CN102850299B - Preparation method for (methyl)glycidyl acrylate - Google Patents
Preparation method for (methyl)glycidyl acrylate Download PDFInfo
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- CN102850299B CN102850299B CN201210320921.7A CN201210320921A CN102850299B CN 102850299 B CN102850299 B CN 102850299B CN 201210320921 A CN201210320921 A CN 201210320921A CN 102850299 B CN102850299 B CN 102850299B
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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 organism preparation field.
Background technology
The structural formula of (methyl) glycidyl acrylate is:
(methyl) glycidyl acrylate has epoxy-functional end group, because both containing carbon-carbon double bond in molecular structure, respond again active and that cementability is extremely strong epoxy group(ing), free radical type and the reaction of ionic type can be carried out respectively, there is very strong reactive behavior, be therefore widely used in the various fields such as organic macromolecule synthesis and modification.Mainly be used in acrylic acid synthesizing resin art, glycidyl methacrylate and other acrylate carry out copolymerization, and preparation has the acrylic resin of property, is mainly used in the spray coatings of automobile.This acrylic resin containing epoxy group(ing) than conventional containing the resin of epoxy group(ing) have better weather-proof, heat-resisting, water-fast, alkaline-resisting, shock-resistance, can process and snappiness.
At present, both at home and abroad (methyl) glycidyl acrylate research and produce nearly all to adopt and first prepare (methyl) vinylformic acid sodium salt, under stopper exists, strict dry sodium salt and greatly excessive epoxy chloropropane are carried out phase-transfer-catalyzed reactions, finally remove side product chlorinated sodium and excess epoxy chloropropane obtains (methyl) glycidyl acrylate.The advantage of the method is the reaction times shorter (2-4 hour), and productive rate generally can reach 90%, and quality product can meet service requirements.But there are following some shortcomings in this synthetic method: one, phase-transfer-catalyzed reactions step requires high to (methyl) sodium acrylate purity salt and moisture content, the water content of sodium salt need be less than 0.5% and could meet production requirement, requires high and sodium salt water content very easily affects product yield on equipment for drying; Two, in phase transfer reaction, epoxy chloropropane consumption is large, and need 4-10 doubly, energy consumption is increased recovery greatly and aftertreatment disengaging time extends greatly; Three, phase transfer reaction is owing to generating a large amount of inorganic salt, and post-processing step is complicated, is separated washing technology difficulty large, there is unfriendly factor to environment and equipment.Therefore, the production cost that employing aforesaid method carries out (methyl) glycidyl acrylate is high, and environmental stress is large.As: application number be 200410027093.3 application discloses a kind of method preparing glycidyl methacrylate, (methyl) vinylformic acid and caustic alkali are reacted in aqueous solvent, generate 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 during product distillation after filter and remove hydrogenchloride, underpressure distillation obtains fine work.
For the production of (methyl) glycidyl acrylate and the deficiency of synthesis, application number is the preparation method that application discloses one (methyl) glycidyl acrylate of 200710025047.3, with (methyl) vinylformic acid for raw material, be that catalyzer and epoxy chloropropane carry out esterification by ring opening reaction with alkaline organic compound under stopper exists; Then obtained (methyl) glycidyl acrylate of ring-closure reaction is carried out with sodium hydroxide; The method completes reaction in an individual system, therefore belongs to single stage method system.Methacrylic acid an alkali metal salt will be first generated before improving, could continue after process to react the technique generating product, decrease operation steps, correspondingly reduce cost, but it still has the following disadvantages: catalyzer amine organic compound has certain toxicity, reclaim difficulty, to operator and environmental influence large; Productive rate is not high, and production cost is still higher.
Summary of the invention
The object of the invention is to: the deficiency that yield is low, preparation cost is high and catalyst recovery is difficult overcoming (methyl) glycidyl acrylate in prior art, a kind of preparation method 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 is realized 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 added 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 excess epoxy chloropropane, solvent, water and chloride salt, obtain (methyl) glycidyl acrylate product.The method adopts esterification-closed loop process, can a still operate continuously, and technical process is simple; Do not need to add quaternary ammonium salt catalyzer, reduce costs, decrease the step reclaiming catalyzer; And be reactive liquid solution, fully, reaction is easily carried out, and this inventive method can obtain the yield of 85% in reactant contact.
Concrete scheme is as follows:
A kind of preparation method of (methyl) glycidyl acrylate, comprises the following steps successively:
A, (methyl) vinylformic acid and alkali metal hydroxide or alkali metal alcoholates are added dropwise in epoxy chloropropane, three kinds of molar ratio of material are 1:(0.1 ~ 0.5): (1.01 ~ 10), and under the existence having stopper and water and organic solvent, react 0.3 ~ 2.0 hour under 45 ~ 110 DEG C of conditions;
B, add alkali metal hydroxide or alkali metal alcoholates again, until the total amount of the alkali metal hydroxide added in steps A and B or alkali metal alcoholates and (methyl) acrylic acid mol ratio reach (1.01 ~ 2.5): 1, then react 0.5 ~ 3.0 hour at 20 ~ 90 DEG C;
C, step B obtained reaction mixture and remove the water and chloride salt that excessive epoxy chloropropane, solvent and reaction generate, obtain required (methyl) glycidyl acrylate.
As optimal way, in 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, in described step B, total amount and (methyl) acrylic acid mol ratio of alkali metal hydroxide or alkali metal alcoholates are (1.01 ~ 1.1): 1.
Further preferably, described alkali metal hydroxide is sodium hydroxide or potassium hydroxide, and alkali metal alcoholates is the sodium alkoxide containing 1 ~ 6 carbon atom.
As optimal way, in described steps A, organic solvent to be carbonatoms be 1 ~ 4 alcohol.As optimal way, described carbonatoms be 1 ~ 4 alcohol be one or more in methyl alcohol, ethanol, Virahol or propyl carbinol.
As optimal way, in described steps A, (methyl) vinylformic acid and alkali metal hydroxide or alkali metal alcoholates add simultaneously, or add alkali metal hydroxide or alkali metal alcoholates again after first adding (methyl) vinylformic acid.
As optimal way, in described steps A, react and carry out 0.5 ~ 1.5 hour at the temperature of 65 ~ 95 DEG C.
As optimal way, in described step B, at the temperature of 40 ~ 70 DEG C, carry out 0.8 ~ 2.5 hour.
As optimal way, in described steps A, in reaction mixture, the content of organic solvent remains on 1.5 ~ 10mol/mol(methyl) in acrylic acid scope.
As optimal way, in described steps A and B, in reaction mixture, the content of water is at maintenance 4 ~ 15mol/mol(methyl) in acrylic acid scope.
Reaction principle of the present invention is as follows:
Reaction formula A:
Reaction formula B:
As can be seen from reaction formula A, because (methyl) of the present invention vinylformic acid drips continuously within the regular hour, epoxy chloropropane can be made like this to reach decades of times relative to the instantaneous excessive multiple of (methyl) vinylformic acid added, even thousands of times, in reaction, epoxy chloropropane exists with excess form, is conducive to the generation of reaction intermediate; In reaction B, the present invention by adding alkali metal hydroxide or alkali metal alcoholates, by converted be desired product, thus reach the target of raising (methyl) vinylformic acid reactivity and effective conversion rate of products.
Contriver is found by a large amount of experiments: the mode adopting (methyl) vinylformic acid and alkali metal hydroxide or alkali metal alcoholates simultaneously to drip continuously can greatly reduce the consumption of epoxy chloropropane, reduce the side reaction because epoxy chloropropane open loop brings, improve the yield of reaction.The usage quantity of epoxy chloropropane is minimum can in 1.01mol/mol acid, alkali metal hydroxide or alkali metal alcoholates usage quantity minimum can 1.01mol/mol acid, the usage quantity of organic solvent is minimum can in 1.5mol/mol acid, under such proportioning raw materials condition, the foreign matter content generated in reaction process is few, does not produce corrosives hydrogenchloride; In still-process, polymkeric substance generation is low, and do not affect product yield and quality, the highest yield can reach 85%, and product highest purity can reach 99%, and product was room temperature preservation 12 months, and colourity is constant, does not produce decomposition or polymerism.
Beneficial effect of the present invention: stable reaction of the present invention, simple to operate, epoxy chloropropane and consumption of organic solvent few, generate waste liquid few, preparation cost is low.(methyl) glycidyl acrylate yield is high, purity is high.Good product quality, can never degenerate for 12 months.
Accompanying drawing explanation
Fig. 1 is reaction process schema of the present invention;
Mark in 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 for illustration of the present invention.
embodiment 1:
As shown in Figure 1, a kind of preparation method of (methyl) glycidyl acrylate, comprises the following steps:
A, to stirring, in the 1L flask of four mouthfuls 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 DEG C, 54g vinylformic acid and 12.3g sodium hydroxide solution (sodium hydroxide weight percent is 50%) are added dropwise in flask, it is 20 minutes that feed time controls, and reacts and carry out 30 minutes under 65 DEG C of conditions;
B, steps A is obtained reaction mixture be cooled to 55 DEG C, water phase separated, then add 35.5g potassium hydroxide and 74g water, then react 30 minutes at 55 DEG C;
C, step B is obtained reaction mixture at pressure is 95.4KPa, temperature is distill at 120 DEG C, then underpressure distillation is continued, until pressure is 30KPa, temperature is 100 DEG C, remove the water that excessive epoxy chloropropane, solvent and reaction generate, cross and filter chloride salt, obtain required glycidyl acrylate.Reaction product is discharged and analyzes: products therefrom epoxy equivalent (weight) value is 144g/mol, and yield is 85%, purity 99%(GC).This product under being placed in sealed vessel room temperature shady and cool dry environment place 12 months, without obvious variable color and polymerism.
embodiment 2:
As shown in Figure 1, a kind of preparation method of (methyl) glycidyl acrylate, comprises the following steps:
A, to stirring, in the 10L reactor A of four mouthfuls of thermometer and backflow, 1500g Virahol, 33g p-tert-butylphenol, 1508g water and 1350g epoxy chloropropane is added by pump, be heated to 75 DEG C, 968g methacrylic acid and 249g sodium hydroxide solution (sodium hydroxide weight percent is 50%) are added dropwise in reactor A, react and carry out 40 minutes under 75 DEG C of conditions;
B, steps A is obtained reaction mixture be cooled to 50 DEG C, enter water-and-oil separator water phase separated, then reaction mixture is squeezed into reactor B by pump, in reactor B, add 330g sodium hydroxide and 1110g water, then react 120 minutes at 50 DEG C;
C, step B is obtained reaction mixture at pressure is 50KPa, temperature is distill at 97 DEG C, then underpressure distillation is continued, until pressure is 30KPa, temperature is 100 DEG C, remove the water that excessive epoxy chloropropane, solvent and reaction generate, cross and filter chloride salt, obtain required (methyl) glycidyl acrylate.Reaction product is discharged and analyzes: products therefrom epoxy equivalent (weight) value is 144g/mol, and yield is 83%.
In described steps A, (methyl) vinylformic acid and sodium hydroxide solution can add simultaneously, add sodium hydroxide solution again after also first can adding (methyl) vinylformic acid.
embodiment 3:
As shown in Figure 1, a kind of preparation method of (methyl) glycidyl acrylate, comprises the following steps:
A, to stirring, in the 10L reactor A of four mouthfuls of thermometer and backflow, 15mol methyl alcohol, 0.2mol p-tert-butylphenol, 45mol water and 11mol epoxy chloropropane is added by pump, be heated to 45 DEG C, by 10mol(methyl) vinylformic acid and 1mol sodium hydroxide solution (sodium hydroxide weight percent is 50%) be added dropwise in reactor A, react and carry out 0.3 hour under 45 DEG C of conditions;
B, steps A is obtained reaction mixture be cooled to 20 DEG C, enter water-and-oil separator water phase separated, then reaction mixture is squeezed into reactor B by pump, in reactor B, add 10mol sodium hydroxide and 45mol water, then react 180 minutes at 30 DEG C;
C, step B is obtained reaction mixture at pressure is 50KPa, temperature is distill at 97 DEG C, then underpressure distillation is continued, until pressure is 30KPa, temperature is 100 DEG C, remove the water that excessive epoxy chloropropane, solvent and reaction generate, cross and filter chloride salt, obtain required (methyl) glycidyl acrylate.Reaction product is discharged and analyzes: products therefrom epoxy equivalent (weight) value is 143g/mol, and yield is 68%.
In described steps A, (methyl) vinylformic acid and sodium hydroxide solution can add simultaneously, add sodium hydroxide solution again after also first can adding (methyl) vinylformic acid.
embodiment 4:
Repeating the process of embodiment 1, is potassium tert.-butoxide unlike esterifying catalyst added in steps A.Products therefrom epoxy equivalent (weight) value is 148g/mol, and yield is 73%.
embodiment 5:
Repeating the process of embodiment 1, is sodium ethylate unlike esterifying catalyst added in steps A.Products therefrom epoxy equivalent (weight) value is 145g/mol, and yield is 75%.
embodiment 6:
A, to stirring, in the 1L flask of four mouthfuls of thermometer and backflow, add 540g Virahol, 3.25g p-tert-butylphenol, 216g water and 920g epoxy chloropropane, be heated to 85 DEG C, 86g methacrylic acid and 40g sodium hydroxide solution (sodium hydroxide weight percent is 50%) are added dropwise in flask, it is 60 minutes that feed time controls, and reacts and carry out 30 minutes under 85 DEG C of conditions;
B, steps A is obtained reaction mixture be cooled to 40 DEG C, water phase separated, then add 60g sodium hydroxide and 120g water, then react 80 minutes at 50 DEG C;
C, step B is obtained reaction mixture at pressure is 100KPa, temperature is distill at 120 DEG C, then underpressure distillation is continued, until pressure is 30KPa, temperature is 100 DEG C, remove the water that excessive epoxy chloropropane, solvent and reaction generate, cross and filter chloride salt, obtain required glycidyl methacrylate.Reaction product is discharged and analyzes: products therefrom epoxy equivalent (weight) value is 154g/mol, and yield is 65%.
embodiment 7:
Repeat the process of embodiment 3, unlike steps A temperature of reaction 100 DEG C, 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, unlike step B temperature of reaction 85 DEG C.Products therefrom epoxy equivalent (weight) value is 157g/mol, and yield is 76%.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, all any amendments done within the spirit and principles in the present invention, equivalent replacement and improvement etc., all should be included within protection scope of the present invention.
Claims (9)
1. the preparation method of (methyl) glycidyl acrylate, is characterized in that comprising the following steps successively:
A, (methyl) vinylformic acid and alkali metal hydroxide or alkali metal alcoholates are added dropwise in epoxy chloropropane, three kinds of molar ratio of material are 1:(0.15 ~ 0.3): (1.3 ~ 4), and under the existence having stopper and water and organic solvent, react 0.3 ~ 2.0 hour under 45 ~ 110 DEG C of conditions;
B, add alkali metal hydroxide or alkali metal alcoholates again, until the total amount of the alkali metal hydroxide added in steps A and B or alkali metal alcoholates and (methyl) acrylic acid mol ratio reach (1.01 ~ 2.5): 1, then react 0.5 ~ 3.0 hour at 20 ~ 90 DEG C;
C, step B obtained reaction mixture and remove the water and chloride salt that excessive epoxy chloropropane, solvent and reaction generate, obtain required (methyl) glycidyl acrylate.
2. the preparation method of (methyl) glycidyl acrylate as claimed in claim 1, it is characterized in that: in described step B, total amount and (methyl) acrylic acid mol ratio of alkali metal hydroxide or alkali metal alcoholates are (1.01 ~ 1.1): 1.
3. the preparation method of (methyl) glycidyl acrylate as claimed in claim 1 or 2, is characterized in that: described alkali metal hydroxide is sodium hydroxide or potassium hydroxide, and alkali metal alcoholates is the sodium alkoxide containing 1 ~ 6 carbon atom.
4. the preparation method of (methyl) glycidyl acrylate as claimed in claim 1, is characterized in that: in described steps A, organic solvent to be carbonatoms be 1 ~ 4 alcohol.
5. the preparation method of (methyl) glycidyl acrylate as claimed in claim 1, it is characterized in that: in described steps A, (methyl) vinylformic acid and alkali metal hydroxide or alkali metal alcoholates add simultaneously, or add alkali metal hydroxide or alkali metal alcoholates again after first adding (methyl) vinylformic acid.
6. the preparation method of (methyl) glycidyl acrylate as claimed in claim 1, is characterized in that: in described steps A, reacts and carry out 0.5 ~ 1.5 hour at the temperature of 65 ~ 95 DEG C.
7. the preparation method of (methyl) glycidyl acrylate as claimed in claim 1, is characterized in that: in described step B, carries out 0.8 ~ 2.5 hour at the temperature of 40 ~ 70 DEG C.
8. the preparation method of (methyl) glycidyl acrylate as claimed in claim 1, it is characterized in that: in described steps A, in reaction mixture, the content of organic solvent remains on 1.5 ~ 10mol/mol(methyl) in acrylic acid scope.
9. the preparation method of (methyl) glycidyl acrylate as claimed in claim 1, is characterized in that: in described steps A and B, in reaction mixture, the content of water is at maintenance 4 ~ 15mol/mol(methyl) in acrylic acid scope.
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| 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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