CN113979971B - Preparation method of 1, 4-butanediol diglycidyl ether - Google Patents
Preparation method of 1, 4-butanediol diglycidyl ether Download PDFInfo
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- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/02—Preparation of ethers from oxiranes
- C07C41/03—Preparation of ethers from oxiranes by reaction of oxirane rings with hydroxy groups
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- C07D303/12—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms
- C07D303/18—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms by etherified hydroxyl radicals
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Abstract
The invention provides a preparation method of 1, 4-butanediol diglycidyl ether, and relates to the technical field of organic synthesis. The invention adopts the high-efficiency Lewis acid catalyst in the etherification reaction stage of the 1, 4-butanediol and the epichlorohydrin, then adds the catalyst through the main reaction, then drops alkali aqueous solution in sections and carries out negative pressure closed loop reflux dehydration in sections, thereby reducing the water content of a reaction system, promoting the forward progress of the reaction, reducing the hydrolysis chlorine of the prepared 1, 4-butanediol diglycidyl ether product, having high yield, reducing the residual alkali content and TOC of wastewater, solving the problems of overhigh residual alkali content and high organic matter content in the brine, and realizing the industrialized clean production of the 1, 4-butanediol diglycidyl ether. In addition, the preparation method provided by the invention has the advantages of stable process, continuous production operation, avoiding the complicated feeding of solid alkali, high safety, low raw material consumption and low production cost.
Description
Technical Field
The invention relates to the technical field of organic synthesis, in particular to a preparation method of 1, 4-butanediol diglycidyl ether.
Background
The 1, 4-butanediol diglycidyl ether is an important organic chemical intermediate, is widely applied to the fields of paint industry and synthetic chemical industry, can be used as an epoxy reactive diluent, belongs to a multifunctional reactive diluent, has the characteristics of good flexibility, low viscosity, low volatility, low odor, low toxicity and the like, and is used as a diluent of epoxy resin to reduce the viscosity of an epoxy system and improve the mechanical property of an epoxy condensate.
At present, most of 1, 4-butanediol diglycidyl ether is synthesized by taking 1, 4-butanediol as a raw material, and carrying out ring opening reaction with epoxy chloropropane and ring closing reaction with alkali under the action of a catalyst (such as Lewis acid or tetrabutylammonium bromide). If the ring-opening reaction is incomplete, more ring-opening products remain in the product, which results in higher hydrolysis chlorine of the product, and too high hydrolysis chlorine content can adversely affect the curing behavior of the epoxy diluent and the performance of the cured product, slowing down the curing reaction, and simultaneously gradually releasing chloride ions can corrode the cured product and affect the insulativity thereof. As the process advances, the use of low-hydrolysis chloroepoxy diluents is becoming more and more widespread.
Chinese patent CN106995421a discloses a method for producing low hydrolysis chlorine 1, 4-butanediol diglycidyl ether, which comprises the following specific steps: A. ring opening reaction: adding 1, 4-butanediol, a catalyst and a solvent into a reaction kettle, and dropwise adding epichlorohydrin, wherein the catalyst is a mixture of boron trifluoride and stannic chloride in a mass ratio of 1:4; the mol ratio of the alcohol to the epoxy chloropropane is 1:2-1:4; the ring-opening temperature is controlled at 60-70 ℃, the dropping is finished for 1.5-2.5 hours, and the heat preservation is continued for 2.5-3.5 hours; B. ring closure reaction: cooling the materials to 10-20 ℃, dropwise adding sodium hydroxide liquid alkali, wherein the molar ratio of epichlorohydrin to sodium hydroxide is 1:0.5-0.98, after 15 min-1.5 h, gradually heating to 40-50 ℃, preserving heat for 1-4 h, then raising the reaction temperature to 60-70 ℃, and preserving heat for 2-6 h; C. draining water and washing: the upper oil phase is rectified to obtain the 1, 4-butanediol diglycidyl ether. The content of the hydrolytic chlorine of the 1, 4-butanediol diglycidyl ether synthesized by the method is 200-300 ppm, the quality is greatly improved, the consumption of liquid alkali can be greatly reduced, and the wastewater discharge in the reaction process is reduced. However, the hydrolysis chlorine of the 1, 4-butanediol diglycidyl ether prepared by the above synthetic method is still relatively high.
Disclosure of Invention
In view of the above, the present invention aims to provide a method for producing 1, 4-butanediol diglycidyl ether, which is characterized by low hydrolysis chlorine and high yield of the produced 1, 4-butanediol diglycidyl ether.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of 1, 4-butanediol diglycidyl ether, which comprises the following steps:
mixing 1, 4-butanediol, a Lewis acid catalyst, epichlorohydrin and a water-insoluble solvent, and carrying out etherification ring-opening reaction to obtain chlorohydrin ether;
mixing the chlorohydrin ether with a water-insoluble solvent, adding a main reaction catalyst, dropwise adding an alkali aqueous solution in sections for negative pressure closed loop reflux dehydration to obtain 1, 4-butanediol diglycidyl ether;
and in the process of carrying out negative pressure closed loop reflux dehydration by dropwise adding the alkali aqueous solution in sections, carrying out one section of negative pressure closed loop reflux dehydration after dropwise adding the alkali aqueous solution in each section.
Preferably, the temperature of each section of dropwise adding alkali aqueous solution and each section of negative pressure closed loop reflux dehydration is independently 40-50 ℃ and the time is independently 0.25-1 h;
the pressure of each section of negative pressure closed loop reflux dehydration is independently 5to 20 Torr.
Preferably, the molar ratio of the 1, 4-butanediol to the epichlorohydrin is 1:2 to 2.5.
Preferably, the mixing mode of the epichlorohydrin is dropwise addition; the temperature of the dripping is 55-65 ℃ and the time is 1-3 h.
Preferably, the lewis acid catalyst comprises one of tin tetrachloride, zinc perchlorate, boron trifluoride and aluminum trichloride;
the mass of the Lewis acid catalyst is 0.6-2% of the mass of the 1, 4-butanediol.
Preferably, the method is characterized in that the heat preservation temperature of the etherification ring-opening reaction is 60-80 ℃ and the heat preservation time is 2-5 h.
Preferably, the main reaction catalyst comprises one or more of polyethylene glycol, alkyl ammonium halide and aromatic ammonium halide;
the mass of the main reaction catalyst is 0.2-1% of the mass of the 1, 4-butanediol.
Preferably, the alkali in the aqueous alkali solution comprises sodium hydroxide and/or potassium hydroxide.
Preferably, the molar ratio of the 1, 4-butanediol to the alkali in the alkali aqueous solution is 1:1.8 to 2.5.
Preferably, the negative pressure closed loop reflux dehydration further comprises post-treatment, and the post-treatment comprises: adding water-soluble salt into the reaction liquid obtained by negative pressure closed loop reflux dehydration, standing for layering, adjusting the pH value of the obtained organic phase to 6-7, standing for layering, washing the obtained organic phase with water, dehydrating to remove the organic solvent, and filtering.
The invention provides a preparation method of 1, 4-butanediol diglycidyl ether, which comprises the following steps: mixing 1, 4-butanediol, a Lewis acid catalyst, epichlorohydrin and a water-insoluble solvent, and carrying out etherification ring-opening reaction to obtain chlorohydrin ether; mixing the chlorohydrin ether with a water-insoluble solvent, adding a main reaction catalyst, dropwise adding an alkali aqueous solution in sections for negative pressure closed loop reflux dehydration to obtain 1, 4-butanediol diglycidyl ether; and in the process of carrying out negative pressure closed loop reflux dehydration by dropwise adding the alkali aqueous solution in sections, carrying out one section of negative pressure closed loop reflux dehydration after dropwise adding the alkali aqueous solution in each section. According to the preparation method provided by the invention, a high-efficiency Lewis acid catalyst is adopted in the etherification reaction stage, and then a ring-closure reaction is carried out by adopting a mode of carrying out one-stage negative pressure ring-closure reflux dehydration after dropwise adding an alkali aqueous solution under the action of a main reaction catalyst, so that the water content of a reaction system is reduced, and the forward progress of the ring-closure reaction is promoted; in addition, the temperature range of the main reaction and the negative pressure closed loop reflux dehydration can be reduced, the constant temperature can be kept, and the occurrence of side reactions is reduced; the prepared 1, 4-butanediol diglycidyl ether product has low hydrolysis chlorine and high yield. The method provided by the invention also reduces the residual alkali amount and TOC of the wastewater, solves the problems of overhigh residual alkali amount and high organic content in the brine in the prior art, and realizes the industrial clean production of the 1, 4-butanediol diglycidyl ether. As shown in the test results of examples, the hydrolysis chlorine content of the 1, 4-butanediol diglycidyl ether prepared by the invention is 95-130 ppm, and the epoxy equivalent is 129.7-131.3 g/eq; the residual quantity of NaOH in the high-concentration brine is 0.77 to 0.84 weight percent, and the total organic carbon content is 8063 to 8130ppm; the unit consumption of the 1, 4-butanediol, the epichlorohydrin and the sodium hydroxide is respectively 0.407-0.416 g/g, 0.947-0.988 g/g and 0.332-0.344 g/g. The method provided by the invention has the advantages that the hydrolysis chlorine of the 1, 4-butanediol diglycidyl ether obtained by the preparation method is low; the residual alkali content in the brine is low; meanwhile, the raw material unit consumption, the residual alkali content in the wastewater and the TOC are obviously reduced.
In addition, the preparation method provided by the invention has the advantages of stable process, continuous production operation, avoiding the complicated feeding of solid alkali, reducing labor intensity and dangerous factors, along with high safety, low raw material consumption and greatly reducing production cost.
Detailed Description
The invention provides a preparation method of 1, 4-butanediol diglycidyl ether, which comprises the following steps:
mixing 1, 4-butanediol, a Lewis acid catalyst, epichlorohydrin and a water-insoluble solvent, and carrying out etherification ring-opening reaction to obtain chlorohydrin ether;
mixing the chlorohydrin ether with a water-insoluble solvent, adding a main reaction catalyst, dropwise adding an alkali aqueous solution in sections for negative pressure closed loop reflux dehydration to obtain 1, 4-butanediol diglycidyl ether;
and in the process of carrying out negative pressure closed loop reflux dehydration by dropwise adding the alkali aqueous solution in sections, carrying out one section of negative pressure closed loop reflux dehydration after dropwise adding the alkali aqueous solution in each section.
In the present invention, all raw material components are commercially available products well known to those skilled in the art unless specified otherwise.
The invention mixes 1, 4-butanediol, lewis acid catalyst, epichlorohydrin and water-insoluble solvent to carry out etherification ring-opening reaction to obtain chlorohydrin ether.
In the present invention, the molar ratio of 1, 4-butanediol to Epichlorohydrin (ECH) is preferably 1:2 to 2.5, more preferably 1:2.1 to 2.4, more preferably 1:2.2 to 2.3.
In the present invention, the lewis acid catalyst preferably includes one of tin tetrachloride, zinc perchlorate, boron trifluoride, or aluminum trichloride. In the present invention, the mass of the Lewis acid catalyst is preferably 0.6 to 2% by mass, more preferably 0.8 to 1.8% by mass, still more preferably 1 to 1.5% by mass, of 1, 4-butanediol.
In the present invention, the water-immiscible solvent preferably includes toluene or methyl isobutyl ketone; the invention has no special limit to the dosage of the solvent which is not mutually soluble in water, and can ensure that the etherification ring-opening reaction is smoothly carried out. In an embodiment of the present invention, the ratio of the amount of the substance of 1, 4-butanediol to the volume of the water-immiscible solvent is preferably 1mol:200 to 600mL, more preferably 1mol: 300-400 mL.
In the present invention, the epichlorohydrin is preferably mixed by dropping. In the present invention, the mixing is preferably to mix 1, 4-butanediol, a Lewis acid catalyst, and a water insoluble solvent and then to drop epichlorohydrin; the dropping temperature is preferably 55 to 65 ℃, more preferably 57 to 62 ℃, and even more preferably 59 to 60 ℃; the time for the dropping is preferably 1 to 3 hours, more preferably 1.5 to 2.5 hours, and still more preferably 2 hours.
In the invention, the heat preservation temperature of the etherification ring-opening reaction is preferably 60-80 ℃, more preferably 65-75 ℃, and even more preferably 70 ℃; the heat preservation time of the etherification ring-opening reaction is preferably 2 to 5 hours, more preferably 2.5 to 4.5 hours, and even more preferably 3 to 4 hours; the heat preservation time of the etherification ring-opening reaction is preferably counted after the addition of the epichlorohydrin is finished. In the present invention, the reaction occurring during the etherification ring-opening reaction is as follows:
in the invention, the chlorohydrin ether reaction solution obtained by the etherification ring-opening reaction is preferably not subjected to post-treatment and is directly subjected to subsequent negative pressure closed loop reflux dehydration.
After obtaining chlorohydrin ether, the invention mixes the chlorohydrin ether and the water-insoluble solvent, adds the main reaction catalyst, and drops alkali aqueous solution in sections to carry out negative pressure closed loop reflux dehydration to obtain 1, 4-butanediol diglycidyl ether.
In the present invention, the water-immiscible solvent is preferably the same as the aforementioned water-immiscible solvent, and will not be described here.
In the present invention, the main reaction catalyst preferably includes one or more of polyethylene glycol, alkyl ammonium halide and aromatic ammonium halide; the polyethylene glycol preferably comprises polyethylene glycol 200 and/or polyethylene glycol 400; the alkyl ammonium halide is preferably tetramethyl chloride; the aromatic ammonium halide preferably comprises one or more of benzyltrimethylammonium bromide, benzyltrimethylammonium chloride, benzyltriethylammonium bromide, benzyltriethylammonium chloride, benzyltributylammonium bromide, benzyltributylammonium chloride, phenyltrimethylammonium bromide and phenyltrimethylammonium chloride; the mass of the main reaction catalyst is preferably 0.2 to 1%, more preferably 0.4 to 0.8%, and even more preferably 0.5 to 0.6% of the mass of 1, 4-butanediol. In the invention, the main reaction catalyst has the functions of improving the reaction efficiency and shortening the reaction time.
In the present invention, the alkali in the aqueous alkali solution includes sodium hydroxide and/or potassium hydroxide; the concentration of the aqueous alkali solution is preferably 48 to 50wt%, more preferably 48.5 to 49.5wt%, and still more preferably 49wt%. In the present invention, the molar ratio of 1, 4-butanediol to alkali in the alkali aqueous solution is preferably 1:1.8 to 2.5, more preferably 1:1.9 to 2.4, more preferably 1:2.0 to 2.1.
In the invention, in the process of carrying out negative pressure closed loop reflux dehydration by dropwise adding alkali aqueous solution in sections, one section of negative pressure closed loop reflux dehydration is carried out after dropwise adding alkali aqueous solution in each section. In the embodiment of the present invention, the number of segments of the segment is preferably 2 to 4 segments, more preferably 3 segments. In the embodiment of the invention, the step of dropwise adding the alkali aqueous solution for closed-loop dehydration comprises sequentially performing first dropwise adding the alkali aqueous solution, first negative pressure closed-loop reflux dehydration, second dropwise adding the alkali aqueous solution, second negative pressure closed-loop reflux dehydration, third dropwise adding the alkali aqueous solution and third negative pressure closed-loop reflux dehydration. In the present invention, the temperature of the dropwise addition of the aqueous alkali solution and the negative pressure closed loop reflux dehydration is independently preferably 40 to 50 ℃, more preferably 40 to 45 ℃, still more preferably 43 ℃; the time for dropwise adding the alkali aqueous solution in each section and the time for negative pressure closed loop reflux dehydration in each section are independently preferably 0.25-1 h, more preferably 0.5-0.9 h, and even more preferably 0.7-0.8 h; the pressure of the negative pressure closed loop reflux dehydration in each stage is independently preferably 5to 20 Torr, more preferably 8to 18 Torr, still more preferably 10to 15 Torr. In the invention, the reaction occurring in the negative pressure closed loop reflux dehydration process is as follows:
the negative pressure closed loop reflux dehydration is followed by post-treatment, wherein the post-treatment comprises: adding water-soluble salt into the reaction liquid obtained by negative pressure closed loop reflux dehydration, standing for layering, regulating the pH value of the obtained organic phase to 6-7, standing for layering, washing the obtained organic phase with water, dehydrating to remove organic solvent, and filtering to obtain the 1, 4-butanediol diglycidyl ether. In the invention, the water for adding the water-soluble salt is preferably hot water, and the temperature of the hot water is preferably 40-80 ℃, more preferably 60 ℃; the water is preferably deionized water; the mass ratio of the 1, 4-butanediol to the first water for washing is preferably 1:4 to 8, more preferably 1: 5to 6. In the present invention, the pH adjusting acid preferably includes phosphoric acid, oxalic acid or sodium dihydrogen phosphate; the acid is preferably used in the form of an aqueous acid solution, and the concentration of the aqueous acid solution is preferably 1 to 5wt%, more preferably 2.5 to 4wt%. In the present invention, the purpose of the first stationary delamination is to separate the 1, 4-butanediol diglycidyl ether-containing organic phase from the high concentration brine phase. In the present invention, the water for washing is preferably hot water, and the temperature of the hot water is preferably 40 to 80 ℃, more preferably 60 ℃; the water is preferably deionized water; the mass ratio of the 1, 4-butanediol to the second water for washing is preferably 1:0.5 to 1.5, more preferably 1:0.94; the number of times of water washing is preferably 2-3, and the water washing is carried out by adopting hot water, so that impurities such as byproducts and the like are removed. In the present invention, the dehydration and organic solvent removal is preferably performed under vacuum conditions, and the pressure of the dehydration and organic solvent removal is preferably 5to 15 Torr, more preferably 10 Torr; the temperature of the dehydration and organic solvent removal is preferably 130-150 ℃, more preferably 140 ℃; the time for dehydration and removal of the organic solvent is not particularly limited, and water and the organic solvent may be removed. In the present invention, the purpose of the filtration is to remove solid by-products.
At present, excessive alkali such as NaOH and the like is needed to be added in the preparation of the 1, 4-butanediol diglycidyl ether with low hydrolysis chlorine, and excessive use of the alkali is finally converted into strong alkaline wastewater, so that reaction byproducts are increased, the organic matter content in the brine is increased, the oxidation treatment difficulty of the brine with concentration is greatly improved, and the environmental protection cost is increased. In order to reduce the amount of waste water, most of the solid alkali is used in the industry, but the solid alkali feeding is greatly exothermic, the condition is not mild enough, the solid alkali is fed in batches to bring a certain labor intensity to site workers, the randomness of the feeding can influence the continuous stability of the production process, and even the accidental injuries such as burn and corrosion can be caused; although the use of liquid alkali is convenient for clean production, the reaction efficiency of the liquid alkali is lower, and particularly, the reaction process of the ring-closure reaction is blocked by excessive water in the system in the latter half of the reaction, so that the liquid alkali used for preparing the 1, 4-butanediol diglycidyl ether with the same low hydrolysis chlorine greatly exceeds the solid alkali amount, the alkali consumption level is improved, the residual alkali in the brine is more, a large amount of neutralizing acid is needed in the later stage, and the raw material consumption level and the production cost are increased. According to the preparation method provided by the invention, the efficient Lewis acid catalyst is adopted in the etherification reaction stage, then the liquid alkali is dropwise added in a sectional manner and is dehydrated under negative pressure in a sectional manner, so that the water content of a reaction system is reduced, the forward reaction progress is promoted, the prepared 1, 4-butanediol diglycidyl ether product is stable in quality, low in hydrolytic chlorine, light in chromaticity and high in yield, the residual alkali amount and TOC of wastewater are reduced, the problems of excessive residual alkali amount and high organic matter content in brine are solved, and the industrial clean production of the 1, 4-butanediol diglycidyl ether is realized.
In addition, the preparation method provided by the invention has stable process, can realize continuous production operation, avoids the complicated feeding of solid alkali, reduces labor intensity and dangerous factors, has low raw material consumption in the whole production process, and saves production cost.
The technical solutions of the present invention will be clearly and completely described in the following in connection with the embodiments of the present invention. It will be apparent that the described embodiments are only some, but not all, embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
160g of 1, 4-butanediol, 160g of toluene and 2.5g of stannic chloride are added into a 2L reaction bottle, uniformly stirred, 380g of epichlorohydrin is added dropwise after the temperature is raised to 60 ℃, the dropwise adding time is 2 hours, and after the dropwise adding is finished, the temperature is raised to 70 ℃, and then the ring-opening reaction is carried out for 4 hours, so as to obtain a chlorohydrin ether solution; adding 480g of toluene and 0.8g of polyethylene glycol 400 into a chlorohydrin ether solution, cooling to 42 ℃, uniformly and first dropwise adding 85g of 50wt% NaOH solution, wherein the first dropwise adding time is 0.5h, first negative pressure closed loop reflux dehydration is carried out for 0.5h under the condition of 42 ℃ and 10Torr, then uniformly and second dropwise adding 85g of 50wt% NaOH solution, the second dropwise adding time is 1h, second negative pressure closed loop reflux dehydration is carried out for 0.5h under the condition of 42 ℃ and 10Torr, third dropwise adding 85g of 50wt% NaOH solution, the third dropwise adding time is 1h, third negative pressure closed loop reflux dehydration is carried out for 0.5h under the condition of 42 ℃ and 10Torr, adding 700g of deionized water, stirring, standing and phase separation, and removing lower saline (namely high-concentration saline) under the temperature of 60 ℃; 200g of deionized water at 60 ℃ is added into the obtained organic phase, the mixture is stirred, 2.50wt% of sodium dihydrogen phosphate aqueous solution is added for neutralization until the pH value is 6, standing and phase separation are carried out, 150g of deionized water at 60 ℃ is added into the obtained organic phase, stirring and standing and phase separation are carried out, the obtained organic phase is dehydrated into toluene with the water and toluene content of less than 1000ppm in the system under the conditions of 10Torr and 140 ℃, and the obtained filtrate is 1, 4-butanediol diglycidyl ether (the yield is 97.7%).
Example 2
Adding 160g of 1, 4-butanediol, 480g of toluene and 2.5g of boron trifluoride into a 2L reaction bottle, uniformly stirring, heating to 60 ℃, then dropwise adding 380g of epichlorohydrin for 1h, heating to 70 ℃ after the dropwise adding is finished, and carrying out heat preservation ring-opening reaction for 5h to obtain chlorohydrin ether solution; adding 160g of toluene and 1.6g of polyethylene glycol 400 into a chlorohydrin ether solution, cooling to 42 ℃, uniformly and first dropwise adding 90g of 50wt% NaOH solution, wherein the first dropwise adding time is 0.5h, first negative pressure closed loop reflux dehydration is carried out for 0.5h under the condition of 42 ℃ and 10Torr, then uniformly and second dropwise adding 90g of 50wt% NaOH solution, the second dropwise adding time is 1h, second negative pressure closed loop reflux dehydration is carried out for 0.5h under the condition of 42 ℃ and 10Torr, uniformly and third dropwise adding 90g of 50wt% NaOH solution, the third dropwise adding time is 1h, third negative pressure closed loop reflux dehydration is carried out for 1h under the condition of 42 ℃ and 10Torr, adding 700g of deionized water, stirring, standing and phase separation at 60 ℃ and removing lower saline (namely high-concentration saline); 200g of deionized water at 60 ℃ is added into the obtained organic phase, stirring is carried out, a phosphoric acid aqueous solution with the concentration of 2.50wt% is added for neutralization until the pH value is 6, standing and phase separation are carried out, 150g of deionized water at 60 ℃ is added into the obtained organic phase, stirring is carried out, standing and phase separation are carried out, the obtained organic phase is dehydrated into toluene with the water and toluene content of less than 1000ppm in the system under the conditions of 10Torr and 140 ℃, and the obtained filtrate is 1, 4-butanediol diglycidyl ether (the yield is 97.9%).
Example 3
160g of 1, 4-butanediol, 320g of methyl isobutyl ketone and 3g of zinc perchlorate are added into a 2L reaction bottle, uniformly stirred, 380g of epoxy chloropropane is added dropwise after the temperature is raised to 60 ℃, the dropwise adding time is 3 hours, and after the dropwise adding is finished, the temperature is raised to 70 ℃, the ring opening reaction is carried out for 2 hours, so as to obtain a chlorohydrin ether solution; adding 320g of methyl isobutyl ketone and 1g of polyethylene glycol 400 into a chlorohydrin ether solution, cooling to 42 ℃, uniformly and first dropwise adding 90g of 50wt% NaOH solution, wherein the first dropwise adding time is 0.5h, first negative pressure closed loop reflux dehydration is carried out for 0.5h under the condition of 42 ℃ and 10Torr, then uniformly and second dropwise adding 90g of 50wt% NaOH solution, the second dropwise adding time is 1h, second negative pressure closed loop reflux dehydration is carried out for 0.5h under the condition of 42 ℃ and 10Torr, uniformly and third dropwise adding 90g of 50wt% NaOH solution, the third dropwise adding time is 1h, third negative pressure closed loop reflux dehydration is carried out for 1h under the condition of 42 ℃ and 10Torr, adding 700g of deionized water, stirring, standing and phase separation, and removing lower saline (namely high-concentration saline) under the temperature of 60 ℃; 200g of deionized water at 60 ℃ is added into the obtained organic phase, the mixture is stirred, 2.50wt% of sodium dihydrogen phosphate aqueous solution is added for neutralization until the pH value is 6, standing and phase separation are carried out, 150g of deionized water at 60 ℃ is added into the obtained organic phase, stirring and standing and phase separation are carried out, the obtained organic phase is dehydrated into toluene with the water and toluene content of less than 1000ppm in the system under the conditions of 10Torr and 140 ℃, and the obtained filtrate is 1, 4-butanediol diglycidyl ether (the yield is 98.2%).
Comparative example 1
1, 4-butanediol diglycidyl ether was prepared as in example 1, with the difference from example 1 in that NaOH solution was added dropwise for the thermal insulation ring closure reaction: after the temperature is reduced to 42 ℃, 315g of NaOH solution with the concentration of 50wt% is dripped at a constant speed, the dripping time is 2 hours, and the heat preservation ring closure reaction is carried out for 4 hours after the dripping is finished, thus obtaining the 1, 4-butanediol diglycidyl ether (the yield is 94.0%).
Comparative example 2
1, 4-butanediol diglycidyl ether was prepared as in example 2, with the difference from example 2 in that NaOH solution was added dropwise for the thermal insulation ring closure reaction: after the temperature is reduced to 42 ℃, 310g of NaOH solution with the concentration of 50wt% is dripped at a constant speed, the dripping time is 2 hours, and the heat preservation ring closure reaction is carried out for 4 hours after the dripping is finished, thus obtaining the 1, 4-butanediol diglycidyl ether (the yield is 91.2%).
Comparative example 3
1, 4-butanediol diglycidyl ether was prepared as in example 3, with the difference from example 3 in that the addition of solid NaOH for the thermal insulation ring closure reaction was: cooling to 42 ℃ after ring opening reaction, uniformly adding 158g of NaOH solid in 3h, and carrying out heat preservation and ring opening reaction for 3h after the addition to obtain the 1, 4-butanediol diglycidyl ether (the yield is 95.4%).
The Epoxy Equivalent Weight (EEW) and the hydrolysis chlorine of the 1, 4-butanediol diglycidyl ether prepared in examples 1 to 3 and comparative examples 1 to 3, the residual sodium hydroxide and Total Organic Carbon (TOC) in high concentration brine, and the raw material unit consumption were as shown in Table 1. Wherein the raw material unit consumption refers to the mass of each raw material consumed for preparing 1g of 1, 4-butanediol diglycidyl ether, and the NaOH raw material unit consumption is calculated by NaOH solid.
TABLE 1 results of 1, 4-butanediol diglycidyl ether, high concentration brine and raw material consumption prepared in examples 1-3 and comparative examples 1-3
As is clear from Table 1, the 1, 4-butanediol diglycidyl ether prepared by the present invention has a hydrolysis chlorine content of 95-130 ppm and an epoxy equivalent of 129.7-131.3 g/eq; the residual quantity of NaOH in the high-concentration brine is 0.77 to 0.84 weight percent, and the total organic carbon content is 8063 to 8130ppm; the unit consumption of the 1, 4-butanediol, the epichlorohydrin and the sodium hydroxide is respectively 0.407-0.416 g/g, 0.947-0.988 g/g and 0.332-0.344 g/g. The method provided by the invention has the advantages that the hydrolysis chlorine of the 1, 4-butanediol diglycidyl ether obtained by the preparation method is low; the residual alkali content in the brine is low; meanwhile, the raw material unit consumption, the residual alkali content in the wastewater and the TOC are obviously reduced.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (8)
1. A preparation method of 1, 4-butanediol diglycidyl ether is characterized by comprising the following steps:
mixing 1, 4-butanediol, a Lewis acid catalyst, epichlorohydrin and a water-insoluble solvent, and carrying out etherification ring-opening reaction to obtain a chlorohydrin ether reaction solution;
mixing the chlorohydrin ether reaction solution with a water-insoluble solvent, adding a main reaction catalyst, and dropwise adding an alkali aqueous solution in sections to carry out negative pressure closed loop reflux dehydration to obtain 1, 4-butanediol diglycidyl ether;
the main reaction catalyst is polyethylene glycol;
in the process of carrying out negative pressure closed loop reflux dehydration by dropwise adding alkali aqueous solution in sections, carrying out one section of negative pressure closed loop reflux dehydration after dropwise adding alkali aqueous solution in each section;
the number of the segmented sections is 2-4;
the negative pressure closed loop reflux dehydration is followed by post-treatment, wherein the post-treatment is as follows: adding water-soluble salt into the reaction liquid obtained by negative pressure closed loop reflux dehydration, performing first standing delamination, adjusting the pH value of the obtained organic phase to 6-7, performing second standing delamination, washing the obtained organic phase, dehydrating to remove organic solvent, and filtering;
the water for adding the water-soluble salt is hot water, and the temperature of the hot water is 40-80 ℃;
the water for washing is hot water, and the temperature of the hot water is 40-80 ℃;
the molar ratio of the 1, 4-butanediol to the alkali in the alkali aqueous solution is 1:1.8 to 1.9.
2. The preparation method according to claim 1, wherein the temperature of each section of dropwise adding alkali aqueous solution and each section of negative pressure closed loop reflux dehydration is independently 40-50 ℃ and the time is independently 0.25-1 h;
the pressure of each section of negative pressure closed loop reflux dehydration is independently 5to 20 Torr.
3. The method according to claim 1, wherein the molar ratio of 1, 4-butanediol to epichlorohydrin is 1:2 to 2.5.
4. The preparation method according to claim 1, wherein the mixing mode of the epichlorohydrin is dropwise addition; the temperature of the dripping is 55-65 ℃ and the time is 1-3 h.
5. The method of claim 1, wherein the lewis acid catalyst comprises one of tin tetrachloride, zinc perchlorate, boron trifluoride, and aluminum trichloride;
the mass of the Lewis acid catalyst is 0.6-2% of the mass of the 1, 4-butanediol.
6. The method according to any one of claims 1 to 5, wherein the etherification ring-opening reaction is carried out at a temperature of 60 to 80 ℃ for 2 to 5 hours.
7. The method according to claim 1, wherein the mass of the main reaction catalyst is 0.2 to 1% of the mass of 1, 4-butanediol.
8. The method according to claim 1, wherein the alkali in the aqueous alkali solution comprises sodium hydroxide and/or potassium hydroxide.
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| CN113429367A (en) * | 2021-06-23 | 2021-09-24 | 江苏扬农锦湖化工有限公司 | Preparation method of alkyl glycidyl ether |
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