CN111170836B - Preparation method of pentaerythritol triallyl ether - Google Patents
Preparation method of pentaerythritol triallyl ether Download PDFInfo
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- CN111170836B CN111170836B CN202010090158.8A CN202010090158A CN111170836B CN 111170836 B CN111170836 B CN 111170836B CN 202010090158 A CN202010090158 A CN 202010090158A CN 111170836 B CN111170836 B CN 111170836B
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- pentaerythritol
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- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
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Abstract
The invention provides a preparation method of pentaerythritol triallyl ether, and particularly relates to the technical field of synthesis of pentaerythritol triallyl ether, which is characterized by comprising the following steps: s1, putting pentaerythritol, pentaerythritol triallyl ether, tetrabutylammonium bromide and 50% aqueous solution of sodium hydroxide into a stirring reaction kettle under normal pressure, and heating to dissolve the pentaerythritol into liquid; s2, dropping chloropropene, keeping chloropropene and water to be distilled out, separating chloropropene and water after condensation, and returning chloropropene to the stirring reaction kettle; and S3, adding water after the reaction is finished, cooling, standing, layering, and carrying out vacuum distillation on the upper layer of organic phase to obtain the pentaerythritol triallyl ether. The preparation method of pentaerythritol triallyl ether provided by the invention adopts pentaerythritol triallyl ether as a solvent during synthesis, optimizes and removes the addition of inert solvent in the prior art, does not need rectification recycling or environmental protection treatment measures of the inert solvent, avoids high-pressure operation by using water as the solvent, and ensures that the reaction is favorable for generating pentaerythritol triallyl ether.
Description
[ technical field ]
The invention relates to a method for synthesizing polyol allyl ether compounds, in particular to synthesis of pentaerythritol triallyl ether.
[ background Art ]
Pentaerythritol triallyl ether has 3 allyl groups and 1 hydroxyl group, has isomerization, oxygen bonding, polymerization and other performances, is used as a polymer monomer or a cross-linking agent for preparing an acrylic polymer type thickening agent and a super absorbent resin, improves the salt resistance of the super absorbent resin, can reduce and eliminate the oxygen inhibition effect by grafting improved unsaturated polyester, polyurethane resin, epoxy resin and UV curing resin, realizes photocuring in the air, is increased year by year in the field of chemical green low-carbon coatings, and is an important organic compound.
At present, williamson etherification is adopted for industrial preparation of pentaerythritol triallyl ether, and the method has the advantages of low price and easiness in obtaining of raw materials and relatively mild reaction, and is a great deal of targeted research of industry workers.
The Zhejiang industrial university patent CN101343213B, the Zhuhai Feiyang chemical company Limited patent CN101200413B and the China petrochemical Qilu petrochemical company patent CN1052970C use inert solvents such as toluene, benzene, ethyl acetate, dichloromethane, ether and dimethyl sulfoxide to participate in synthesis to improve the yield and the product quality, and because a large amount of organic solvents are used, the post-treatment needs to adopt rectification recycling and environmental protection treatment measures.
The patent CN100410304C of Nanjing Will chemical industry Limited company selects water as a solvent to synthesize under the pressure of 0.2MPa so as to reduce the by-product and improve the selectivity, and because a pressurizing device is adopted for reaction, the equipment investment is large, and the operation is difficult.
[ summary of the invention ]
In order to overcome the defects of the prior art, the invention provides a preparation method of pentaerythritol triallyl ether, and the technical scheme is as follows.
A preparation method of pentaerythritol triallyl ether is characterized by comprising the following steps:
s1, putting a solid raw material pentaerythritol, a solvent pentaerythritol triallyl ether, a phase transfer catalyst tetrabutylammonium bromide and a raw material 50% aqueous solution of sodium hydroxide into a stirring reaction kettle according to a certain proportion under the normal pressure condition, and heating to 90-100 ℃ to completely dissolve the pentaerythritol into liquid;
s2, dropwise adding chloropropene serving as a raw material, maintaining the reaction temperature at 95-105 ℃, keeping the chloropropene and water to be continuously evaporated, separating chloropropene and water after condensation, returning the chloropropene to the stirring reaction kettle, controlling the feeding speed of the chloropropene according to the water separation condition, and keeping the reaction for 10-16 hours;
and S3, adding a certain amount of water after the reaction is finished, cooling to 30-50 ℃, standing for layering, and carrying out vacuum distillation on the upper layer organic phase to obtain the product pentaerythritol triallyl ether.
Further, in the step S1, the mass ratio of pentaerythritol serving as a solid raw material to pentaerythritol triallyl ether serving as a solvent is 100:8 to 12.
Further, in the step S1, the mass ratio of the solid raw material pentaerythritol to the phase transfer catalyst tetrabutylammonium bromide is 100:3 to 5.
Further, in the step S1, the mass ratio of pentaerythritol to 50% sodium hydroxide aqueous solution as solid raw materials is 100: 190-220.
Further, in the step S2, the mass ratio of pentaerythritol to chloropropene added is 100:150 to 200.
Further, the water in the step S2 as the cooling stratified water in the step S3 can also be used as a sodium hydroxide solution to prepare water.
Further, the mass ratio of the pentaerythritol to the added water in the step S3 is 100:50 to 300.
Furthermore, the total ether content of the pentaerythritol triallyl ether product in the step S3 is more than 99%, and the product yield is more than 85%.
The invention has the beneficial effects that:
the preparation method of pentaerythritol triallyl ether provided by the invention specifically adopts pentaerythritol triallyl ether as a solvent during synthesis, optimizes and removes the addition of inert solvent in the prior art, does not need rectification recycling of the inert solvent or environmental protection treatment measures, avoids high-pressure operation with water as the solvent, and ensures that the reaction is favorable for generating pentaerythritol triallyl ether.
[ detailed description of the invention ]
The present invention may be embodied in many different forms and is not limited to the embodiments described herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
A preparation method of pentaerythritol triallyl ether comprises the following steps:
s1, putting a solid raw material pentaerythritol, a solvent pentaerythritol triallyl ether, a phase transfer catalyst tetrabutylammonium bromide and a raw material 50% aqueous solution of sodium hydroxide into a stirring reaction kettle according to a certain proportion under the condition of normal pressure, and heating to 90-100 ℃ to completely dissolve the pentaerythritol into liquid.
S2, dropwise adding chloropropene serving as a raw material, maintaining the reaction temperature at 95-105 ℃, continuously evaporating chloropropene and water, separating chloropropene and water after condensation, returning chloropropene to the stirring reaction kettle, controlling the feeding speed of chloropropene according to the water separation condition, and keeping the reaction for 10-16 hours.
And S3, adding a certain amount of water after the reaction is finished, cooling to 30-50 ℃, standing for layering, and carrying out vacuum distillation on the upper layer to obtain the pentaerythritol triallyl ether product.
The reaction mechanism of the invention is as follows:
solid pentaerythritol is added into a solvent pentaerythritol triallyl ether, so that the melting temperature can be effectively reduced, the solid pentaerythritol is completely dissolved into liquid at the temperature of 90-100 ℃, the collision with a sodium hydroxide aqueous solution is increased, the generated pentaerythritol sodium salt is dissolved in the pentaerythritol triallyl ether under the action of a phase transfer catalyst according to a similar compatibility principle, and the generated pentaerythritol sodium salt and chloropropene dripped into the solvent are subjected to substitution reaction, so that the contact between the chloropropene and sodium hydroxide and water is reduced, and the generation of byproducts is inhibited.
As the selected solvent is a product, the dosage of the solvent is very critical, the excessive addition inhibits the generation of reaction products, and the excessive addition can not completely dissolve the solid pentaerythritol raw material.
The mass ratio of the solid raw material pentaerythritol to the solvent pentaerythritol triallyl ether in the invention is preferably 100:8 to 12.
The mass ratio of the solid raw material pentaerythritol to the phase transfer catalyst tetrabutylammonium bromide in the invention is preferably 100:3 to 5.
In order to ensure that the conversion of pentaerythritol is complete, the molar weight of sodium hydroxide is added to be more than 3 times that of pentaerythritol, and the mass ratio of the solid raw material pentaerythritol to 50% aqueous solution of sodium hydroxide is preferably 100: 190-220.
In order to ensure that the pentaerythritol is completely converted and simultaneously take out water generated in the reaction process, the mol weight of chloropropene added in the pentaerythritol is more than 3 times that of chloropropene, and the mass ratio of pentaerythritol to chloropropene as a solid raw material is preferably 100:150 to 200.
After the reaction is finished, a certain amount of water is added to separate the generated salt from the product organic phase, the salt water treatment cost is increased when the adding amount of the water is too much, the separation effect is poor when the adding amount of the water is too little, the organic phase impurities are more, and the mass ratio of the solid pentaerythritol to the added water is preferably 100:50 to 300.
The water produced in the reaction process and the sodium hydroxide solution water are continuously taken out by chloropropene, and the condensed and layered water can be used as the cooling layered water in the steps and can also be used as the sodium hydroxide solution to prepare water.
The organic phase is distilled under the pressure of-0.095 MPa and the fraction at the temperature of 150-180 ℃ is collected to obtain the product, the total ether content of pentaerythritol triallyl ether is more than 99 percent, and the product yield is more than 85 percent.
Example 1
Raw materials and dosage:
pentaerythritol (> 98%) 100g
190g of aqueous sodium hydroxide solution (50%)
Pentaerythritol triallyl ether 10g
Chloropropene 150g
Tetrabutylammonium bromide 3g
Respectively adding pentaerythritol, aqueous solution (50 percent) of sodium hydroxide, pentaerythritol triallyl ether and tetrabutylammonium bromide into a four-neck flask provided with a reflux condenser, a stirrer, a thermometer and a dropping funnel, heating and stirring until the temperature is raised to 90 ℃ until the pentaerythritol is completely dissolved into liquid, beginning to dropwise add 150g of chloropropene, controlling the dropwise adding speed to be slow, and finishing dropwise adding within about 3 hours; refluxing is large during dripping, chloropropene and water are continuously distilled out, and layered water is collected; the reaction temperature was observed, and the temperature was raised to 110 ℃ to continue the reflux reaction for 1 hour to stop the reaction.
And adding 50g of collecting water into the mixture after the reaction, stirring uniformly, standing for layering, separating out lower-layer water, and collecting an organic layer. Carrying out rotary evaporation on the organic layer, removing light components and water, distilling and collecting distillate at the temperature of 150-180 ℃ under the pressure of-0.095 MPa to obtain 161g of a product; wherein the content of pentaerythritol diallyl ether is 4.74 percent, the content of pentaerythritol triallyl ether is 85.91 percent, the content of pentaerythritol tetraallyl ether is 8.72 percent, and the total ether content is 99.37 percent; the molar yield based on pentaerythritol was 85.5%.
Example 2
Raw materials and dosage:
pentaerythritol (> 98%) 100g
220g of aqueous sodium hydroxide solution (50%)
Pentaerythritol triallyl ether 12g
Chloropropene 200g
Tetrabutylammonium bromide 5g
The procedure was as in example 1 to give 167g of product; wherein the content of pentaerythritol diallyl ether is 3.28 percent, the content of pentaerythritol triallyl ether is 84.76 percent, the content of pentaerythritol tetraallyl ether is 11.04 percent, and the total ether content is 99.08 percent; the molar yield based on pentaerythritol was 88.7%.
Example 3
Raw materials and dosage:
2500kg of pentaerythritol (> 98%) (III)
4750kg of sodium hydroxide aqueous solution (50 percent)
200kg of pentaerythritol triallyl ether
3750kg of chloropropene
75kg of tetrabutylammonium bromide
Putting pentaerythritol, sodium hydroxide aqueous solution (50%), pentaerythritol triallyl ether and tetrabutylammonium bromide according to the formula ratio into a reaction kettle provided with a stirring device, a heating coil, a condenser and a water separation tank, closing a feeding valve, heating to 90 ℃ until the pentaerythritol is completely melted, starting stirring, uniformly stirring, and slowly dropwise adding chloropropene.
Gradually increasing the dropping speed according to the kettle temperature, continuously dividing water in the dropping process, continuously increasing the kettle temperature in the whole dropping process, sampling and analyzing chloropropene when the temperature is increased to 110 ℃, continuously dropping chloropropene according to the analysis result, and controlling the dropping time to be 10-16 hours. After the dropwise addition, the reaction was stopped after maintaining the reflux reaction for two hours.
Keeping the temperature for half an hour, adding 1250kg of water in the water separation tank, cooling, stirring and washing, cooling to 50 ℃, stirring and washing for 30min, and separating out lower layer water.
Distilling the upper organic phase to remove light components, reducing the pressure to-0.095 MPa, and collecting 150-180 ℃ fractions to obtain 4030kg of a product, wherein the content of pentaerythritol diallyl ether is 5.28%, the content of pentaerythritol triallyl ether is 87.64%, the content of pentaerythritol tetraallyl ether is 6.14%, and the content of total ether is 99.06%; the molar yield based on pentaerythritol was 85.63%.
The preparation of pentaerythritol triallyl ether in the technical scheme of the invention adopts a pentaerythritol triallyl ether product as a synthetic solvent, optimizes and removes the addition of inert solvent in the prior art, and does not need the rectification recycling of the inert solvent or environmental protection treatment measures. The invention can be operated under normal pressure, avoids the high-pressure operation of using water as a solvent, and ensures that the reaction is favorable for generating pentaerythritol triallyl ether. The invention does not introduce external solvent of product, the rectification process is simple, the product quality is high, and the yield is improved. The preparation method is suitable for the requirement of industrial production.
The above description is only a preferred embodiment of the present invention, and the protection scope of the present invention is not limited to the above embodiment, and all technical solutions belonging to the principle of the present invention belong to the protection scope of the present invention. Modifications to the disclosed embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention.
Claims (3)
1. A preparation method of pentaerythritol triallyl ether is characterized by comprising the following steps:
s1, putting a solid raw material pentaerythritol, a solvent pentaerythritol triallyl ether, a phase transfer catalyst tetrabutylammonium bromide and a raw material 50% aqueous solution of sodium hydroxide into a stirring reaction kettle in proportion under normal pressure, and heating to 90-100 ℃ to completely dissolve the pentaerythritol into liquid; the mass ratio of pentaerythritol as a solid raw material to pentaerythritol triallyl ether as a solvent is 100:8 to 12; the mass ratio of pentaerythritol as a solid raw material to tetrabutylammonium bromide as a phase transfer catalyst is 100:3 to 5; the mass ratio of pentaerythritol and 50% aqueous solution of sodium hydroxide which are solid raw materials is 100: 190-220;
s2, dropwise adding chloropropene serving as a raw material, maintaining the reaction temperature at 95-105 ℃, continuously evaporating chloropropene and water, separating chloropropene and water after condensation, returning chloropropene to the stirring reaction kettle, controlling the feeding speed of chloropropene according to the water separation condition, and keeping the reaction for 10-16 hours; the mass ratio of the pentaerythritol to the added chloropropene is 100:150 to 200;
s3, adding water after the reaction is finished; the mass ratio of the pentaerythritol to the added water is 100: 50-300, cooling to 30-50 ℃, standing for layering, and carrying out vacuum distillation on the upper layer of organic phase to obtain the product pentaerythritol triallyl ether.
2. The method for preparing pentaerythritol triallyl ether according to claim 1, characterized in that: and (3) taking the water in the step S2 as the cooling stratified water in the step S3 as sodium hydroxide solution to prepare water.
3. The method for preparing pentaerythritol triallyl ether according to claim 1, characterized in that: the content of pentaerythritol triallyl ether in the product in the step S3 is more than 99 percent, and the product yield is more than 85 percent.
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| CN111715283B (en) * | 2020-07-28 | 2023-05-05 | 浙江皇马科技股份有限公司 | Catalyst for synthesizing pentaerythritol diallyl ether and preparation method thereof |
| CN111848366B (en) * | 2020-07-28 | 2022-08-30 | 浙江皇马科技股份有限公司 | Pentaerythritol diallyl ether and preparation method of catalyst adopted by same |
| CN112479833B (en) * | 2020-12-11 | 2022-09-27 | 浙江皇马科技股份有限公司 | Preparation method of pentaerythritol triallyl ether |
| CN113582898A (en) * | 2021-08-26 | 2021-11-02 | 襄阳金达成精细化工有限公司 | Methylthio-diafenthiuron and preparation method thereof |
| CN117069568A (en) * | 2023-08-16 | 2023-11-17 | 深圳市普利凯新材料股份有限公司 | Preparation method of pentaerythritol triallyl ether |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101200413A (en) * | 2006-12-11 | 2008-06-18 | 肖阳 | Method for preparing pentaerythrite allyl ether |
| CN102382290A (en) * | 2011-11-02 | 2012-03-21 | 浙江合诚化学有限公司 | Method for synthesizing triallyl polyether |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101200413A (en) * | 2006-12-11 | 2008-06-18 | 肖阳 | Method for preparing pentaerythrite allyl ether |
| CN102382290A (en) * | 2011-11-02 | 2012-03-21 | 浙江合诚化学有限公司 | Method for synthesizing triallyl polyether |
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