CN112592261A - Preparation method of trimethylolpropane diallyl ether - Google Patents
Preparation method of trimethylolpropane diallyl ether Download PDFInfo
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- CN112592261A CN112592261A CN202011520595.5A CN202011520595A CN112592261A CN 112592261 A CN112592261 A CN 112592261A CN 202011520595 A CN202011520595 A CN 202011520595A CN 112592261 A CN112592261 A CN 112592261A
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- alkali metal
- metal hydroxide
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- JQRRFDWXQOQICD-UHFFFAOYSA-N biphenylen-1-ylboronic acid Chemical compound C12=CC=CC=C2C2=C1C=CC=C2B(O)O JQRRFDWXQOQICD-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims abstract description 104
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 65
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims abstract description 46
- 238000006243 chemical reaction Methods 0.000 claims abstract description 44
- OWXJKYNZGFSVRC-NSCUHMNNSA-N (e)-1-chloroprop-1-ene Chemical compound C\C=C\Cl OWXJKYNZGFSVRC-NSCUHMNNSA-N 0.000 claims abstract description 43
- 239000007864 aqueous solution Substances 0.000 claims abstract description 41
- 239000000203 mixture Substances 0.000 claims abstract description 19
- 239000000047 product Substances 0.000 claims abstract description 18
- 238000002156 mixing Methods 0.000 claims abstract description 6
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 4
- 239000012044 organic layer Substances 0.000 claims description 22
- 239000000243 solution Substances 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 17
- 239000007787 solid Substances 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 9
- 239000010410 layer Substances 0.000 claims description 8
- 238000004817 gas chromatography Methods 0.000 claims description 7
- 238000004090 dissolution Methods 0.000 claims description 5
- 238000004448 titration Methods 0.000 claims description 5
- 230000002411 adverse Effects 0.000 abstract 1
- 239000000376 reactant Substances 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 30
- ATVJXMYDOSMEPO-UHFFFAOYSA-N 3-prop-2-enoxyprop-1-ene Chemical compound C=CCOCC=C ATVJXMYDOSMEPO-UHFFFAOYSA-N 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 8
- 230000001276 controlling effect Effects 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 6
- 238000001816 cooling Methods 0.000 description 5
- 229910052783 alkali metal Inorganic materials 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 239000011780 sodium chloride Substances 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- -1 Trimethylolpropane allyl ethers Chemical class 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 150000001340 alkali metals Chemical class 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 238000010327 methods by industry Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- LZDXRPVSAKWYDH-UHFFFAOYSA-N 2-ethyl-2-(prop-2-enoxymethyl)propane-1,3-diol Chemical compound CCC(CO)(CO)COCC=C LZDXRPVSAKWYDH-UHFFFAOYSA-N 0.000 description 1
- 229910001514 alkali metal chloride Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/16—Preparation of ethers by reaction of esters of mineral or organic acids with hydroxy or O-metal groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/34—Separation; Purification; Stabilisation; Use of additives
- C07C41/38—Separation; Purification; Stabilisation; Use of additives by liquid-liquid treatment
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a preparation method of trimethylolpropane diallyl ether, which comprises the following steps: controlling trimethylolpropane, alkali metal hydroxide and water to form a mixture in a reactor, wherein part or all of the alkali metal hydroxide is dripped into the reactor in the form of an aqueous solution of the alkali metal hydroxide within a preset time to form the mixture, chloropropene is dripped into the reactor within the preset time, the adding amount of the water is controlled to be 1-10 in molar ratio to the trimethylolpropane, and the molar ratio of the trimethylolpropane to the alkali metal hydroxide to the water is 1: a-1: b-9, wherein a is more than 0 and less than 1, and b is more than 0 and less than 9; after the dropwise addition is finished and the reaction is finished, separating the reaction product to obtain the trimethylolpropane diallyl ether. Wherein, by controlling the mixing and introducing mode of the alkali metal hydroxide and the water and controlling the molar ratio of the mixed reactants, the adverse factor of the water is overcome, the operation is simplified, the cost is reduced, and the product is easy to separate.
Description
Technical Field
The invention relates to the technical field of allyl ether synthesis, and particularly relates to a preparation method of trimethylolpropane diallyl ether.
Background
Trimethylolpropane allyl ethers, especially diethers, are suitable initially as modifiers for polyesters and later as starting materials and intermediates for resins. The preparation of trimethylolpropane diallyl ether belongs to the synthesis process of allyl ether, and is one simplified process to obtain diether in high yield.
In recent years, although there have been many reports on a production method in which trimethylolpropane and chloropropene are reacted in the presence of an alkali metal hydroxide to produce allyl ether, there is no method that can satisfy the industrial demand.
The process for producing allyl ether by reacting trimethylolpropane, alkali metal hydroxide and chloropropene together comprises first reacting trimethylolpropane with alkali metal hydroxide to produce alkali metal trimethylolpropane and water, and then reacting the alkali metal salt with chloropropene to produce allyl ether and alkali metal chloride. This completes the conversion of trimethylolpropane allyl ether. In the above reaction system, the presence of moisture in the system slows down the reaction rate, thereby inhibiting the formation of allyl ether. Followed by severe hydrolysis of chloropropene. The aqueous alkali metal hydroxide solution contains a large amount of water, which is disadvantageous for the reaction.
To overcome this disadvantage, there is a method of continuing the reaction by azeotroping water with toluene, which complicates the work.
Solid alkali metal hydroxides are also used, but their solubility in trimethylolpropane is very low, as is the solubility of the alkali metal trimethylolpropane, which significantly worsens the reaction. Further, the presence of a large amount of solid makes stirring difficult, and in order to improve this, uk 821977 reports that solid alkali metal hydroxide is alternately added with chloropropene, but addition of solid alkali metal hydroxide in a reaction vessel filled with chloropropene vapor is also difficult for industrialization.
In addition, in order to make the reaction proceed smoothly, there is also a method of using a phase transfer agent, for example: german 178840 patent, Japanese patent No. 52-73806 patent and British patent No. 821977 patent all use phase transfer agents. In this case, a problem arises in that the by-product salt is separated from the phase transfer agent, and the reaction process becomes complicated.
Disclosure of Invention
In view of the above, a method for preparing trimethylolpropane diallyl ether, which is easy to separate and low in cost, is provided to overcome the problems that a phase transfer agent needs to be recovered and the engineering is complex in the prior art.
A preparation method of trimethylolpropane diallyl ether comprises the following steps:
controlling trimethylolpropane, alkali metal hydroxide and water to form a mixture in a reactor, wherein part or all of the alkali metal hydroxide is dripped into the reactor in the form of an aqueous solution of the alkali metal hydroxide within a preset time to form the mixture, chloropropene is dripped into the reactor within the preset time, the addition amount of the water is controlled to be 1-10 in molar ratio to the trimethylolpropane, and the molar ratio of the trimethylolpropane to the alkali metal hydroxide to the water is 1: a-1: b-9, wherein a is more than 0 and less than 1, and b is more than 0 and less than 9;
and after the alkali metal hydroxide aqueous solution and chloropropene are dripped, separating a reaction product when the reaction is finished, and obtaining the trimethylolpropane diallyl ether.
Preferably, the trimethylolpropane is added into a reactor in advance, the alkali metal hydroxide is completely prepared into an aqueous solution, and all the alkali metal hydroxide aqueous solution and all the chloropropene are respectively added into the reactor dropwise to react with the trimethylolpropane.
Preferably, the alkali metal hydroxide is divided into solid alkali metal hydroxide and an alkali metal hydroxide aqueous solution, the trimethylolpropane and the solid alkali metal hydroxide are respectively and previously added into the reactor, after stirring and mixing, part of the alkali metal hydroxide aqueous solution and all chloropropene are respectively and dropwise added into the reactor for reaction.
Preferably, the total addition amount of the alkali metal hydroxide is 2 to 5 in a molar ratio to trimethylolpropane.
Preferably, the form of introduction of water into the mixture comprises the introduction of all of the water by the aqueous alkali metal hydroxide solution alone or the introduction of water by the aqueous alkali metal hydroxide solution separately from the water.
Preferably, the mass concentration of the alkali metal hydroxide in the mixture or the aqueous alkali metal hydroxide solution is 75% or less.
In some preferred embodiments, the form in which the alkali metal hydroxide is introduced to form the mixture includes any of:
(1) dissolving all or part of the alkali metal hydroxide into the limited total water amount, and then dropwise adding the alkali metal hydroxide into the reactor;
(2) firstly preparing an aqueous solution of alkali metal hydroxide, firstly adding one part of the aqueous solution of alkali metal hydroxide into the rest part of the reactor, and then dropwise adding;
(3) a part of the amount of the alkali metal hydroxide is charged in a solid state into the reactor, and the remainder is added dropwise in the form of an aqueous alkali metal hydroxide solution.
Preferably, the time for dropping the alkali metal hydroxide aqueous solution into the reactor is equal to or less than the time for dropping all chloropropene into the reactor, the time for dropping the alkali metal hydroxide aqueous solution into the reactor is less than 2 hours, and the chloropropene titration time is 0.5-5 hours.
Preferably, the mol ratio of the chloropropene to the trimethylolpropane is 1.8-2.5.
Preferably, the reaction temperature is 60-120 ℃, when the reaction is finished, water is added for dissolving, cooling and standing, an organic layer and a water layer are separated, the result of the organic layer is analyzed by gas chromatography, the organic layer is subjected to vacuum rectification to obtain a trimethylolpropane diallyl ether product, the purity is over 99%, and the light components are recycled in the next reaction.
In the preparation method of the trimethylolpropane diallyl ether, the shortage that the allyl ether is inhibited from being formed due to the existence of water in the traditional water reaction system is avoided by controlling the mixing and introducing mode of the alkali metal hydroxide and the water and controlling the alkali metal hydroxide aqueous solution to be dripped into the reactor and the chloropropene to be dripped into the reactor, and the reaction process can be flexibly and accurately regulated. Meanwhile, the adding amount of water is controlled to be 1-10 mol% of trimethylolpropane, the mol ratio of trimethylolpropane to alkali metal hydroxide to water is 1: 0-9, and the total water amount is controlled, so that the reaction can be rapidly carried out, the operation is simplified, the cost is reduced, the product is easy to separate, and the purity of a finished product with the purity of more than 99% can be easily obtained. The whole preparation process is simple and convenient to operate, the phase transfer agent does not need to be recovered, the traditional complex process engineering is avoided, and the production efficiency and the yield are improved.
Detailed Description
The present invention will be described in detail with reference to specific examples.
The embodiment of the invention provides a preparation method of trimethylolpropane diallyl ether, which comprises the following steps:
step S10, controlling trimethylolpropane, alkali metal hydroxide and water to form a mixture in a reactor, wherein, part or all of the alkali metal hydroxide is dripped into the reactor in the form of an aqueous solution of the alkali metal hydroxide within a preset time to form the mixture, chloropropene is dripped into the reactor within the preset time, the addition amount of the water is controlled to be between 1 and 10 in molar ratio with trimethylolpropane, and the molar ratio of the trimethylolpropane, the alkali metal hydroxide and the water is 1: a-1: b-9, wherein, 0< a <1, 0< b < 9;
and step S20, separating the reaction product to obtain trimethylolpropane diallyl ether when the alkali metal hydroxide aqueous solution and chloropropene are added dropwise and the reaction is finished.
Specifically, in an alternative embodiment, the trimethylolpropane is added into the reactor in advance, the alkali metal hydroxide is all prepared into an aqueous solution, all the alkali metal hydroxide aqueous solution and all the chloropropene are respectively added into the reactor dropwise to react with the trimethylolpropane, both of them can be added dropwise at the same time, for example, the two titrators are used for simultaneously titrating and adding into the reactor, or the alkali metal hydroxide aqueous solution is added dropwise for 0.5 to 1 hour first and then the chloropropene is added dropwise.
In another alternative embodiment, the alkali metal hydroxide is divided into solid alkali metal hydroxide and aqueous alkali metal hydroxide, the trimethylolpropane and the solid alkali metal hydroxide are respectively and previously added into the reactor, and after stirring and mixing, part of the aqueous alkali metal hydroxide and all of the chloropropene are respectively and dropwise added into the reactor to react.
Preferably, the form of introduction of water into the mixture comprises the introduction of all of the water by the aqueous alkali metal hydroxide solution alone or the introduction of water by the aqueous alkali metal hydroxide solution separately from the water.
Taking 1 mol of trimethylolpropane as a reference, controlling the total water content added in the reaction system to be 1-10 mol and less than 1 mol, separating out solids to make stirring difficult, and decomposing chloropropene in water is aggravated when the total water content is more than 10 mol. The above various adding modes are methods for adding water into a reaction system to form a mixture, preferably all water is introduced in the form of the alkali metal hydroxide aqueous solution, so that the operation is convenient, the total amount of water required by preparation is only required, and the influence of more water on the reaction speed can be avoided.
When the amount of the alkali metal hydroxide added is in consideration of the yield of trimethylolpropane diether, the total amount of the alkali metal hydroxide added is preferably in a molar ratio of 2 to 5 to trimethylolpropane. If the total amount of the alkali metal hydroxide added is less than 2 moles, the trimethylolpropane conversion is low, the diether is low, and the amount of the diether does not increase even after more than 5 moles.
In this example, it is necessary to control the mass concentration of the alkali metal hydroxide to 75% or less, because the operation is facilitated by preventing the precipitation of crystals of the alkali metal hydroxide while using the above-mentioned limitations on the amount of the alkali metal hydroxide and the total amount of water. Preferably, the mass concentration of the alkali metal hydroxide in the mixture or the aqueous alkali metal hydroxide solution is 75% or less.
In some preferred embodiments, the form in which the alkali metal hydroxide is introduced to form the mixture includes any of:
(1) dissolving all or part of the alkali metal hydroxide into the limited total water amount, and then dropwise adding the alkali metal hydroxide into the reactor;
(2) firstly preparing an aqueous solution of alkali metal hydroxide, firstly adding one part of the aqueous solution of alkali metal hydroxide into the rest part of the reactor, and then dropwise adding;
(3) a part of the amount of the alkali metal hydroxide is charged in a solid state into the reactor, and the remainder is added dropwise in the form of an aqueous alkali metal hydroxide solution.
In any of the above forms, the molar amount of the alkali metal hydroxide is equivalent to that of trimethylolpropane, and if the amount is exceeded, the resulting trimethylolpropane metal salt sticks to the wall of the reactor, thus inhibiting the reaction.
Preferably, the time for dropping the alkali metal hydroxide aqueous solution into the reactor is equal to or less than the time for dropping all chloropropene into the reactor, the time for dropping the alkali metal hydroxide aqueous solution into the reactor is less than 2 hours, and the chloropropene titration time is 0.5-5 hours.
In order to obtain more diethers, the mol ratio of chloropropene to trimethylolpropane is preferably 1.8 to 2.5. When the molar ratio of the two is lower than 1.8, the yield of diether is low; above 2.5, the yield of diether is not increased and is uneconomical. When the chloropropene titration time is less than 0.5, a large amount of unconverted chloropropene is evaporated and refluxed, and the reaction temperature cannot be controlled. Chloropropene titration times of more than 5 hours are not even more effective. The reaction end-point product obtained according to the embodiments of the present invention is a layered system comprising an organic layer of allyl ether and an inorganic layer of alkali metal salt aqueous solution as by-product, which is more advantageous for industrialization.
Preferably, the reaction temperature is 60-120 ℃, and preferably 70-110 ℃. The reaction is too slow below 60 ℃ and by-products are exacerbated above 120 ℃. And (3) adding water to dissolve and cool and standing when the reaction is finished, separating an organic layer from a water layer, analyzing the result of the organic layer by using gas chromatography, and performing reduced pressure rectification on the organic layer to obtain a trimethylolpropane diallyl ether product with the purity of over 99 percent and the light component for next reaction and recycling.
In the preparation method of the trimethylolpropane diallyl ether, the shortage that the allyl ether is inhibited from being formed due to the existence of water in the traditional water reaction system is avoided by controlling the mixing and introducing mode of the alkali metal hydroxide and the water and controlling the alkali metal hydroxide aqueous solution to be dripped into the reactor and the chloropropene to be dripped into the reactor, and the reaction process can be flexibly and accurately regulated. Meanwhile, the adding amount of water is controlled to be 1-10 mol% of trimethylolpropane, the mol ratio of trimethylolpropane to alkali metal hydroxide to water is 1: 0-9, and the total water amount is controlled, so that the reaction can be rapidly carried out, the operation is simplified, the cost is reduced, the product is easy to separate, and the purity of a finished product with the purity of more than 99% can be easily obtained. The whole preparation process is simple and convenient to operate, the phase transfer agent does not need to be recovered, the traditional complex process engineering is avoided, and the production efficiency and the yield are improved.
The preparation method of trimethylolpropane diallyl ether and the aspects of purity thereof according to the embodiments of the present invention are described below by specific examples.
Example 1
A stirrer, a reflux cooler, a thermometer and 2 dropping funnels are charged with nitrogen, 67 g of trimethylolpropane is added, the temperature is raised to 90 ℃, the temperature is kept, stirring is stopped, and 150 g of 40% sodium hydroxide aqueous solution and 88 g of chloropropene are dropwise added into the flask. Two different funnels were used to drop in simultaneously. The sodium hydroxide aqueous solution was added dropwise over 2 hours, and chloropropene was added dropwise over 3 hours. When the reaction is finished, sodium chloride which is not dissolved is present to enable the solution to be turbid, water is added for dissolution, cooling and standing are carried out, an organic layer and a water layer are separated, the organic layer is analyzed by gas chromatography, the organic layer is subjected to vacuum rectification to obtain a product, the purity of the product is more than 99%, and the light component is recycled in the next reaction.
Example 2
A stirrer, a reflux cooler, a thermometer and 2 dropping funnels are charged with nitrogen, 67 g of trimethylolpropane is added, the temperature is raised to 90 ℃, the temperature is kept, stirring is stopped, and 150 g of 40% sodium hydroxide aqueous solution and 94.9 g of chloropropene are dropwise added into the flask. Two different funnels were used to drop in simultaneously. The sodium hydroxide aqueous solution was added dropwise over 2 hours, and chloropropene was added dropwise over 3 hours. When the reaction is finished, sodium chloride which is not dissolved is present to enable the solution to be turbid, water is added for dissolution, cooling and standing are carried out, an organic layer and a water layer are separated, the organic layer is analyzed by gas chromatography, the organic layer is subjected to vacuum rectification to obtain a product, the purity of the product is more than 99%, and the light component is recycled in the next reaction.
Example 3
A stirrer, a reflux cooler, a thermometer and 2 dropping funnels are arranged on a 500 ml flask, nitrogen is filled, solid sodium hydroxide 10 and 67 g of trimethylolpropane are put into the flask, the temperature is increased to 90 ℃, the temperature is kept, stirring is not stopped, and 74 g of 46% sodium hydroxide aqueous solution and 73 g of chloropropene are dripped into the flask. Two different funnels were used to drop in simultaneously. The sodium hydroxide aqueous solution was added dropwise over 2 hours, and chloropropene was added dropwise over 3 hours. When the reaction is finished, sodium chloride which is not dissolved is present to enable the solution to be turbid, water is added for dissolution, cooling and standing are carried out, an organic layer and a water layer are separated, the organic layer is analyzed by gas chromatography, the organic layer is subjected to vacuum rectification to obtain a product, the purity of the product is more than 99%, and the light component is recycled in the next reaction.
Example 4
A stirrer, a reflux cooler, a thermometer and 2 dropping funnels are arranged on a 500 ml flask, nitrogen is filled, solid sodium hydroxide 20 and 67 g of trimethylolpropane are put into the flask, the temperature is increased to 90 ℃, the temperature is kept, stirring is not stopped, and 47 g of 52% sodium hydroxide aqueous solution and 73 g of chloropropene are dripped into the flask. Two different funnels were used to drop in simultaneously. The sodium hydroxide aqueous solution was added dropwise over 2 hours, and chloropropene was added dropwise over 3 hours. When the reaction is finished, sodium chloride which is not dissolved is present to enable the solution to be turbid, water is added for dissolution, cooling and standing are carried out, an organic layer and a water layer are separated, the organic layer is analyzed by gas chromatography, the organic layer is subjected to vacuum rectification to obtain a product, the purity of the product is more than 99%, and the light component is recycled in the next reaction.
It should be noted that the present invention is not limited to the above-mentioned embodiments, and other changes and modifications can be made by those skilled in the art according to the spirit of the present invention, and these changes and modifications made according to the spirit of the present invention should be included in the scope of the present invention as claimed.
Claims (10)
1. A preparation method of trimethylolpropane diallyl ether comprises the following steps:
controlling trimethylolpropane, alkali metal hydroxide and water to form a mixture in a reactor, wherein part or all of the alkali metal hydroxide is dripped into the reactor in the form of an aqueous solution of the alkali metal hydroxide within a preset time to form the mixture, chloropropene is dripped into the reactor within the preset time, the addition amount of the water is controlled to be 1-10 in molar ratio to the trimethylolpropane, and the molar ratio of the trimethylolpropane to the alkali metal hydroxide to the water is 1: a-1: b-9, wherein a is more than 0 and less than 1, and b is more than 0 and less than 9;
and after the alkali metal hydroxide aqueous solution and chloropropene are dripped, separating a reaction product when the reaction is finished, and obtaining the trimethylolpropane diallyl ether.
2. The method of producing trimethylolpropane diallyl ether according to claim 1, wherein the trimethylolpropane is preliminarily charged into a reactor, the alkali metal hydroxide is entirely prepared as an aqueous solution, and the entire alkali metal hydroxide aqueous solution and the entire chloropropene are separately added dropwise into the reactor to react with the trimethylolpropane.
3. The method according to claim 1, wherein the alkali metal hydroxide is divided into a solid alkali metal hydroxide and an aqueous alkali metal hydroxide solution, the trimethylolpropane and the solid alkali metal hydroxide are separately and previously charged into the reactor, and after stirring and mixing, a part of the aqueous alkali metal hydroxide solution and the whole chloropropene are separately and dropwise charged into the reactor to react.
4. The method of producing trimethylolpropane diallyl ether according to claim 1, wherein the total amount of the alkali metal hydroxide added is 2 to 5 mol% based on trimethylolpropane.
5. The method of claim 1, wherein the form of water introduced into the mixture comprises introducing all of the water separately through an aqueous alkali metal hydroxide solution or introducing the water separately from the aqueous alkali metal hydroxide solution.
6. The method of producing trimethylolpropane diallyl ether according to claim 1, wherein the mass concentration of the alkali metal hydroxide in the mixture or the aqueous solution of the alkali metal hydroxide is 75% or less.
7. The method of claim 1, wherein the form in which the alkali metal hydroxide is introduced to form a mixture comprises any one of:
(1) dissolving all or part of the alkali metal hydroxide into the limited total water amount, and then dropwise adding the alkali metal hydroxide into the reactor;
(2) firstly preparing an aqueous solution of alkali metal hydroxide, firstly adding one part of the aqueous solution of alkali metal hydroxide into the rest part of the reactor, and then dropwise adding;
(3) a part of the amount of the alkali metal hydroxide is charged in a solid state into the reactor, and the remainder is added dropwise in the form of an aqueous alkali metal hydroxide solution.
8. The method according to claim 5, wherein the time for dropping the aqueous solution of the alkali metal hydroxide into the reactor is equal to or less than the time for dropping all chloropropene into the reactor, the time for dropping the aqueous solution of the alkali metal hydroxide into the reactor is less than 2 hours, and the chloropropene titration time is 0.5 to 5 hours.
9. The method for preparing trimethylolpropane diallyl ether according to claim 1, wherein the mol ratio of chloropropene to trimethylolpropane is 1.8-2.5.
10. The method for preparing trimethylolpropane diallyl ether according to claim 1, wherein the reaction temperature is 60-120 ℃, when the reaction is finished, water is added for dissolution, the mixture is cooled and kept stand, an organic layer and a water layer are separated, the result of the organic layer is analyzed by gas chromatography, the organic layer is subjected to vacuum rectification to obtain a trimethylolpropane diallyl ether product, the purity of the trimethylolpropane diallyl ether product is more than 99%, and the light components are recycled in the next reaction.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113501749A (en) * | 2021-07-07 | 2021-10-15 | 浙江皇马科技股份有限公司 | Preparation method of multifunctional gas drying agent |
| CN113917019A (en) * | 2021-10-01 | 2022-01-11 | 赤峰瑞阳化工有限公司 | Method for detecting trimethylolpropane and byproduct thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60231625A (en) * | 1984-05-02 | 1985-11-18 | Nippon Shokubai Kagaku Kogyo Co Ltd | Production of allyl ether of trimethylolpropane |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60231625A (en) * | 1984-05-02 | 1985-11-18 | Nippon Shokubai Kagaku Kogyo Co Ltd | Production of allyl ether of trimethylolpropane |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113501749A (en) * | 2021-07-07 | 2021-10-15 | 浙江皇马科技股份有限公司 | Preparation method of multifunctional gas drying agent |
| CN113501749B (en) * | 2021-07-07 | 2023-10-03 | 浙江皇马科技股份有限公司 | Preparation method of multifunctional air-drying agent |
| CN113917019A (en) * | 2021-10-01 | 2022-01-11 | 赤峰瑞阳化工有限公司 | Method for detecting trimethylolpropane and byproduct thereof |
| CN113917019B (en) * | 2021-10-01 | 2022-05-27 | 赤峰瑞阳化工有限公司 | Method for detecting trimethylolpropane and byproduct thereof |
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