CN105693526A - Preparation method of 4,4'-methylene-bis-(3-chloro-2,6-diethylaniline) - Google Patents
Preparation method of 4,4'-methylene-bis-(3-chloro-2,6-diethylaniline) Download PDFInfo
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- C07C209/68—Preparation of compounds containing amino groups bound to a carbon skeleton from amines, by reactions not involving amino groups, e.g. reduction of unsaturated amines, aromatisation, or substitution of the carbon skeleton
- C07C209/78—Preparation of compounds containing amino groups bound to a carbon skeleton from amines, by reactions not involving amino groups, e.g. reduction of unsaturated amines, aromatisation, or substitution of the carbon skeleton from carbonyl compounds, e.g. from formaldehyde, and amines having amino groups bound to carbon atoms of six-membered aromatic rings, with formation of methylene-diarylamines
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- C07C209/74—Preparation of compounds containing amino groups bound to a carbon skeleton from amines, by reactions not involving amino groups, e.g. reduction of unsaturated amines, aromatisation, or substitution of the carbon skeleton by halogenation, hydrohalogenation, dehalogenation, or dehydrohalogenation
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Abstract
The invention discloses a preparation method of 4,4'-methylene-bis-(3-chloro-2,6-diethylaniline). The preparation method comprises the following steps: (1) in a nitrogen protective atmosphere, carrying out reaction on raw materials 2,6-diethylaniline and hydrochloric acid to generate 2,6-diethylaniline hydrochloride, and dropwisely adding formalin to carry out condensation reaction; after the reaction finishes, neutralizing with liquid caustic soda, and carrying out water separation to obtain 4,4'-methylene-bis-(2,6-diethylaniline); (2) dissolving the product in the step (1) in a solvent, and introducing chlorine to carry out chlorination reaction; after the reaction finishes, neutralizing with liquid caustic soda, and carrying out water separation to obtain a 4,4'-methylene-bis-(3-chloro-2,6-diethylaniline) crude product; and (3) dissolving the product in the step (2) in a solvent, decolorizing with activated carbon, cooling to crystallize, filtering, and drying to obtain the final product. The method has the advantages of simple technique, accessible raw materials, low price and high product purity and yield, and can easily implement industrial production.
Description
Technical field
The invention belongs to synthesis of polymer material field, relate to a kind of polyurethane chain extender 4, the preparation method of 4 '-methylene-bis--(3-chloro-2,6-diethyl aniline) [M-CDEA]。
Background technology
The research and development history of existing more than 60 year of polyurethane (abbreviation PU) material, along with the continuous extension of PU materials application, the quantity of its product has leapt to first of the big synthetic material in the world six at present, and whole world yield is at about more than 1,000 ten thousand tons。
PU material, because of the performance of its excellence, is widely used in the every field of national economy and the various aspects of people's clothing, food, lodging and transportion--basic necessities of life。As: the various nonmetallic materials in aerospace industry, spacesuit, various insulation materials, mine conveyer belt, the maskant material of aircraft tank, the general health care material such as artificial blood vessel, artificial kidney, biological adhesive and microcellular polyurethane shoe sole etc.。
PU material is usually and is formed by polyethers or PEPA and polyisocyanates polycondensation, in order to expand the range of application of PU material, improve its various physical properties, need to add one or more small molecule materials being referred to as chain extender in synthesis PU technical recipe, such as polyalcohols, aliphatic alcohols, aromatic alcohols, aromatic diamines etc.。Wherein 4, the aromatic diamines class chain extender that 4 '-methylene-bis--(the chloro-aniline of 2-) [MOCA] is representative, PU and the good physical and mechanical properties of polyether-type elastomer and result of use can be given, and cheap, thus being widely used。But MOCA toxicity is relatively big, after the U.S. in 1973 has people that the proposition of this product is had carcinogenic possibility, this has been carried out the toxicity Journal of Sex Research of decades by relevant departments, and present MOCA is classified as a class carcinogen by IARC。Therefore now the developed country such as European Union, the U.S., Japan has begun to that MOCA carries out restriction and uses, and phases out the use of MOCA, searching succedaneum。
In view of the foregoing, in recent years, start both at home and abroad progressively to use internationally recognized the 3rd class polyurethane chain extender to animal low toxicity instead。As: 4,4 '-methylene-bis--(the chloro-2,6-diethylaniline of 3-) [M-CDEA]。
The preparation method of current M-CDEA, is all adopt with 3-chloro-2,6-diethyl aniline for primary raw material according to bibliographical information both domestic and external, through with formaldehyde condensation reaction and prepared method。The feature of this preparation method is, adopts the raw material that chlorination is good, namely obtains product through a step condensation, and technique is simple。But raw material 3-chloro-2, the production requirement of 6-diethylaniline is highly difficult greatly, supply more difficult, because 3-chloro-2,6-diethyl aniline is to adopt high-temperature high-pressure craft preparation to obtain, yield is very low, price is significantly high, causes 4,4 '-methylene-bis--(3-chloro-2,6-diethylaniline) production cost of [M-CDEA] is also significantly high, and application is extremely restricted。
Summary of the invention
It is an object of the invention to provide a kind of 4, the preparation method of 4 '-methylene-bis--(3-chloro-2,6-diethyl aniline), the feature of this method is to adopt the raw material 2 being conveniently easy to get, 6-diethylaniline, first prepares intermediate 4,4 '-methylene-bis--(2 with formaldehyde condensation, 6-diethylaniline), pass into chlorine again and carry out chlorination reaction, prepare final products, constant product quality by comparatively gentle reaction condition, preparation cost is low, adapts to industrialized production。
In order to solve above-mentioned technical problem, the technical solution used in the present invention is a kind of 4, the preparation method of 4 '-methylene-bis--(3-chloro-2,6-diethyl aniline), it is characterised in that comprise the following steps:
(1) in glass reaction bottle, add water and hydrochloric acid, pass into nitrogen protection simultaneously, then drip raw material 2; 6-diethylaniline, stirs after adding, by controlling reaction temperature; raw material 2,6-diethylaniline is made to generate 2,6-diethylaniline hydrochloride with hydrochloric acid reaction in water; then formalin it is added dropwise to; after adding, insulation carries out condensation reaction, and reaction neutralizes with liquid caustic soda after terminating, and obtains 4 after point water filtration; 4 '-methylene-bis--(2,6-diethylaniline)。
(2) 4 after step (1) being obtained by reacting, 4 '-methylene-bis--(2,6-diethylaniline) join in reaction bulb, dissolve it in solvent by stirring, carrying out chlorination reaction with the chlorine being passed in this reaction bulb simultaneously, reaction neutralizes with liquid caustic soda after terminating, and obtains 4 after point water filtration, 4 '-methylene-bis--(3-chloro-2,6-diethyl aniline) crude product。
(3) 4 after step (2) being obtained by reacting, 4 '-methylene-bis--(3-chloro-2,6-diethylaniline) crude product heating for dissolving is in recrystallisation solvent, through activated carbon decolorizing, crystallisation by cooling, filtration, drying, obtain 4,4 '-methylene-bis--(3-chloro-2,6-diethyl aniline) product。
Further, in step (1), the mol ratio of 2,6-diethylanilines, hydrochloric acid, formalin and chlorine is: 1.0: 1.0～2.5: 0.5～0.8: 0.95～1.5。
Further, in step (1), the concentration of hydrochloric acid is 26%～36%, and the concentration of formalin is 28%～37%。
Further, in step (1), the dropping temperature of formalin and holding temperature are 50 DEG C～100 DEG C, and temperature retention time is 2～6 hours。
Further, in step (2), solvent is one or more the mixture in dichloromethane, chloroform, dichloroethanes, acetic acid and sulphuric acid。
Further, in step (2), solvent and 4, the mass ratio of 4 '-methylene-bis--(2,6-diethylaniline) is 1.0～3.5: 1.0。
Further, in step (2), 4, the mol ratio of 4 '-methylene-bis--(2,6-diethylaniline) and chlorine is 1.0: 0.95～1.5。
Further, in step (2), the time of chlorination reaction is 10～30 hours, and temperature is 0 DEG C～70 DEG C。
Further, in step (3), recrystallisation solvent is one or more the mixture in ethanol, isopropanol, n-butyl alcohol, petroleum ether, hexane, heptane, hexamethylene, hexahydrotoluene, ethyl cyclohexane, benzene and toluene, recrystallisation solvent and 4, the mass ratio of 4 '-methylene-bis--(3-chloro-2,6-diethyl aniline) crude product is 1.0～3.0: 1.0。
The reaction scheme of the preparation method of the one 4,4 '-methylene of the present invention-bis--(3-chloro-2,6-diethylaniline) is as follows:
The invention provides a kind of 4, the preparation method of 4 '-methylene-bis--(3-chloro-2,6-diethyl aniline), the technique of this preparation method is simple, reaction condition is not harsh, raw material is easy to get and price mental retardation embodiment preparation cost is low, and the purity of product and yield are high, are prone to again industrialized production。
Detailed description of the invention
The present invention is a kind of 4, and the preparation method of 4 '-methylene-bis--(3-chloro-2,6-diethyl aniline) comprises the following steps:
(1) in glass reaction bottle, water and hydrochloric acid are added, pass into nitrogen protection simultaneously, drip raw material 2 again, 6-diethylaniline, stir after adding, by controlling reaction temperature, make raw material 2, 6-diethylaniline generates 2 with hydrochloric acid reaction in water, 6-diethylaniline hydrochloride, then formalin it is added dropwise to, the concentration of hydrochloric acid is 26%～36%, the concentration of formalin is 28%～37%, after adding, insulation carries out condensation reaction, the dropping temperature of formalin and holding temperature are 50 DEG C～100 DEG C, temperature retention time is 2～6 hours, reaction neutralizes with liquid caustic soda after terminating, 4 are obtained after dividing water filtration, 4 '-methylene-bis--(2, 6-diethylaniline), 2, 6-diethylaniline, hydrochloric acid, the mol ratio of formalin and chlorine is: 1.0: 1.0～2.5: 0.5～0.8: 0.95～1.5。
(2) 4 after step (1) being obtained by reacting, 4 '-methylene-bis--(2, 6-diethylaniline) join in reaction bulb, it is made to be substantially dissolved in solvent by stirring, solvent is dichloromethane, chloroform, dichloroethanes, one or more mixture in acetic acid and sulphuric acid, solvent and 4, 4 '-methylene-bis--(2, 6-diethylaniline) mass ratio be 1.0～3.5: 1.0, chlorination reaction is carried out with the chlorine being passed in this reaction bulb simultaneously, the time of chlorination reaction is 10～30 hours, temperature is 0 DEG C～70 DEG C, 4, 4 '-methylene-bis--(2, 6-diethylaniline) it is 1.0: 0.95～1.5 with the mol ratio of chlorine, reaction neutralizes with liquid caustic soda after terminating, 4 are obtained after dividing water filtration, 4 '-methylene-bis--(3-chloro-2, 6-diethylaniline) crude product。
(3) 4 after step (2) being obtained by reacting, 4 '-methylene-bis--(3-chloro-2, 6-diethylaniline) crude product heating for dissolving is in recrystallisation solvent, through activated carbon decolorizing, crystallisation by cooling, filter, dry, obtain 4, 4 '-methylene-bis--(3-chloro-2, 6-diethylaniline) product, recrystallisation solvent is ethanol, isopropanol, n-butyl alcohol, petroleum ether, hexane, heptane, hexamethylene, hexahydrotoluene, ethyl cyclohexane, one or more mixture in benzene and toluene, recrystallisation solvent and 4, 4 '-methylene-bis--(3-chloro-2, 6-diethylaniline) mass ratio of crude product is 1.0～3.0: 1.0。
By the following examples the present invention is carried out more specific description, but the present invention is not limited to described embodiment。
Embodiment 1
Glass reaction bottle adds in 600ml water with 85ml hydrochloric acid (36%); logical nitrogen protection, drips 149g2,6-diethylaniline; stir 30 minutes after adding; heat to 50-55 DEG C, be then added dropwise to 41g37% formalin, be warmed up to 90～95 DEG C after adding and react 2 hours; reaction is cooled to 30 DEG C after terminating, is neutralized to PH=7 with 30% liquid caustic soda; filter 4,4 '-methylene-bis--(2,6-diethylaniline)。
4 will obtained, 4 '-methylene-bis--(2,6-diethylaniline) adds in reaction bulb, add 350g acetic acid, be stirred and heated to 50-55 DEG C, be slowly introducing chlorine, when 4, stopping logical chlorine during the content 95% of 4 '-methylene-bis--(3-chloro-2,6-diethyl aniline), reaction is cooled to 30 DEG C, adds 200ml water after terminating, it is neutralized to PH=7 with 30% liquid caustic soda, it is filtrated to get 4,4 '-methylene-bis-(3-chloro-2,6-diethyl aniline) crude product。
4 will obtained, 4 '-methylene-bis-(3-chloro-2,6-diethyl aniline) crude product 250g ethanol dissolves, activated carbon decolorizing, crystallization, dries and obtains 176g4,4 '-methylene-bis--(3-chloro-2,6-diethyl aniline)。Yield 92.8%, purity (HPLC) 98.6%, fusing point 87.9～89.1 DEG C。
Embodiment 2
Glass reaction bottle adds in 600ml water with 288ml hydrochloric acid (26%); logical nitrogen gas protection; dropping 149g2; 6-diethylaniline; stir 30 minutes after adding; heat to 90～95 DEG C, be then added dropwise to 85g28% formalin, be warmed up to 100 DEG C after adding and react 6 hours。Reaction is cooled to 30 DEG C, is neutralized to PH=7 with 30% liquid caustic soda after terminating, filter 4,4 '-methylene-bis--(2,6-diethylaniline)。
4 will obtained, 4 '-methylene-bis--(2,6-diethylaniline) adds in reaction bulb, add 525g dichloroethanes, be stirred and heated to 60-70 DEG C, be slowly introducing chlorine, logical chlorine is stopped when the content 95% of 4,4 '-methylene-bis--(3-chloro-2,6-diethyl aniline), reaction is cooled to 30 DEG C, adds 200ml water after terminating, it is neutralized to PH=7 with 30% liquid caustic soda, filters, obtain 4,4 '-methylene-bis-(3-chloro-2,6-diethyl aniline) crude product。
4 will obtained, 4 '-methylene-bis-(3-chloro-2,6-diethyl aniline) crude product 175g hexamethylene dissolves, activated carbon decolorizing, crystallization, dries and obtains 155g4,4 '-methylene-bis--(3-chloro-2,6-diethyl aniline)。Yield 82.1%, purity (HPLC) 98.2%, fusing point 87.1～88.2 DEG C。
Embodiment 3
Glass reaction bottle adds in 600ml water with 150ml hydrochloric acid (30%), logical nitrogen protection, drip 149g2; 6-diethylaniline, stirs 30 minutes after adding, heats to 70～75 DEG C; then it is added dropwise to 56g32% formalin, is warmed up to 90 DEG C after adding and reacts 4 hours。Reaction is cooled to 30 DEG C, is neutralized to PH=7 with 30% liquid caustic soda after terminating, filter 4,4 '-methylene-bis--(2,6-diethylaniline)。
4 will obtained, 4 '-methylene-bis--(2,6-diethylaniline) adds in reaction bulb, adding the concentrated sulphuric acid of 150g98%, stirring is cooled to 0～10 DEG C, is slowly introducing chlorine, logical chlorine is stopped when the content 95% of 4,4 '-methylene-bis--(3-chloro-2,6-diethyl aniline), reaction adds 200ml water after terminating, it is neutralized to PH=7 with 30% liquid caustic soda, filters, obtain 4,4 '-methylene-bis-(3-chloro-2,6-diethyl aniline) crude product。
4 will obtained, 4 '-methylene-bis-(3-chloro-2,6-diethyl aniline) crude product 350g toluene dissolves, activated carbon decolorizing, crystallization, dries and obtains 162g4,4 '-methylene-bis--(3-chloro-2,6-diethyl aniline)。Yield 85.6%, purity (HPLC) 98.5%, fusing point 87.3～89.1 DEG C。
Embodiment 4
Glass reaction bottle adds in 600ml water with 160ml hydrochloric acid (28%); logical nitrogen protection; dropping 149g2; 6-diethylaniline; stir 30 minutes after adding; heat to 75～80 DEG C, be then added dropwise to 41g37% formalin, be warmed up to 90～100 DEG C after adding and react 3 hours。Reaction is cooled to 30 DEG C, is neutralized to PH=7 with 30% liquid caustic soda after terminating, filter 4,4 '-methylene-bis--(2,6-diethylaniline)。
4 will obtained, 4 '-methylene-bis--(2,6-diethylaniline) adds in reaction bulb, adding the dichloromethane of 400g, stirring is cooled to 50～60 DEG C, is slowly introducing chlorine, logical chlorine is stopped when the content 95% of 4,4 '-methylene-bis--(3-chloro-2,6-diethyl aniline), reaction is cooled to 30 DEG C, adds 200ml water after terminating, it is neutralized to PH=7 with 30% liquid caustic soda, filters, obtain 4,4 '-methylene-bis-(3-chloro-2,6-diethyl aniline) crude product。
4 will obtained, 4 '-methylene-bis-(3-chloro-2,6-diethyl aniline) crude product 500g isopropanol dissolves, activated carbon decolorizing, crystallization, dries and obtains 162g4,4 '-methylene-bis--(3-chloro-2,6-diethyl aniline)。Yield 90.6%, purity (HPLC) 99.0%, fusing point 87.5～89.6 DEG C。
Result of the test refers to table 1 and table 2:
The reaction condition of table 14,4 '-methylene-bis-(the chloro-2,6-diethylaniline of 3-)
The reaction result of table 24,4 '-methylene-bis-(the chloro-2,6-diethylaniline of 3-)
These are only specific embodiments of the invention, but the technical characteristic of the present invention is not limited thereto。Any based on the present invention, for realizing essentially identical technique effect, done ground simple change, equivalent replacement or modification etc., all it is covered by among protection scope of the present invention。
Claims (9)
1. one kind 4, the preparation method of 4 '-methylene-bis--(3-chloro-2,6-diethyl aniline), it is characterised in that comprise the following steps:
(1) in glass reaction bottle, add water and hydrochloric acid, pass into nitrogen protection simultaneously, then drip raw material 2; 6-diethylaniline, stirs after adding, by controlling reaction temperature; raw material 2,6-diethylaniline is made to generate 2,6-diethylaniline hydrochloride with hydrochloric acid reaction in water; then formalin it is added dropwise to; after adding, insulation carries out condensation reaction, and reaction neutralizes with liquid caustic soda after terminating, and obtains 4 after point water filtration; 4 '-methylene-bis--(2,6-diethylaniline)；
(2) 4 after step (1) being obtained by reacting, 4 '-methylene-bis--(2,6-diethylaniline) join in reaction bulb, dissolve it in solvent by stirring, carrying out chlorination reaction with the chlorine being passed in this reaction bulb simultaneously, reaction neutralizes with liquid caustic soda after terminating, and obtains 4 after point water filtration, 4 '-methylene-bis--(3-chloro-2,6-diethyl aniline) crude product；
(3) 4 after step (2) being obtained by reacting, 4 '-methylene-bis--(3-chloro-2,6-diethylaniline) crude product heating for dissolving is in recrystallisation solvent, through activated carbon decolorizing, crystallisation by cooling, filtration, drying, obtain 4,4 '-methylene-bis--(3-chloro-2,6-diethyl aniline) product。
2. according to claim 1 a kind of 4,4 '-methylene-bis--(3-chloro-2,6-diethylaniline) preparation method, it is characterized in that: in described step (1), the mol ratio of described 2,6-diethylanilines, described hydrochloric acid, described formalin and described chlorine is: 1.0: 1.0～2.5: 0.5～0.8: 0.95～1.5。
3. according to claim 1 a kind of 4, the preparation method of 4 '-methylene-bis--(3-chloro-2,6-diethyl aniline), it is characterised in that: in described step (1), the concentration of described hydrochloric acid is 26%～36%, and the concentration of described formalin is 28%～37%。
4. according to claim 1 a kind of 4,4 '-methylene-bis--(3-chloro-2,6-diethylaniline) preparation method, it is characterized in that: in described step (1), the dropping temperature of described formalin and holding temperature are 50 DEG C～100 DEG C, and temperature retention time is 2～6 hours。
5. according to claim 1 a kind of 4,4 '-methylene-bis--(3-chloro-2,6-diethylaniline) preparation method, it is characterized in that: in described step (2), described solvent is one or more the mixture in dichloromethane, chloroform, dichloroethanes, acetic acid and sulphuric acid。
6. according to claim 1 a kind of 4,4 '-methylene-bis--(3-chloro-2,6-diethylaniline) preparation method, it is characterized in that: in described step (2), described solvent and described 4, the mass ratio of 4 '-methylene-bis--(2,6-diethylaniline) is 1.0～3.5: 1.0。
7. according to claim 1 a kind of 4,4 '-methylene-bis--(3-chloro-2,6-diethylaniline) preparation method, it is characterized in that: in described step (2), described 4, the mol ratio of 4 '-methylene-bis--(2,6-diethylaniline) and described chlorine is 1.0: 0.95～1.5。
8. according to claim 1 a kind of 4, the preparation method of 4 '-methylene-bis--(3-chloro-2,6-diethyl aniline), it is characterised in that: in described step (2), the time of described chlorination reaction is 10～30 hours, and temperature is 0 DEG C～70 DEG C。
9. according to claim 1 a kind of 4,4 '-methylene-bis--(3-chloro-2,6-diethylaniline) preparation method, it is characterized in that: in described step (3), described recrystallisation solvent is one or more the mixture in ethanol, isopropanol, n-butyl alcohol, petroleum ether, hexane, heptane, hexamethylene, hexahydrotoluene, ethyl cyclohexane, benzene and toluene, described recrystallisation solvent and described 4, the mass ratio of 4 '-methylene-bis--(3-chloro-2,6-diethyl aniline) crude product is 1.0～3.0: 1.0。
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