.At this moment, on one side flask uses frozen water cooling, Yi Bian temperature of reaction is remained on to 15～30 ℃.React after 3 hours, by vapor-phase chromatography, analyze, reaction conversion rate is 99.9%, therefore finishes reaction.In the liquid finishing in reaction, add toluene 100g, carry out oily water separation, only take out organic layer.Use separating funnel to clean after organic layer with the sodium bicarbonate aqueous solution 70g of 5 quality %, with the salt solution 70g of 17 quality %, clean.Organic layer is fetched in eggplant type flask, uses Rotary Evaporators, under reduced pressure distillation is removed after excessive toluene, by suction filtration, filters, and obtains the methacrylic acid 4-hydroxyl butyl ester 398g (yield 92.8%, purity 99.2%) as object.
Embodiment 5
Temperature of reaction is the manufacture method of 60 ℃ of methacrylic acid 4-hydroxyl butyl esters when above
In the detachable flask of four-hole of 1L, pack tosic acid 16g, pure water 200g into, stirrer, thermometer, air leading-in conduit are set and with the vacuum pump of cooling clip.In flask, add methacrylic acid vinyloxy group butyl ester 500g synthetic in embodiment 1 quickly, rapidly system internal pressure is made as to 20kPa, under agitation, on one side from removing the acetaldehyde of generation in system, advance reaction on one side.At this moment, flask does not carry out cooling and while placing, temperature of reaction rises to 65 ℃.React after 3 hours, by vapor-phase chromatography, analyze, reaction conversion rate is almost 100%, therefore finishes reaction.The salt solution 50g that adds toluene 100g, 17 quality % in the liquid finishing in reaction, carries out oily water separation, only takes out organic layer.Use separating funnel to clean after organic layer with the sodium bicarbonate aqueous solution 70g of 5 quality %, with the salt solution 70g of 17 quality %, clean.Organic layer is fetched in eggplant type flask, uses Rotary Evaporators, under reduced pressure distillation is removed after excessive toluene, by suction filtration, filters, and obtains the methacrylic acid 4-hydroxyl butyl ester 385g (yield 89.9%, purity 97.0%) as object.
When known temperature of reaction like this surpasses 60 ℃, compare yield slight reduction with embodiment 1.
Comparative example 1
The manufacture method of the methacrylic acid 4-hydroxyl butyl ester under glycol coexists
In the detachable flask of four-hole of 1L, pack tosic acid 16g, ethylene glycol 200g into, stirrer, thermometer, air leading-in conduit are set and with the vacuum pump of cooling clip.In flask, slowly add synthetic methacrylic acid vinyloxy group butyl ester 500g in synthesis example 1.System internal pressure is made as to 20kPa, under agitation, on one side from removing the acetal of generation in system, advance reaction on one side.At this moment, on one side flask uses frozen water cooling, Yi Bian temperature of reaction is remained on to 15～30 ℃.React after 3 hours, by vapor-phase chromatography, analyze, reaction conversion rate is 78%.In addition, due to by analyzing in reaction system also remaining acetal compound, be therefore heated to 50 ℃, continue to react.After heating starts, the reaction conversion rate of 1 hour is 98.4%, therefore finishes reaction.The salt solution 150g that adds toluene 200g, 5 quality % in the liquid finishing in reaction, carries out oily water separation, only takes out organic layer.Use separating funnel to clean after organic layer with the sodium bicarbonate aqueous solution 70g of 5 quality %, with the salt solution 70g of 17 quality %, clean.Organic layer is fetched in eggplant type flask, uses Rotary Evaporators, under reduced pressure distillation is removed after excessive toluene, by suction filtration, filters, and obtains the methacrylic acid 4-hydroxyl butyl ester 395g (yield 87.6%, purity 92.3%) as object.
From above result, in order to obtain (methyl) acrylic acid hydroxy alkyl ester, when de-vinylation reaction, by water is coexisted, can obtain highly purified (methyl) acrylic acid hydroxy alkyl ester with high yield.In addition, from embodiment 4, recycling in the de-vinylation reaction of the water layer of separated recovery in can the manufacture after next time after de-vinylation.
Claims (2)
1. the manufacture method of (methyl) acrylic acid hydroxy alkyl ester, it is characterized in that, by ester-interchange method, the alcohol that contains vinyl ether being carried out to (methyl) acroleic acid esterification generates after (methyl) acrylate that contains vinyl ether, while taking off vinylation reaction under acid catalyst exists, water is coexisted, the usage quantity of water, take (methyl) acrylate of containing vinyl ether as benchmark is more than waiting mole
Wherein, the alcohol that contains vinyl ether represents with following general formula (I) or (II),
In general formula (I), n represents 3～11 integer,
In general formula (II), A represents cyclopentylidene or cyclohexylidene.
2. the manufacture method of (methyl) according to claim 1 acrylic acid hydroxy alkyl ester, wherein, temperature of reaction during de-vinylation reaction is below 60 ℃.
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| PCT/JP2009/068798 WO2010064514A1 (en) | 2008-12-01 | 2009-11-04 | Method for producing hydroxyalkyl(meth)acrylic acid ester |
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