CN102850299A - Preparation method for (methyl)glycidyl acrylate - Google Patents
Preparation method for (methyl)glycidyl acrylate Download PDFInfo
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- CN102850299A CN102850299A CN2012103209217A CN201210320921A CN102850299A CN 102850299 A CN102850299 A CN 102850299A CN 2012103209217 A CN2012103209217 A CN 2012103209217A CN 201210320921 A CN201210320921 A CN 201210320921A CN 102850299 A CN102850299 A CN 102850299A
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Abstract
The invention discloses a preparation method for (methyl)glycidyl acrylate, and belongs to the field of organic matter preparation. The method sequentially comprises the following steps: A, adding (methyl)acrylic acid and an alkali metal hydroxide or an alkali metal alkoxide to epichlorohydrin in a dropwise manner, and carrying out a reaction for 0.3-2.0 hours at a temperature of 45-110 DEG C in the presence of a polymerization inhibitor, water and an organic solvent, wherein a molar ratio of the three materials is 1:(0.1-0.5):(1.01-10); B, adding the alkali metal hydroxide or the alkali metal alkoxide until a molar ratio of the total amount of the alkali metal hydroxide or the alkali metal alkoxide in the step A and the step B to the (methyl)acrylic acid is (1.01-2.5):1, and then carrying out a reaction for 0.5-3.0 hours at a temperature of 20-90 DEG C; and C, removing impurities to obtain the product. The (methyl)glycidyl acrylate prepared by the preparation method of the present invention has characteristics of high yield, high purity, and low preparation cost.
Description
Technical field
The invention belongs to the organism preparation field.
Background technology
The structural formula of (methyl) glycidyl acrylate is:
(methyl) glycidyl acrylate has the epoxy-functional end group, because both contained carbon-carbon double bond in the molecular structure, active and the extremely strong epoxy group(ing) of cementability respond again, can carry out respectively free radical type and the reaction of ionic type, have very strong reactive behavior, therefore be widely used in organic macromolecule synthetic with the various fields such as modification.Mainly be used in synthesizing propylene acid resin field, glycidyl methacrylate and other acrylate carry out copolymerization, prepare the acrylic resin with property, are mainly used in the spray coatings of automobile.This acrylic resin that contains epoxy group(ing) has better weather-proof, heat-resisting, water-fast, alkaline-resisting, shock-resistance, can process and snappiness than the conventional resin that does not contain epoxy group(ing).
At present, first preparation (methyl) vinylformic acid sodium salt is nearly all adopted in the research of (methyl) glycidyl acrylate both at home and abroad and production, the sodium salt of the lower strictly drying of stopper existence and greatly excessive epoxy chloropropane carry out phase-transfer-catalyzed reactions, remove at last by product sodium-chlor and excessive epoxy chloropropane and obtain (methyl) glycidyl acrylate.The advantage of the method is that the reaction times lacks (2-4 hour), and productive rate generally can reach 90%, and quality product can satisfy service requirements.But there are following some shortcomings in this synthetic method: one, the phase-transfer-catalyzed reactions step requires high to (methyl) sodium acrylate purity salt and moisture content, the water content need of sodium salt could satisfy production requirement less than 0.5%, require height and sodium salt water content very easily to affect product yield on equipment for drying; Two, the epoxy chloropropane consumption is large in the phase transfer reaction, needs 4-10 doubly, and recovery is so that energy consumption increases greatly and the aftertreatment disengaging time prolongs greatly; Three, phase transfer reaction is owing to generate a large amount of inorganic salt, and post-processing step is complicated, and separation washing technology difficulty is large, and there are unfriendly factor in environment and equipment.Therefore, adopt aforesaid method to carry out the production cost height of (methyl) glycidyl acrylate, environmental stress is large.A kind of method for preparing glycidyl methacrylate that has been 200410027093.3 Patent Application Publication such as: application number, (methyl) vinylformic acid and caustic alkali are reacted in aqueous solvent, generate the methacrylic acid alkali metal salt, react under stopper and catalyzer Tetramethyl Ethylene Diamine existence condition with epoxy chloropropane again, obtain crude product, add diethyl phthalate when product distills after the filter and remove hydrogenchloride, underpressure distillation obtains elaboration.
For the production of (methyl) glycidyl acrylate and synthetic deficiency, the application number preparation method of a kind of (methyl) glycidyl acrylate that has been 200710025047.3 Patent Application Publication, take (methyl) vinylformic acid as raw material, in the presence of stopper take alkaline organic compound as catalyzer and epoxy chloropropane carry out esterification by ring opening reaction; Then carry out ring-closure reaction with sodium hydroxide and make (methyl) glycidyl acrylate; The method is finished reaction in an individual system, therefore belongs to the single stage method system.To generate first the methacrylic acid an alkali metal salt before having improved, could continue the technique that reaction generates product after the processing, reduced operation steps, the corresponding cost that reduced, but it still has the following disadvantages: catalyzer amine organic compound has certain toxicity, reclaim difficulty, large to operator and environmental influence; Productive rate is not high, and production cost is still higher.
Summary of the invention
The object of the invention is to: overcome the deficiency that yield is low, preparation cost is high and catalyst recovery is difficult of (methyl) glycidyl acrylate in the prior art, the preparation method of a kind of (methyl) glycidyl acrylate is provided.(methyl) glycidyl acrylate yield of this preparation method is high, purity is high, and preparation cost is low.
The object of the invention realizes by following technical proposals:
One, methacrylic acid and epoxy chloropropane generate esterification open loop intermediate product under alkali metal hydroxide or alkali metal alcoholates catalysis, and the water that adds in this process and organic solvent can reduce temperature of reaction, greatly reduce the hydrolysis reaction of epoxy chloropropane; Two, this intermediate product generates target product at alkali metal hydroxide or alkali metal alcoholates condition ShiShimonoseki ring; Three, remove excessive epoxy chloropropane, solvent, water and chloride salt, obtain (methyl) glycidyl acrylate product.The method adopts esterification-closed loop technique, can a still operate continuously, and technical process is simple; Do not need to add the quaternary ammonium salt catalyzer, reduce cost, reduced the step that reclaims catalyzer; And be reactive liquid solution, the reactant contact is fully reacted and is carried out easily, and this inventive method can obtain 85% yield.
Concrete scheme is as follows:
The preparation method of a kind of (methyl) glycidyl acrylate may further comprise the steps successively:
A, (methyl) vinylformic acid and alkali metal hydroxide or alkali metal alcoholates are added dropwise in the epoxy chloropropane, three kinds of molar ratio of material are 1:(0.1～0.5): (1.01～10), and have stopper and water and organic solvent in the presence of, under 45～110 ℃ of conditions, reacted 0.3～2.0 hour;
B, add alkali metal hydroxide or alkali metal alcoholates again, until the total amount of the alkali metal hydroxide that adds among steps A and the B or alkali metal alcoholates reaches (1.01～2.5) with (methyl) acrylic acid mol ratio: 1, then 20～90 ℃ of lower reactions 0.5～3.0 hour;
C, step B is obtained reaction mixture remove water and the chloride salt that excessive epoxy chloropropane, solvent and reaction generate, obtain required (methyl) glycidyl acrylate.
As optimal way, in the described steps A, the mol ratio of (methyl) vinylformic acid and alkali metal hydroxide or alkali metal alcoholates and epoxy chloropropane is 1:(0.15～0.3): (1.3～4).
As optimal way, among the described step B, the total amount of alkali metal hydroxide or alkali metal alcoholates is (1.01～1.1) with (methyl) acrylic acid mol ratio: 1.
Further preferred, described alkali metal hydroxide is sodium hydroxide or potassium hydroxide, and alkali metal alcoholates is the sodium alkoxide that contains 1～6 carbon atom.
As optimal way, in the described steps A, organic solvent is that carbonatoms is 1～4 alcohol.As optimal way, described carbonatoms is that 1～4 alcohol is one or more in methyl alcohol, ethanol, Virahol or the propyl carbinol.
As optimal way, in the described steps A, (methyl) vinylformic acid and alkali metal hydroxide or alkali metal alcoholates add simultaneously, perhaps add alkali metal hydroxide or alkali metal alcoholates behind adding (methyl) vinylformic acid first again.
As optimal way, in the described steps A, reaction was carried out under 65～95 ℃ temperature 0.5～1.5 hour.
As optimal way, among the described step B, carried out under 40～70 ℃ the temperature 0.8～2.5 hour.
As optimal way, in the described steps A, the content of organic solvent remains on 1.5～10mol/mol(methyl in the reaction mixture) in acrylic acid scope.
As optimal way, among described steps A and the B, the content of water is keeping 4～15mol/mol(methyl in the reaction mixture) in acrylic acid scope.
Reaction principle of the present invention is as follows:
Reaction formula A:
Reaction formula B:
Can find out from reaction formula A, because (methyl) of the present invention vinylformic acid drips within the regular hour continuously, can make like this epoxy chloropropane reach decades of times with respect to the excessive multiple of (methyl) vinylformic acid of instantaneous adding, even thousands of times, epoxy chloropropane exists with excessive form in the reaction, is conducive to the generation of reaction intermediate; In reaction B, the present invention is converted into desired product by adding alkali metal hydroxide or alkali metal alcoholates with intermediate, thereby reaches the target of raising (methyl) vinylformic acid reactivity and effective conversion rate of products.
The contriver finds by a large amount of experiments: the mode that adopts (methyl) vinylformic acid and alkali metal hydroxide or alkali metal alcoholates to drip continuously simultaneously can greatly reduce the consumption of epoxy chloropropane, the side reaction that minimizing brings because of the epoxy chloropropane open loop improves the yield of reaction.The usage quantity of epoxy chloropropane is minimum can be in 1.01mol/mol acid, alkali metal hydroxide or alkali metal alcoholates usage quantity are minimum can be in 1.01mol/mol acid, the usage quantity of organic solvent is minimum can be in 1.5mol/mol acid, under such proportioning raw materials condition, the foreign matter content that generates in the reaction process is few, does not produce corrosives hydrogenchloride; The polymkeric substance generation is low in still-process, does not affect product yield and quality, and the highest yield can reach 85%, and the product highest purity can reach 99%, and product was room temperature preservation 12 months, and colourity is constant, does not produce and decomposes or polymerism.
Beneficial effect of the present invention: stable reaction of the present invention, simple to operate, epoxy chloropropane and consumption of organic solvent are few, and it is few to generate waste liquid, and preparation cost is low.(methyl) glycidyl acrylate yield is high, purity is high.Good product quality can never degenerate in 12 months.
Description of drawings
Fig. 1 is reaction process schema of the present invention;
Mark among the figure: 1 (methyl) vinylformic acid storage tank, 2 reactors, 3 sodium hydroxide storage tanks, 4 water coolers, 5 water-and-oil separators, 6 thick products pots.
Embodiment
Following non-limiting examples is used for explanation the present invention.
Embodiment 1:
As shown in Figure 1, the preparation method of a kind of (methyl) glycidyl acrylate may further comprise the steps:
A, to stirring, in the 1L flask of the four-hole of thermometer and backflow, add the 124.9g trimethyl carbinol, 2.25g p-tert-butylphenol, 100.5g water and 234.9g epoxy chloropropane, be heated to 65 ℃, 54g vinylformic acid and 12.3g sodium hydroxide solution (the sodium hydroxide weight percent is 50%) are added dropwise in the flask, feed time is controlled to be 20 minutes, and reaction was carried out 30 minutes under 65 ℃ of conditions;
B, steps A is obtained reaction mixture be cooled to 55 ℃, water phase separated adds 35.5g potassium hydroxide and 74g water again, then 55 ℃ of lower reactions 30 minutes;
C, step B is obtained reaction mixture is 95.4KPa at pressure, temperature is to distill under 120 ℃, then continue underpressure distillation, until pressure is 30KPa, temperature is 100 ℃, remove the water that excessive epoxy chloropropane, solvent and reaction generate, remove by filter chloride salt, obtain required glycidyl acrylate.The reaction product discharge is analyzed: products therefrom epoxy equivalent (weight) value is 144g/mol, and yield is 85%, purity 99%(GC).This product places under the sealed vessel room temperature shady and cool dry environment to place 12 months, without obviously variable color and polymerism.
Embodiment 2:
As shown in Figure 1, the preparation method of a kind of (methyl) glycidyl acrylate may further comprise the steps:
A, to stirring, among the 10L reactor A of the four-hole of thermometer and backflow, add 1500g Virahol, 33g p-tert-butylphenol, 1508g water and 1350g epoxy chloropropane by pump, be heated to 75 ℃, 968g methacrylic acid and 249g sodium hydroxide solution (the sodium hydroxide weight percent is 50%) are added dropwise among the reactor A, and reaction was carried out 40 minutes under 75 ℃ of conditions;
B, steps A is obtained reaction mixture be cooled to 50 ℃, enter the water-and-oil separator water phase separated, again reaction mixture is squeezed into reactor B by pump, in reactor B, add 330g sodium hydroxide and 1110g water, then 50 ℃ of lower reactions 120 minutes;
C, step B is obtained reaction mixture is 50KPa at pressure, temperature is to distill under 97 ℃, then continue underpressure distillation, until pressure is 30KPa, temperature is 100 ℃, remove the water that excessive epoxy chloropropane, solvent and reaction generate, remove by filter chloride salt, obtain required (methyl) glycidyl acrylate.The reaction product discharge is analyzed: products therefrom epoxy equivalent (weight) value is 144g/mol, and yield is 83%.
In the described steps A, (methyl) vinylformic acid and sodium hydroxide solution can add simultaneously, add sodium hydroxide solution after also can adding first (methyl) vinylformic acid again.
Embodiment 3:
As shown in Figure 1, the preparation method of a kind of (methyl) glycidyl acrylate may further comprise the steps:
A, to stirring, among the 10L reactor A of the four-hole of thermometer and backflow, add 15mol methyl alcohol, 0.2mol p-tert-butylphenol, 45mol water and 11mol epoxy chloropropane by pump, be heated to 45 ℃, with the 10mol(methyl) vinylformic acid and 1mol sodium hydroxide solution (the sodium hydroxide weight percent is 50%) be added dropwise among the reactor A, and reaction was carried out 0.3 hour under 45 ℃ of conditions;
B, steps A is obtained reaction mixture be cooled to 20 ℃, enter the water-and-oil separator water phase separated, again reaction mixture is squeezed into reactor B by pump, in reactor B, add 10mol sodium hydroxide and 45mol water, then 30 ℃ of lower reactions 180 minutes;
C, step B is obtained reaction mixture is 50KPa at pressure, temperature is to distill under 97 ℃, then continue underpressure distillation, until pressure is 30KPa, temperature is 100 ℃, remove the water that excessive epoxy chloropropane, solvent and reaction generate, remove by filter chloride salt, obtain required (methyl) glycidyl acrylate.The reaction product discharge is analyzed: products therefrom epoxy equivalent (weight) value is 143g/mol, and yield is 68%.
In the described steps A, (methyl) vinylformic acid and sodium hydroxide solution can add simultaneously, add sodium hydroxide solution after also can adding first (methyl) vinylformic acid again.
Embodiment 4:
Repeat the process of embodiment 1, different is, and to add esterifying catalyst in the steps A be potassium tert.-butoxide.Products therefrom epoxy equivalent (weight) value is 148g/mol, and yield is 73%.
Embodiment 5:
Repeat the process of embodiment 1, different is, and to add esterifying catalyst in the steps A be sodium ethylate.Products therefrom epoxy equivalent (weight) value is 145g/mol, and yield is 75%.
Embodiment 6:
A, to stirring, in the 1L flask of the four-hole of thermometer and backflow, add 540g Virahol, 3.25g p-tert-butylphenol, 216g water and 920g epoxy chloropropane, be heated to 85 ℃, 86g methacrylic acid and 40g sodium hydroxide solution (the sodium hydroxide weight percent is 50%) are added dropwise in the flask, feed time is controlled to be 60 minutes, and reaction was carried out 30 minutes under 85 ℃ of conditions;
B, steps A is obtained reaction mixture be cooled to 40 ℃, water phase separated adds 60g sodium hydroxide and 120g water again, then 50 ℃ of lower reactions 80 minutes;
C, step B is obtained reaction mixture is 100KPa at pressure, temperature is to distill under 120 ℃, then continue underpressure distillation, until pressure is 30KPa, temperature is 100 ℃, remove the water that excessive epoxy chloropropane, solvent and reaction generate, remove by filter chloride salt, obtain required glycidyl methacrylate.The reaction product discharge is analyzed: products therefrom epoxy equivalent (weight) value is 154g/mol, and yield is 65%.
Embodiment 7:
Repeat the process of embodiment 3, different is 100 ℃ of steps A temperature of reaction, 100 minutes reaction times.Products therefrom epoxy equivalent (weight) value is 158g/mol, and yield is 81%.
Embodiment 8:
Repeat the process of embodiment 3, different is 85 ℃ of step B temperature of reaction.Products therefrom epoxy equivalent (weight) value is 157g/mol, and yield is 76%.
The above only is preferred embodiment of the present invention, not in order to limiting the present invention, all any modifications of doing within the spirit and principles in the present invention, is equal to and replaces and improvement etc., all should be included within protection scope of the present invention.
Claims (10)
1. the preparation method of (methyl) glycidyl acrylate is characterized in that may further comprise the steps successively:
A, (methyl) vinylformic acid and alkali metal hydroxide or alkali metal alcoholates are added dropwise in the epoxy chloropropane, three kinds of molar ratio of material are 1:(0.1～0.5): (1.01～10), and have stopper and water and organic solvent in the presence of, under 45～110 ℃ of conditions, reacted 0.3～2.0 hour;
B, add alkali metal hydroxide or alkali metal alcoholates again, until the total amount of the alkali metal hydroxide that adds among steps A and the B or alkali metal alcoholates reaches (1.01～2.5) with (methyl) acrylic acid mol ratio: 1, then 20～90 ℃ of lower reactions 0.5～3.0 hour;
C, step B is obtained reaction mixture remove water and the chloride salt that excessive epoxy chloropropane, solvent and reaction generate, obtain required (methyl) glycidyl acrylate.
2. the preparation method of (methyl) as claimed in claim 1 glycidyl acrylate, it is characterized in that: in the described steps A, the mol ratio of (methyl) vinylformic acid and alkali metal hydroxide or alkali metal alcoholates and epoxy chloropropane is 1:(0.15～0.3): (1.3～4).
3. the preparation method of (methyl) as claimed in claim 1 glycidyl acrylate is characterized in that: among the described step B, the total amount of alkali metal hydroxide or alkali metal alcoholates is (1.01～1.1) with (methyl) acrylic acid mol ratio: 1.
4. such as the preparation method of claim 1,2 or 3 described (methyl) glycidyl acrylate, it is characterized in that: described alkali metal hydroxide is sodium hydroxide or potassium hydroxide, and alkali metal alcoholates is the sodium alkoxide that contains 1～6 carbon atom.
5. the preparation method of (methyl) as claimed in claim 1 glycidyl acrylate, it is characterized in that: in the described steps A, organic solvent is that carbonatoms is 1～4 alcohol.
6. the preparation method of (methyl) as claimed in claim 1 glycidyl acrylate, it is characterized in that: in the described steps A, (methyl) vinylformic acid and alkali metal hydroxide or alkali metal alcoholates add simultaneously, perhaps add alkali metal hydroxide or alkali metal alcoholates behind adding (methyl) vinylformic acid first again.
7. the preparation method of (methyl) as claimed in claim 1 glycidyl acrylate is characterized in that: in the described steps A, react and carried out under 65～95 ℃ temperature 0.5～1.5 hour.
8. the preparation method of (methyl) as claimed in claim 1 glycidyl acrylate is characterized in that: among the described step B, carried out under 40～70 ℃ the temperature 0.8～2.5 hour.
9. the preparation method of (methyl) as claimed in claim 1 glycidyl acrylate, it is characterized in that: in the described steps A, the content of organic solvent remains on 1.5～10mol/mol(methyl in the reaction mixture) in acrylic acid scope.
10. the preparation method of (methyl) as claimed in claim 1 glycidyl acrylate is characterized in that: among described steps A and the B, the content of water is keeping 4～15mol/mol(methyl in the reaction mixture) in acrylic acid scope.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104086509A (en) * | 2014-07-10 | 2014-10-08 | 中昊(大连)化工研究设计院有限公司 | Synthetic method of glycidyl methacrylate |
| JP2015017076A (en) * | 2013-07-12 | 2015-01-29 | 三菱瓦斯化学株式会社 | Highly transparent adamantane carboxylic acid glycidyl ester compound |
| CN105073722A (en) * | 2013-03-22 | 2015-11-18 | 三菱丽阳株式会社 | Process for producing glycidyl (meth)acrylate |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102408396A (en) * | 2010-09-26 | 2012-04-11 | 西南化工研究设计院 | Method for preparing versatate glycidyl |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102408396A (en) * | 2010-09-26 | 2012-04-11 | 西南化工研究设计院 | Method for preparing versatate glycidyl |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105073722A (en) * | 2013-03-22 | 2015-11-18 | 三菱丽阳株式会社 | Process for producing glycidyl (meth)acrylate |
| CN105073722B (en) * | 2013-03-22 | 2017-09-26 | 三菱化学株式会社 | The manufacture method of (methyl) glycidyl acrylate |
| JP2015017076A (en) * | 2013-07-12 | 2015-01-29 | 三菱瓦斯化学株式会社 | Highly transparent adamantane carboxylic acid glycidyl ester compound |
| CN104086509A (en) * | 2014-07-10 | 2014-10-08 | 中昊(大连)化工研究设计院有限公司 | Synthetic method of glycidyl methacrylate |
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