CN102898306A - Synthetic method of monomethyl adipate - Google Patents
Synthetic method of monomethyl adipate Download PDFInfo
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- CN102898306A CN102898306A CN2012103786604A CN201210378660A CN102898306A CN 102898306 A CN102898306 A CN 102898306A CN 2012103786604 A CN2012103786604 A CN 2012103786604A CN 201210378660 A CN201210378660 A CN 201210378660A CN 102898306 A CN102898306 A CN 102898306A
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Abstract
The invention discloses a synthetic method of monomethyl adipate, belonging to the technical field of organic chemistry and drug synthesis. The synthetic method disclosed herein comprises the following steps: firstly successively immersing macroporous cation exchange resin in acid solution, alkali liquor and acid solution, then washing the immersed macroporous cation exchange resin with water until the pH value of the resin is neutral, then filtering and removing the moisture attached to the surface of the macroporous cation exchange resin to obtain a pretreated resin; adding adipic acid and the pretreated resin in toluene, and conducting esterification with adding organic ethyl gallate dropwisely, filtering after reaction finished to separate the resin, filtering the toluene liquid after the toluene liquid is cooled to leach unreacted adipic acid, washing the monomethyl adipate toluene liquid, conducting reduced pressure condensation and recovering the solvent, and then conducting distillation to obtain the monomethyl adipate. According to the invention, the method has the advantages of high yield, convenient the post-treatment, no pollution, and reusability; and the resin can be directly reused, the solvent is recovered, thus the resource can be saved, and environmental protection property is achieved.
Description
Technical field
The invention belongs to organic chemistry and technical field of medicine synthesis, be specifically related to a kind of synthetic method of monoethyl adipatee.
Background technology
The English name of monoethyl adipatee is: Adipic acid monoethyl ester; Molecular formula is: C
8H
14O
4Molecular weight is: 174.2.It at room temperature is white in color or the red crystalline solid of micro mist.Fusing point: 28～29 ℃, boiling point: 285 ℃ (760mmHg), refractive index: n
20 D1.4390, relative density: 0.986.Water insoluble, be soluble in the organic solvents such as alcohol, ether.Monoethyl adipatee and derivative thereof have widely purposes as the important organic intermediate of a class in technical field of medicine synthesis.
The synthetic method of monoethyl adipatee mainly contains following three kinds:
The one, under alkaline condition or issue the first portion hydrolysis reaction in the catalysis of bioactive enzyme (pork liver lipase etc.) and obtain monoethyl adipatee (such as document Blaise; Koehler; Bulletin de la Societe Chimique deFrance; Vol. (4) 7; (1910); P.219).
The 2nd, by hexanodioic acid or adipic anhydride and ethanol, as catalyzer, the control reaction conditions carries out esterification and obtains monoethyl adipatee (such as document Chem.Zentralbl. with acid; Vol.97; (1926; P.126));
The 3rd, by the people such as Swann nineteen forty-three with hexanodioic acid, diethylene adipate and ethanol with the condition of acid as catalyst under control reaction conditions obtain monoethyl adipatee (document such as Swann; Oehler; Buswell; Org.synth.Coll.Vol.11; (1943); P.227).
The drawback such as above-mentioned three kinds of methods all exist the amount of reactant species wayward, side reaction is many, yield is low and aftertreatment is cumbersome, employed catalyzer has the vitriol oil, hydrochloric acid, tosic acid, triethylamine, sodium methylate and liquid caustic soda etc. simultaneously, it is large and should not reclaim all to exist corrosive equipment, contaminate environment, consumption, and causes easily the shortcomings such as secondary pollution of target product.
Chinese invention patent application publication No. CN102351691A discloses a kind of synthetic method of monoethyl adipatee, the preparation method of this patent scheme is identical with above-mentioned the second synthetic method, done at the vitriol oil by hexanodioic acid to generate adipic anhydride under the catalysis of catalyzer, again hexanodioic acid and ethanol generation alcoholysis reaction are obtained monoethyl adipatee, but because the adipic anhydride chemical property is unstable, therefore need existing preparation existing with (namely system is namely used), and the preparation adipic anhydride needs a large amount of vitriol oils, the shortcomings such as same corrosive equipment and contaminate environment.
In view of above-mentioned prior art, the applicant has done useful making repeated attempts, and has finally formed technical scheme described below.
Summary of the invention
Task of the present invention is to provide a kind of synthetic method of monoethyl adipatee, and the method has the generation that reduces by product, avoid environmental pollution, improve yield and quality product and satisfy the environmental protection production requirement.
Task of the present invention is finished like this, and a kind of synthetic method of monoethyl adipatee may further comprise the steps:
A) resin pre-treatment, by the order of acid solution, alkali lye and acid soak large pores cation exchange resin is soaked successively first, water flushing after each the immersion, and it is neutral that the pH value that finally makes large pores cation exchange resin is, then filter and remove the moisture content that is built-up in the large pores cation exchange resin surface, obtain the pre-treatment resin;
B) esterification, hexanodioic acid and pre-treatment resin dropped in the toluene and under the state that drips the organic acid ethyl ester carry out esterification, filtered while hot after reaction finishes, to separate resin, obtain toluene liquid, but afterwards toluene liquid is filtered until the toluene liquid cooling, with the unreacted hexanodioic acid of leaching, obtain monoethyl adipatee toluene liquid, monoethyl adipatee toluene liquid is washed, to remove the reaction product organic acid, again through decompression condensation and reclaim solvent, then distillation, obtain monoethyl adipatee, the described resin direct repeat that separates is used in step of esterification, and solvent recuperation is applied mechanically, and the unreacted hexanodioic acid of described leaching uses when waiting until next synthesizing adipic acid mono ethyl ester.
In a specific embodiment of the present invention, steps A) acid solution described in and the weight ratio of described large pores cation exchange resin are 3-5: 1; The weight ratio of described alkali lye and large pores cation exchange resin is 3-5: 1; The time of described immersion is 150-210min.
In another specific embodiment of the present invention, described acid solution is that mass percent concentration is hydrochloric acid soln or the sulphuric acid soln of 3-5%; Described alkali lye is that mass percent concentration is sodium hydroxide solution or the potassium hydroxide solution of 3-5%.
In another specific embodiment of the present invention, steps A) the used water of water flushing described in is deionized water; Described pH value is neutrality and refers to that pH is 5-7.
In another specific embodiment of the present invention, described large pores cation exchange resin is the polystyrene large pores cation exchange resin.
Also have in the specific embodiment step B of the present invention) described in hexanodioic acid and the weight ratio of described pre-treatment resin be 1: 1-12; The weight ratio of hexanodioic acid and described toluene is 1: 4-20; Described organic acid ethyl ester is 1-3 with the mol ratio of hexanodioic acid: 1.
The time of the esterification more of the present invention and in specific embodiment, step B) is 60-300min, and temperature of reaction is 20-100 ℃.
In of the present invention and then specific embodiment, step B) the toluene liquid cooling for the treatment of described in refers to that but toluene liquid is cooled to 15-25 ℃; Described is deionized water to the used water of monoethyl adipatee toluene liquid washing, and deionized water and hexanodioic acid toluene liquid weight ratio are 4-6: 1.
The pressure of the concentrating under reduced pressure of the present invention again more and in specific embodiment, step B) is-0.09～-0.1MPa, the temperature of concentrating under reduced pressure is 45-80 ℃.
In again of the present invention and then specific embodiment, described organic acid ethyl ester is ethyl formate, ethyl acetate or ethyl propionate.
Technical scheme provided by the invention is owing to the single-esterification that has adopted by large pores cation exchange resin catalysis hexanodioic acid, thereby avoided using in the prior art strong acid to make catalyzer, can embody the yield height, convenient post-treatment, pollution-free, can repeat strong point such as regeneration use etc., the total recovery of the monoethyl adipatee that obtains can reach 95.8 ~ 96.8%, content GC reaches more than 98.5%, and impurity free acid GC is below 0.3%; The resin direct repeat uses, and solvent recuperation is applied mechanically, thereby both can economize on resources, and can embody the feature of environmental protection again.
Embodiment
The invention will be further described below by embodiment; the described preparation method of the embodiment of the invention is only used for illustrating the present invention; rather than limitation of the present invention, the pro forma improvement to preparation method of the present invention under design prerequisite of the present invention all belongs to the scope of protection of present invention.
Embodiment 1
A) resin pre-treatment, press successively first acid soak, dipping by lye and again the order of acid soak polystyrene macroporous type cation exchange tree is soaked, and after each the immersion, use deionized water rinsing, specifically: be that 3% hydrochloric acid soln soaks the polystyrene large pores cation exchange resin with mass percent concentration first, wherein mass percent concentration is that 3% hydrochloric acid soln and the weight ratio of polystyrene large pores cation exchange resin are 5: 1, the time of soaking is 150min, drain after soak finishing that hydrochloric acid soln namely drains acid solution and with deionized water rinsing to pH7, using mass percent concentration instead again and be 3% sodium hydroxide solution soaks, the weight ratio of this sodium hydroxide solution and polystyrene large pores cation exchange resin is 5: 1, the time of dipping by lye is 150min, drain sodium hydroxide solution after dipping by lye finishes and namely drain alkali lye, and again with deionized water rinsing to pH10, and then be that 3% hydrochloric acid soln soaks 150min with mass percent concentration, the weight ratio of this hydrochloric acid soln and polystyrene large pores cation exchange resin is 5: 1, drain after again soak finishing acid solution and and then to be flushed to pH with deionized water be neutral, then filter, namely to resin filter, and remove the moisture content that attaches at resin surface, obtain the pre-treatment resin, the polystyrene large pores cation exchange resin described in this step preferably uses that produce by Chinese Shanghai China shake Science and Technology Ltd. and the trade mark that widely sold in market before present patent application proposes is D001, HD-8, HD-81 or HZ-6 etc.;
B) esterification, with hexanodioic acid with by steps A) the pre-treatment resin that obtains adds in the toluene, the weight ratio of hexanodioic acid and pre-treatment resin is 1: 8, the weight of hexanodioic acid and toluene is 1: 10, drip ethyl formate, carry out the constant temperature single-esterification, the mol ratio of ethyl formate and hexanodioic acid is 2: 1, esterification reaction temperature is 50 ℃, esterification is that the time for adding of ethyl formate is 180min, and filtered while hot obtained toluene liquid to separate resin after reaction finished, toluene liquid is cooled to 20 ℃, filtration obtains the unreacted hexanodioic acid, reuses when waiting until next synthesizing adipic acid mono ethyl ester, and filtrate is faint yellow monoethyl adipatee toluene liquid, this liquid (monoethyl adipatee toluene liquid) is by water (deionized water) eccysis dereaction product formic acid, the water of washing be that the weight ratio of deionized water and hexanodioic acid is 5:1, concentrating under reduced pressure toluene, thickening temperature are 70 ℃, decompression pressure is-0.09Mpa that distillation obtains monoethyl adipatee.Total recovery 96.5%, product content GC is 99.38%, impurity free acid GC is 0.15%.The resin direct repeat uses, and solvent recuperation is applied mechanically.
Embodiment 2
A) resin pre-treatment, be that 5% hydrochloric acid soln soaks the polystyrene large pores cation exchange resin with mass percent concentration first, wherein mass percent concentration is that 5% hydrochloric acid soln and the weight ratio of polystyrene large pores cation exchange resin are 4: 1, the time of soaking is 210min, drain after soak finishing that hydrochloric acid soln namely drains acid solution and with deionized water rinsing to pH5, using mass percent concentration instead again and be 5% sodium hydroxide solution soaks, the weight ratio of this sodium hydroxide solution and polystyrene large pores cation exchange resin is 4: 1, the time of dipping by lye is 210min, drain sodium hydroxide solution after dipping by lye finishes and namely drain alkali lye, and again with deionized water rinsing to pH7, and then be that 5% hydrochloric acid soln soaks 210min with mass percent concentration, the weight ratio of this hydrochloric acid soln and polystyrene large pores cation exchange resin is 4: 1, drain after again soak finishing acid solution and and then to be flushed to pH with deionized water be neutral, be that pH is 7, then filter, namely to resin filter, and remove the moisture content that attaches at resin surface and obtain the pre-treatment resin;
B) esterification, with hexanodioic acid with by steps A) the pre-treatment resin that obtains adds in the toluene, the weight ratio of hexanodioic acid and pre-treatment resin is 1:4, the weight of hexanodioic acid and toluene is 1:4, drip ethyl acetate, carry out the constant temperature single-esterification, the mol ratio of ethyl acetate and hexanodioic acid is 1:1, esterification reaction temperature is 100 ℃, and esterification is that the time for adding of ethyl acetate is 300min.Filtered while hot was to separate resin after reaction finished, obtain toluene liquid, toluene liquid is cooled to 15 ℃, filter and obtain the unreacted hexanodioic acid, wait until synthetic reusing next time, filtrate is faint yellow monoethyl adipatee toluene liquid, and this solution is removed reaction product acetic acid by washing, and the amount of washing is that the weight ratio of deionized water and hexanodioic acid is 6:1, concentrating under reduced pressure toluene, thickening temperature is 45 ℃, and decompression pressure is-0.1Mpa that distillation obtains monoethyl adipatee.Total recovery 96.8%, product content GC is 99.51%, impurity free acid GC is 0.08%.The resin direct repeat uses, and solvent recuperation is applied mechanically.The content that does not relate in the present embodiment is all with the description to embodiment 1.
Embodiment 3
A) resin pre-treatment, be that 4% hydrochloric acid soln soaks the polystyrene large pores cation exchange resin with mass percent concentration first, wherein mass percent concentration is that 4% hydrochloric acid soln and the weight ratio of polystyrene large pores cation exchange resin are 3: 1, the time of soaking is 180min, drain after soak finishing that hydrochloric acid soln namely drains acid solution and with deionized water rinsing to pH6, using mass percent concentration instead again and be 4% sodium hydroxide solution soaks, the weight ratio of this sodium hydroxide solution and polystyrene large pores cation exchange resin is 3: 1, the time of dipping by lye is 180min, drain sodium hydroxide solution after dipping by lye finishes and namely drain alkali lye, and again with deionized water rinsing to pH8, and then be that 4% hydrochloric acid soln soaks 180min with mass percent concentration, the weight ratio of this hydrochloric acid soln and polystyrene large pores cation exchange resin is 3: 1, drain after again soak finishing acid solution and and then to be flushed to pH with deionized water be neutral, be that pH is 6, then filter, namely to resin filter, and remove the moisture content that attaches at resin surface, obtain the pre-treatment resin;
B) esterification, with hexanodioic acid with by steps A) the pre-treatment resin that obtains adds in the toluene, the weight ratio of hexanodioic acid and pre-treatment resin is 1:12, the weight of hexanodioic acid and toluene is 1:20, drip ethyl propionate, carry out the constant temperature single-esterification, the mol ratio of ethyl propionate and hexanodioic acid is 3:1, esterification reaction temperature is 20 ℃, and esterification is that the time for adding of ethyl propionate is 60min.Filtered while hot was to separate resin after reaction finished, obtain toluene liquid, toluene liquid is cooled to 25 ℃, filtration obtains the unreacted hexanodioic acid, wait until synthetic reusing next time, filtrate is faint yellow monoethyl adipatee toluene liquid, this solution (monoethyl adipatee toluene liquid) is by water (deionized water) eccysis dereaction product propionic acid, the amount of the water of washing is that the weight ratio of deionized water and hexanodioic acid is 4:1, concentrating under reduced pressure toluene, thickening temperature is 80 ℃, and decompression pressure is-0.092Mpa that distillation obtains monoethyl adipatee.Total recovery 95.8%, product content GC is 98.43%, impurity free acid GC is 0.85%.The resin direct repeat uses, and solvent recuperation is applied mechanically.The content that does not relate in the present embodiment is all with the description to embodiment 1.
Embodiment 4
A) resin pre-treatment, be that 3% sulphuric acid soln soaks the polystyrene large pores cation exchange resin with mass percent concentration first, wherein mass percent concentration is that 3% sulphuric acid soln and the weight ratio of polystyrene large pores cation exchange resin are 3: 1, the time of soaking is 180min, drain after soak finishing that sulphuric acid soln namely drains acid solution and with deionized water rinsing to pH6, using mass percent concentration instead again and be 3% potassium hydroxide solution soaks, the weight ratio of this potassium hydroxide solution and polystyrene large pores cation exchange resin is 3: 1, the time of dipping by lye is 180min, drain potassium hydroxide solution after dipping by lye finishes and namely drain alkali lye, and again with deionized water rinsing to pH8, and then be that 3% sulphuric acid soln soaks 180min with mass percent concentration, the weight ratio of this sulphuric acid soln and polystyrene large pores cation exchange resin is 3: 1, drain after again soak finishing acid solution and and then to be flushed to pH with deionized water be neutral, be that pH is 6.5, then filter, namely to resin filter, and remove the moisture content that attaches at resin surface, obtain the pre-treatment resin;
B) esterification, with hexanodioic acid with by steps A) the pre-treatment resin that obtains adds in the toluene, the weight ratio of hexanodioic acid and pre-treatment resin is 1:1, the weight of hexanodioic acid and toluene is 1:15, drip ethyl formate, carry out the constant temperature single-esterification, the mol ratio of ethyl formate and hexanodioic acid is 2:1, esterification reaction temperature is 60 ℃, and the time that esterification namely drips ethyl formate is 120min.Filtered while hot was to separate resin after reaction finished, obtain toluene liquid, toluene liquid is cooled to 20 ℃, filtration obtains the unreacted hexanodioic acid, wait until synthetic reusing next time, filtrate is faint yellow monoethyl adipatee toluene liquid, this solution (monoethyl adipatee toluene liquid) is by water (deionized water) eccysis dereaction product formic acid, the amount of washing is that the weight ratio of deionized water and hexanodioic acid is 5.5:1, concentrating under reduced pressure toluene, thickening temperature is 60 ℃, and decompression pressure is-0.098Mpa that distillation obtains monoethyl adipatee.Total recovery 96.0%, product content GC is 99.16%, impurity free acid GC is 0.11%.The resin direct repeat uses, and solvent recuperation is applied mechanically.The content that does not relate in the present embodiment is all with the description to embodiment 1.
Embodiment 5
A) resin pre-treatment, be that 4% sulphuric acid soln soaks the polystyrene large pores cation exchange resin with mass percent concentration first, wherein mass percent concentration is that 4% sulphuric acid soln and the weight ratio of polystyrene large pores cation exchange resin are 5: 1, the time of soaking is 120min, drain after soak finishing that sulphuric acid soln namely drains acid solution and with deionized water rinsing to pH5, using mass percent concentration instead again and be 4% potassium hydroxide solution soaks, the weight ratio of this potassium hydroxide solution and polystyrene large pores cation exchange resin is 5: 1, the time of dipping by lye is 120min, drain potassium hydroxide solution after dipping by lye finishes and namely drain alkali lye, and again with deionized water rinsing to pH8, and then be that 4% sulphuric acid soln soaks 120min with mass percent concentration, the weight ratio of this sulphuric acid soln and polystyrene large pores cation exchange resin is 5: 1, drain after again soak finishing acid solution and and then to be flushed to pH with deionized water be neutral, then filter, namely to resin filter, and remove the moisture content that attaches at resin surface, obtain the pre-treatment resin;
B) esterification, with hexanodioic acid with by steps A) the pre-treatment resin that obtains adds in the toluene, the weight ratio of hexanodioic acid and pre-treatment resin is 1:6, the weight of hexanodioic acid and toluene is 1:8, drip ethyl acetate, carry out the constant temperature single-esterification, the mol ratio of ethyl acetate and hexanodioic acid is 3:1, the temperature of esterification is 80 ℃, and the time that esterification namely drips ethyl acetate is 240min.Filtered while hot was to separate resin after reaction finished, obtain toluene liquid, toluene liquid is cooled to 25 ℃, filtration obtains the unreacted hexanodioic acid, wait until synthetic reusing next time, filtrate is faint yellow monoethyl adipatee toluene liquid, this solution (faint yellow monoethyl adipatee toluene liquid) is removed reaction product acetic acid by washing, the amount of washing is that the weight ratio of deionized water and hexanodioic acid is 5:1, concentrating under reduced pressure toluene, thickening temperature is 50 ℃, and decompression pressure is-0.096Mpa that distillation obtains monoethyl adipatee.Total recovery 96.3%, product content GC is 99.27%, impurity free acid GC is 0.31%.The resin direct repeat uses, and solvent recuperation is applied mechanically.All the other are all with the description to embodiment 1.
Embodiment 6
A) resin pre-treatment, be that 3% sulphuric acid soln soaks the polystyrene large pores cation exchange resin with mass percent concentration first, wherein mass percent concentration is that 3% sulphuric acid soln and the weight ratio of polystyrene large pores cation exchange resin are 3: 1, the time of soaking is 120min, drain after soak finishing that sulphuric acid soln namely drains acid solution and with deionized water rinsing to pH5, using mass percent concentration instead again and be 3% sodium hydroxide solution soaks, the weight ratio of this sodium hydroxide solution and polystyrene large pores cation exchange resin is 3: 1, the time of dipping by lye is 120min, drain sodium hydroxide solution after dipping by lye finishes and namely drain alkali lye, and again with deionized water rinsing to pH8, and then be that 3% sulphuric acid soln soaks 120min with mass percent concentration, the weight ratio of this sulphuric acid soln and polystyrene large pores cation exchange resin is 3: 1, drain after again soak finishing acid solution and and then to be flushed to pH with deionized water be neutral, be that the pH value is 6.8, then filter, namely to resin filter, and remove the moisture content that attaches at resin surface, obtain the pre-treatment resin;
B) esterification, with hexanodioic acid with by steps A) in the pre-treatment resin that obtains add in the toluene, the weight ratio of hexanodioic acid and pre-treatment resin is 1: 5, the weight of hexanodioic acid and toluene is 1: 6, drip ethyl acetate, carry out the constant temperature single-esterification, the mol ratio of ethyl acetate and hexanodioic acid is 2: 1, esterification reaction temperature is 50 ℃, and the time that reaction time of esterification namely drips ethyl acetate is 180min.Filtered while hot was to separate resin after reaction finished, obtain toluene liquid, toluene liquid is cooled to 25 ℃, filtration obtains the unreacted hexanodioic acid, wait until synthetic reusing next time, filtrate is faint yellow monoethyl adipatee toluene liquid, this solution (faint yellow monoethyl adipatee benzene liquid) is by water (deionized water) eccysis dereaction product acetic acid, the amount of washing is that the weight ratio of deionized water and hexanodioic acid is 6: 1, concentrating under reduced pressure toluene, thickening temperature is 60 ℃, and decompression pressure is-0.096Mpa that distillation obtains monoethyl adipatee.Total recovery 96.1%, product content GC is 99.37%, impurity free acid GC is 0.26%.The resin direct repeat uses, and solvent recuperation is applied mechanically.All the other are all with the description to embodiment 1.
Claims (10)
1. the synthetic method of a monoethyl adipatee is characterized in that may further comprise the steps:
A) resin pre-treatment, by the order of acid solution, alkali lye and acid soak large pores cation exchange resin is soaked successively first, water flushing after each the immersion, and it is neutral that the pH value that finally makes large pores cation exchange resin is, then filter and remove the moisture content that is built-up in the large pores cation exchange resin surface, obtain the pre-treatment resin;
B) esterification, hexanodioic acid and pre-treatment resin dropped in the toluene and under the state that drips the organic acid ethyl ester carry out esterification, filtered while hot after reaction finishes, to separate resin, obtain toluene liquid, but afterwards toluene liquid is filtered until the toluene liquid cooling, with the unreacted hexanodioic acid of leaching, obtain monoethyl adipatee toluene liquid, monoethyl adipatee toluene liquid is washed, to remove the reaction product organic acid, again through decompression condensation and reclaim solvent, then distillation, obtain monoethyl adipatee, the described resin direct repeat that separates is used in step of esterification, and solvent recuperation is applied mechanically, and the unreacted hexanodioic acid of described leaching uses when waiting until next synthesizing adipic acid mono ethyl ester.
2. the synthetic method of a kind of monoethyl adipatee according to claim 1 is characterized in that steps A) described in acid solution and the weight ratio of described large pores cation exchange resin be 3-5: 1; The weight ratio of described alkali lye and large pores cation exchange resin is 3-5: 1; The time of described immersion is 150-210min.
3. the synthetic method of a kind of monoethyl adipatee according to claim 1 and 2 is characterized in that described acid solution is that mass percent concentration is hydrochloric acid soln or the sulphuric acid soln of 3-5%; Described alkali lye is that mass percent concentration is sodium hydroxide solution or the potassium hydroxide solution of 3-5%.
4. the synthetic method of a kind of monoethyl adipatee according to claim 1 is characterized in that steps A) described in the used water of water flushing be deionized water; Described pH value is neutrality and refers to that pH is 5-7.
5. the synthetic method of a kind of monoethyl adipatee according to claim 1 and 2 is characterized in that described large pores cation exchange resin is the polystyrene large pores cation exchange resin.
6. the synthetic method of a kind of monoethyl adipatee according to claim 1 is characterized in that step B) described in hexanodioic acid and the weight ratio of described pre-treatment resin be 1: 1-12; The weight ratio of hexanodioic acid and described toluene is 1: 4-20; Described organic acid ethyl ester is 1-3 with the mol ratio of hexanodioic acid: 1.
7. the synthetic method of a kind of monoethyl adipatee according to claim 1 is characterized in that step B) described in time of esterification be 60-300min, temperature of reaction is 20-100 ℃.
8. the synthetic method of a kind of monoethyl adipatee according to claim 1 is characterized in that step B) described in the toluene liquid cooling for the treatment of refer to that but toluene liquid is cooled to 15-25 ℃; Described is deionized water to the used water of monoethyl adipatee toluene liquid washing, and deionized water and hexanodioic acid toluene liquid weight ratio are 4-6: 1.
9. the synthetic method of a kind of monoethyl adipatee according to claim 1 is characterized in that step B) described in the pressure of concentrating under reduced pressure be-0.09～-0.1MPa, the temperature of concentrating under reduced pressure is 45-80 ℃.
10. according to claim 5 or the synthetic method of 6 described a kind of monoethyl adipatees, it is characterized in that described organic acid ethyl ester is ethyl formate, ethyl acetate or ethyl propionate.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103990499A (en) * | 2014-06-06 | 2014-08-20 | 四川恒达环境技术有限公司 | Preprocessing method for ion exchange resin for treating waste water at tail end of electrolytic manganese manufacturing technique |
| CN107043327A (en) * | 2017-05-12 | 2017-08-15 | 苏州富士莱医药股份有限公司 | A kind of synthetic method of monoethyl adipatee |
| CN114940648A (en) * | 2022-06-30 | 2022-08-26 | 常州夏青科技有限公司 | Method for preparing mono-tert-butyl malonate by catalysis of strong acid resin |
| CN115894229A (en) * | 2022-11-15 | 2023-04-04 | 福州大学 | Selective synthesis process of monoethyl adipate |
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| CN103990499A (en) * | 2014-06-06 | 2014-08-20 | 四川恒达环境技术有限公司 | Preprocessing method for ion exchange resin for treating waste water at tail end of electrolytic manganese manufacturing technique |
| CN103990499B (en) * | 2014-06-06 | 2016-01-06 | 四川恒达环境技术有限公司 | A kind of preprocess method of the ion exchange resin for the treatment of electrolytic manganese production technique tail end wastewater |
| CN107043327A (en) * | 2017-05-12 | 2017-08-15 | 苏州富士莱医药股份有限公司 | A kind of synthetic method of monoethyl adipatee |
| CN107043327B (en) * | 2017-05-12 | 2020-11-03 | 苏州富士莱医药股份有限公司 | Synthesis method of monoethyl adipate |
| CN114940648A (en) * | 2022-06-30 | 2022-08-26 | 常州夏青科技有限公司 | Method for preparing mono-tert-butyl malonate by catalysis of strong acid resin |
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| CN115894229A (en) * | 2022-11-15 | 2023-04-04 | 福州大学 | Selective synthesis process of monoethyl adipate |
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