CN102604072B - Preparation method of polyether amine - Google Patents
Preparation method of polyether amine Download PDFInfo
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- CN102604072B CN102604072B CN 201210052388 CN201210052388A CN102604072B CN 102604072 B CN102604072 B CN 102604072B CN 201210052388 CN201210052388 CN 201210052388 CN 201210052388 A CN201210052388 A CN 201210052388A CN 102604072 B CN102604072 B CN 102604072B
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Abstract
The invention relates to a preparation method of polyether amine. In the structure of polyether amine, the main chain is polypropylene oxide, polyethylene oxide, polytetrahydrofuran or a copolymer of polypropylene oxide, polyethylene oxide and polytetrahydrofuran; and one end of the main chain is hydroxyl, and the other end of the main chain is an alcohol amine compound terminated end having a H2N-R-O-H structure. Polyether amine is prepared by the following steps: (1) protecting the amino of the alcohol amine compound by using BOC (tertbutyloxycarbonyl) and maintaining hydroxyl to obtain BOC-NH-R-OH; (2) in the catalysis of strong base or double-metal cyanide, by using BOC-NH-R-OH, initiating polyethylene oxide, polypropylene oxide, tetrahydrofuran or the mixture of polyethylene oxide, polypropylene oxide and tetrahydrofuran to react for ring opening polymerization; and (3) under the acidic condition, carrying out BOC deprotection reaction to obtain polyether amine. According to the invention, polyether main chains having different hydrophilic properties can be obtained by regulating the ratio of polypropylene oxide to polyethylene oxide to polytetrahydrofuran in the polyether chain; and one end of the polyether chain contains the amino, thus the amino can provide strong hydrophilic property after acidification. Polyether amine prepared by using the method can be applied to the fields of a surfactant, a flocculant, textile dyeing and finishing auxiliary, electrophoretic paint and the like.
Description
Technical field
The present invention relates to a kind of preparation method of polyetheramine, an especially a kind of end contains amido, and the other end is the preparation method of the polyetheramine of hydroxyl, belongs to chemical technology field.
Background technology
Polyetheramine is that a class main chain contains the polyoxygenated alkyl structure, and active function groups is the compound of amido.By selecting different polyoxygenated alkyl structures, can regulate a series of performances such as toughness, viscosity and wetting ability of polyetheramine, and amido offers the possibility of polyetheramine and multiple compounds reaction.Because of its special structure, polyetheramine shows unique performance in numerous Application Areass, and its range of application is also more and more wider.
Present published synthetic method, the terminal method of introducing amido of polyethers mainly comprises three kinds: (1) polyethers terminal hydroxyl utilizes ammonia/hydrogen direct aminatin under catalyst action; (2) by introducing cyano group, obtain amido behind the shortening; (3) by compound and the polyether reactant of amino-contained, introduce amido.Wherein front two kinds of methods are had relatively high expectations to equipment and process, by comparison, the third technique ratio is easier to realize, but because the aminated compounds of selecting often contains several amidos simultaneously, other contain the group of active hydrogen atom perhaps to contain hydroxyl, carboxyl etc., therefore when being connected with polyether chain, be difficult to guarantee that an aminated compounds only connects a polyether backbone, therefore selecting suitable aminated compounds, and selectively it is linked to each other with polyether chain, is the key of these class methods.
CN1546550A discloses under the metal catalyst effect, by the still reaction at intermittence, prepares the amido polyethers with polyether glycol.CN1803882A discloses a kind of hydroxy benzylamine end capped polyether polyvalent alcohol, the synthetic method that contains the polyetheramine of phenyl ring.CN102212191A discloses a kind of by utilizing dicarbapentaborane imidazoles activation polyether glycol hydroxyl, and direct and reacting ethylenediamine obtains the method for Amino Terminated polyether(ATPE).CN102086263A discloses a kind of synthetic method of azanol base polyethers, and reaching operational path mainly is polyether glycol and epoxy chloropropane synthesizing glycidol ether, again with the unit primary amine reaction.CN101001902 discloses a kind of utilize epoxy chloropropane and polyether glycol reaction, then utilizes aliphatic amide to react with it, and amido is linked to each other with polyether chain.
Because show stronger wetting ability after the ionization of polyetheramine amido, and the polyether structure main chain can be selected by monomer, control it and show wetting ability or hydrophobicity, therefore an end shows splendid performance for amino polyetheramine in fields such as tensio-active agent, flocculation agent, dyeing and finishing auxiliaries and electrocoating paints.By structure design, synthetic backbone structure is controlled, and an end is the polyetheramine of amido, has a wide range of applications in these fields.
Summary of the invention
The objective of the invention is to overcome the deficiencies in the prior art, a kind of preparation method of polyetheramine is provided, can effectively avoid two or above polyether backbone to be connected on the same pure amine molecule, can obtain more regular single-ended of structure and be the polyetheramine structure of amido.
According to technical scheme provided by the invention, the main chain of described polyetheramine is poly(propylene oxide), polyethylene oxide, polytetrahydrofuran or three's multipolymer, and the polymerization degree is 5～100, and an end of main chain is hydroxyl, and the other end of main chain is for having general formula H
2The alcamine compound end-blocking of N-R-OH (I) structure;
Wherein R is the C of straight or branched
nH
2n, n=2～18 or
X=0～10, y=0～10 or
X=0～10, y=0～10 or
N=0～10.
The present invention also protects a kind of preparation method of polyetheramine, and feature is to adopt following processing step:
(1) will have general formula H
2In the mixed solvent of the alcamine compound of N-R-OH (I) structure water-soluble or water and organic solvent, concentration is 10～60%; Described organic solvent is tetrahydrofuran (THF) or dioxane, and the ratio of organic solvent and water is 5: 95～40: 60 in the mixed solvent;
(2) drip catalyzer and tert-Butyl dicarbonate in the compound that obtains to step (1), the temperature during dropping is-10～40 ℃, is added dropwise to complete in 1～6 hour; After being added dropwise to complete, reacted 4～48 hours under-10～40 ℃ the condition in temperature, the pH value after reaction finishes is 10～14; Described catalyzer is NaOH, Na
2CO
3Perhaps triethylamine, the mol ratio of catalyzer and alcamine compound is 0.5～3: 1, the mol ratio of tert-Butyl dicarbonate and alcamine compound is 1～1.1: 1, described tert-Butyl dicarbonate is pure tert-Butyl dicarbonate or the mixing solutions of tert-Butyl dicarbonate and organic solvent, the concentration of the mixing solutions of described tert-Butyl dicarbonate and organic solvent is 10～60%, and described organic solvent is acetone, tetrahydrofuran (THF) or dioxane;
(3) compound that step (2) is obtained carries out underpressure distillation, and to remove the organic solvent in the compound, vacuum pressure is less than 500Pa, and distillation temperature is 40～100 ℃;
(4) add organic solvent in the compound that obtains to step (3) and extract, obtain water layer and organic layer; After extracting again once with organic solvent water layer, organic phase and the organic layer that obtains merged; With organic layer saturated common salt water washing, added anhydrous sodium sulfate drying 2～6 hours, organic solvent is removed in underpressure distillation, obtains the alcamine compound BOC-NH-R-OH by tertbutyloxycarbonyl (BOC) protection; Described organic solvent is ethyl acetate, benzene, toluene, hexanaphthene, methylene dichloride or chloroform;
(5) to oxide compound or oxyhydroxide or double metal cyanide by adding basic metal or alkaline-earth metal among the alcamine compound BOC-NH-R-OH of tertbutyloxycarbonyl (BOC) protection, the add-on of the oxide compound of basic metal or alkaline-earth metal or oxyhydroxide or double metal cyanide is 0.1～5%wt by the alcamine compound BOC-NH-R-OH of tertbutyloxycarbonyl (BOC) protection, in reaction system, rush nitrogen to remove oxygen, be warming up to 50～100 ℃, be evacuated to pressure less than 500Pa, kept 0.5～2 hour, and removed the water in the reaction system;
(6) add monomer in the product that obtains to step (5) and react, temperature of reaction is 80～120 ℃, and reaction pressure is 0.1～0.6MPa, adds a kind of monomer at every turn, and the question response Pressure Drop adds lower a kind of monomer to the normal pressure or reaction finishes; The add-on of described monomer and the mol ratio of BOC-NH-R-OH are 5～100: 1, and described monomer is one or more in oxyethane, propylene oxide or the tetrahydrofuran (THF);
(7) hydrochloric acid that adds 0.5～5mol/L in the product that obtains to step (6), regulating pH value is 1～2, the maintenance temperature is 50～80 ℃, reacts 1～4 hour, to slough tertbutyloxycarbonyl (BOC) group;
(8) keeping the temperature of the product that step (7) obtains is 40～100 ℃, vacuumize to make pressure less than 500Pa, and, after forming without water droplet to the return line tube wall, kept again 0.5～1 hour; Filter; Add sorbent material and adsorb, keeping temperature in the adsorption process is 100～120 ℃, and adsorption time is 1～3 hour; Be cooled to 30～50 ℃, filter, namely obtain described polyetheramine product.
The oxide compound of described basic metal or alkaline-earth metal or oxyhydroxide are sodium hydroxide, potassium hydroxide, strontium oxide, barium oxide, strontium hydroxide or hydrated barta.
After step (5) was processed, the water content of reaction system was less than 0.5%.
Described sorbent material is hexa-magnesium silicate or six pure aluminium silicate.
The add-on of described sorbent material is 0.1～5% of the product total amount that obtains of step (7).
In the step (2), the adding mode of catalyzer and tert-Butyl dicarbonate adds first catalyzer for (1), tert-Butyl dicarbonate is dissolved in dripping behind the organic solvent again adding; Or (2) add first tert-Butyl dicarbonate, drips to add catalyzer again; Or (3) drip adding catalyzer and tert-Butyl dicarbonate simultaneously.
With existing single-ended be amido the polyetheramine synthetic method relatively, the present invention has realized the synthetic of target product under normal condition, avoided the high requirement of hydroxyl direct aminatin for conversion unit and reaction conditions; Adopt simultaneously the BOC group to protect for amido, effectively reduced the side reaction when aminated compounds links to each other with polyether chain, obtain the polyetheramine product of compound with regular structure.Product can be applicable to the fields such as tensio-active agent, flocculation agent, dyeing and finishing auxiliaries and electrocoating paint.
Embodiment
The invention will be further described below in conjunction with specific embodiment.
The main chain of polyetheramine of the present invention is poly(propylene oxide), polyethylene oxide, polytetrahydrofuran or three's multipolymer, and the polymerization degree is 5～100, and an end of main chain is hydroxyl, and the other end of main chain is for having general formula H
2The alcamine compound end-blocking of N-R-OH (I) structure;
Wherein R is the C of straight or branched
nH
2n, n=2～18 or
X=0～10, y=0～10 or
X=0～10, y=0～10 or
N=0～10.
Polyetheramine of the present invention prepares by following method: (1) utilizes the amido of the alcamine compound of tertbutyloxycarbonyl (BOC) protection general formula (I) structure, and hydroxyl keeps, and obtains BOC-NH-R-OH; (2) gained BOC-NH-R-OH under highly basic or double metal cyanide (DMC) catalysis, causes oxyethane, propylene oxide, tetrahydrofuran (THF) or three's mixture reaction, carries out ring-opening polymerization; (3) under acidic conditions, carry out the protective reaction of sloughing of BOC, obtain described polyetheramine.The polyetheramine that adopts the method to obtain, by regulating the ratio of propylene oxide, oxyethane and tetrahydrofuran (THF) in the polyether chain, can get the polyether backbone of different hydrophilic, one end of polyether chain contains amido, can provide stronger wetting ability after the acidifying, can be applicable to the fields such as tensio-active agent, flocculation agent, dyeing and finishing auxiliaries and electrocoating paint.
Embodiment 1: a kind of preparation method of polyetheramine, adopt following processing step:
(1) 100g thanomin (1.64mol) and 131gNaOH (3.28mol) are dissolved in the 500ml water, are cooled to 0 ℃, with the tert-Butyl dicarbonate (BOC of 375g
2O) be dissolved in the acetone soln that 500g acetone obtains tert-Butyl dicarbonate, the acetone soln of tert-Butyl dicarbonate slowly is added drop-wise in the thanomin, the control dropping temperature is 0 ℃, be added dropwise to complete in 2 hours, keeping temperature is 0 ℃, continues reaction 4 hours, and the pH value after reaction finishes is about 11;
(2) product that step (1) is obtained carries out underpressure distillation, removes the acetone in the product, and vacuum pressure is 500Pa, and distillation temperature is 60 ℃;
(3) add the 500ml ethyl acetate in the product that obtains to step (2) and extract, obtain water layer and organic layer; After extracting again once with the 250ml ethyl acetate water layer, organic phase and the organic layer that obtains merged; Organic layer with 300ml saturated aqueous common salt washed twice, was added anhydrous sodium sulfate drying 2 hours; Underpressure distillation, control pressure are 500Pa, and slowly are warming up to 100 ℃, remove ethyl acetate, obtain the thanomin BOC-MEA by tertbutyloxycarbonyl (BOC) protection, 221.8g;
(4) the thanomin BOC-MEA by tertbutyloxycarbonyl (BOC) protection with 161g puts into autoclave pressure, the KOH that adds 3g, be warming up to 80 ℃, in reaction system, rush nitrogen to remove oxygen, being evacuated to pressure is 500Pa, keeps 1 hour, removes the water in the reaction system, after the reaction, the water content of reaction system is less than 0.5%;
(5) close vacuum, add 440g oxyethane in the product that obtains to step (4) and react, temperature of reaction is 100 ℃, and the control reaction pressure is 0.6MPa, and question response Pressure Drop to normal pressure afterreaction finishes;
(6) add the hydrochloric acid of 0.5mol/L in the product that obtains to step (5), regulating pH value is 2, and the maintenance temperature is 70 ℃, reacts 2 hours, to slough tertbutyloxycarbonyl (BOC) group;
(7) keeping the temperature of the product that step (6) obtains is 70 ℃, and vacuumizing and making pressure is 500Pa,, after forming without water droplet to the return line tube wall, continue to keep 0.5 hour; Filter; Add the 8g hexa-magnesium silicate and adsorb, keeping temperature in the adsorption process is 105 ℃, and adsorption time is 1 hour; Be cooled to 30 ℃, filter, namely obtain described polyetheramine product, 489g.
Embodiment 2: a kind of preparation method of polyetheramine, adopt following processing step:
(1) 100g thanomin (1.64mol) and 375g tert-Butyl dicarbonate (1.72mol) are dissolved in the 1000ml water, be cooled to-5 ℃, the NaOH (3.28mol) of 131g is dissolved in obtains the NaOH aqueous solution in the 500ml water, under agitation slowly be added drop-wise in the thanomin NaOH aqueous solution, be added dropwise to complete in 2 hours, dropping temperature is-5 ℃; Be added dropwise to complete rear maintenance-5 ℃, continue reaction 6 hours, after the reaction knot was whole, the pH value of reaction system was 10;
(2) add the 500ml ethyl acetate in the compound that obtains to step (1) and extract, obtain water layer and organic layer; After extracting again once with the 250ml ethyl acetate water layer, organic phase and the organic layer that obtains merged; Organic layer with 300ml saturated aqueous common salt washed twice, was added anhydrous sodium sulfate drying 3 hours, underpressure distillation, control pressure is 450Pa, and slowly is warming up to 100 ℃, removes ethyl acetate, obtain the thanomin BOC-MEA by tertbutyloxycarbonyl (BOC) protection, 240.3g;
(3) the thanomin BOC-MEA that 161g is protected by tertbutyloxycarbonyl (BOC) puts into autoclave pressure, adds the KOH of 5g, is warming up to 80 ℃, being evacuated to pressure is 450Pa, keeps 1 hour, removes the water in the reaction system, after the reaction, the water content of reaction system is less than 0.5%;
(4) close vacuum, add 300g oxyethane in the product that obtains to step (3), keeping temperature of reaction is 80 ℃, reaction pressure is 0.5MPa, the question response Pressure Drop is to normal pressure, add the 640g propylene oxide, keeping temperature of reaction is 100 ℃, finishes until reaction pressure is down to the normal pressure afterreaction;
(5) add the hydrochloric acid of 5mol/L in the product that obtains to step (4), regulating pH value is 1, and the maintenance temperature is 50 ℃, reacts 4 hours, to slough tertbutyloxycarbonyl (BOC) group;
(6) temperature that keeps the product that step (5) obtains is greater than 70 ℃, and vacuumizing and making pressure is 450Pa,, after forming without water droplet to the return line tube wall, continue to keep 0.5 hour; Filter; Add 8g six pure aluminium silicate, keeping temperature in the adsorption process is 105 ℃, and adsorption time is 1 hour; Be cooled to 30 ℃, filter, namely obtain described polyetheramine product, 990g.
Embodiment 3: a kind of preparation method of polyetheramine, adopt following processing step:
(1) 100g thanomin (1.64mol) is dissolved in the 1000ml water, be cooled to 5 ℃, the NaOH (3.28mol) of 131g is dissolved in obtains the NaOH aqueous solution in the 500ml water, under agitation simultaneously slowly be added drop-wise in the thanomin NaOH aqueous solution and 375g tert-Butyl dicarbonate (1.72mol), be added dropwise to complete in 3 hours, dropping temperature is 5 ℃; Be added dropwise to complete 5 ℃ of rear maintenances, continue reaction 6 hours, after the reaction knot was whole, the pH value of reaction system was 11;
(2) add 500ml toluene in the compound that obtains to step (1) and extract, obtain water layer and organic layer; After extracting again once with 250ml toluene water layer, organic phase and the organic layer that obtains merged; Organic layer with 300ml saturated aqueous common salt washed twice, was added anhydrous sodium sulfate drying 2 hours, underpressure distillation, control pressure is less than 500Pa, and slowly is warming up to 80 ℃, removes toluene, obtain the thanomin BOC-MEA by tertbutyloxycarbonyl (BOC) protection, 240.3g;
(3) the thanomin BOC-MEA that 161g is protected by tertbutyloxycarbonyl (BOC) puts into autoclave pressure, adds the KOH of 4.5g, is warming up to 80 ℃, be evacuated to pressure less than 500Pa, kept 1 hour, remove the water in the reaction system, after the reaction, the water content of reaction system is less than 0.5%;
(4) close vacuum, add the 940g propylene oxide in the product that obtains to step (3), keeping temperature of reaction is 100 ℃, and reaction pressure finishes until reaction pressure is down to the normal pressure afterreaction less than 0.6MPa;
(5) add the hydrochloric acid of 5mol/L in the product that obtains to step (4), regulating pH value is 1, and the maintenance temperature is 50 ℃, reacts 2 hours, to slough tertbutyloxycarbonyl (BOC) group;
(6) temperature that keeps the product that step (5) obtains is greater than 70 ℃, vacuumizes to make pressure less than 500Pa, and, after forming without water droplet to the return line tube wall, continue to keep 0.5 hour; Filter; Add 5g six pure aluminium silicate, keeping temperature in the adsorption process is 110 ℃, and adsorption time is 2 hours; Be cooled to 30 ℃, filter, namely obtain described polyetheramine product, 992g.
Embodiment 4: a kind of preparation method of polyetheramine, adopt following processing step:
(1) polyetheramine that 250g embodiment 1 is obtained (0.5mol) and 115.5g tert-Butyl dicarbonate (0.53mol) are dissolved in the 1000ml water, be cooled to 0 ℃, again 131gNaOH (3.28mol) is dissolved in and obtains the NaOH aqueous solution in the 500ml water, under agitation slowly be added drop-wise in the polyetheramine NaOH aqueous solution, be added dropwise to complete in 2 hours, dropping temperature is 0 ℃; Be added dropwise to complete 0 ℃ of rear maintenance, continue reaction 8 hours;
(2) add the 1000ml ethyl acetate in the compound that obtains to step (1) and extract, obtain water layer and organic layer; After extracting again once with the 500ml ethyl acetate water layer, organic phase and the organic layer that obtains merged; Organic layer with 500ml saturated aqueous common salt washed twice, was added anhydrous sodium sulfate drying 4 hours, underpressure distillation, control pressure is less than 500Pa, and slowly is warming up to 100 ℃, removes ethyl acetate, obtain the polyetheramine BOC-PEA by tertbutyloxycarbonyl (BOC) protection, 274.4g;
(3) will put into autoclave pressure by the polyetheramine BOC-PEA of tertbutyloxycarbonyl (BOC) protection, add 2gKOH, be warming up to 80 ℃, in reaction system, rush nitrogen to remove oxygen, be evacuated to pressure less than 500Pa, kept 1 hour, and removed the water in the reaction system, the water content of reaction afterreaction system is less than 0.5%;
(4) close vacuum, add the 200g propylene oxide in the product that obtains to step (3) and react, temperature of reaction is 80 ℃, and reaction pressure is less than 0.6MPa, and question response Pressure Drop to normal pressure afterreaction finishes;
(5) add the hydrochloric acid of 2mol/L in the product that obtains to step (4), regulating pH value is 1, and the maintenance temperature is 70 ℃, reacts 2 hours, to slough tertbutyloxycarbonyl (BOC) group;
(8) temperature that keeps the product that step (7) obtains is greater than 70 ℃, vacuumizes to make pressure less than 500Pa, and, after forming without water droplet to the return line tube wall, continue to keep 0.5 hour; Filter; Add the 4g hexa-magnesium silicate and adsorb, keeping temperature in the adsorption process is 70 ℃, and adsorption time is 1 hour; Be cooled to 50 ℃, filter, namely obtain described polyetheramine product, 396g.
Embodiment 5: a kind of preparation method of polyetheramine, adopt following processing step:
(1) 123g α-amino isopropyl alcohol (1.64mol) and 375g tert-Butyl dicarbonate (1.72mol) are dissolved in the 1000ml water, be cooled to 0 ℃, the NaOH (3.28mol) of 131g is dissolved in 500ml water, slowly be added drop-wise in the α-amino isopropyl alcohol under stirring, be added dropwise to complete 2 ℃ of dropping temperatures in 2 hours; After being added dropwise to complete, keep 2 ℃ to continue reaction 4 hours, the pH value that reaction finishes the afterreaction system is 10;
(2) add the 500ml ethyl acetate in the compound that obtains to step (1) and extract, obtain water layer and organic layer; After extracting again once with the 250ml ethyl acetate water layer, organic phase and the organic layer that obtains merged; Organic layer with the water washing of 300ml saturated common salt, was added anhydrous sodium sulfate drying 3 hours, and the underpressure distillation control pressure is less than 500Pa, and slowly be warming up to 100 ℃, remove ethyl acetate, obtain the α-amino isopropyl alcohol BOC-IPA by tertbutyloxycarbonyl (BOC) protection, 272.3g;
(3) the α-amino isopropyl alcohol BOC-IPA by tertbutyloxycarbonyl (BOC) protection with 175g puts into autoclave pressure, adds the KOH of 3g, is warming up to 80 ℃, be evacuated to pressure less than 500Pa, kept 1 hour, remove the water in the reaction system, after the reaction, the water content of reaction system is less than 0.5%;
(4) close vacuum, add 440g oxyethane in the product that obtains to step (3) and react, temperature of reaction is 100 ℃, and the control reaction pressure is no more than 0.6MPa, and question response Pressure Drop to normal pressure afterreaction finishes;
(5) add the hydrochloric acid of 0.5mol/L in the product that obtains to step (4), regulating pH value is 2, and the maintenance temperature is 70 ℃, reacts 2 hours, to slough tertbutyloxycarbonyl (BOC) group;
(6) temperature that keeps the product that step (5) obtains is greater than 70 ℃, vacuumizes to make pressure less than 500Pa, and, after forming without water droplet to the return line tube wall, continue to keep 0.5 hour; Filter; Add the 8g hexa-magnesium silicate and adsorb, keeping temperature in the adsorption process is 105 ℃, and adsorption time is 1 hour; Be cooled to 30 ℃, filter, namely obtain described polyetheramine product, 501.5g.
Embodiment 6: a kind of preparation method of polyetheramine, adopt following processing step:
(1) 146.1g 4-amido-n-butyl alcohol (1.64mol) is dissolved in the 1000ml water, be cooled to 0 ℃, the NaOH (3.28mol) of 131g is dissolved in obtains the NaOH aqueous solution in the 500ml water, under agitation simultaneously slowly be added drop-wise in the thanomin NaOH aqueous solution and 370.6g tert-Butyl dicarbonate (1.70mol), be added dropwise to complete in 4 hours, dropping temperature is 10～20 ℃; Be added dropwise to complete 10～20 ℃ of rear maintenances, continue reaction 8 hours, after the reaction knot was whole, the pH value of reaction system was 10～11;
(2) add 500ml benzene in the compound that obtains to step (1) and extract, obtain water layer and organic layer; After extracting again once with 250ml benzene water layer, organic phase and the organic layer that obtains merged; Organic layer with 300ml saturated aqueous common salt washed twice, was added anhydrous sodium sulfate drying 4 hours, underpressure distillation, control pressure is less than 500Pa, and slowly is warming up to 60 ℃, removes benzene, obtain by the 4-amido of tertbutyloxycarbonyl (BOC) protection-n-butyl alcohol BOC-BA, 240.3g;
(3) the 4-amido of 189g being protected by tertbutyloxycarbonyl (BOC)-n-butyl alcohol BOC-BA puts into autoclave pressure, the KOH that adds 4.5g, be warming up to 70 ℃, be evacuated to pressure less than 500Pa, kept 1.5 hours, remove the water in the reaction system, after the reaction, the water content of reaction system is less than 0.5%;
(4) close vacuum, add 912g oxyethane in the product that obtains to step (3), keeping temperature of reaction is 105 ℃, and reaction pressure finishes until reaction pressure is down to the normal pressure afterreaction less than 0.6MPa;
(5) add the hydrochloric acid of 3mol/L in the product that obtains to step (4), regulating pH value is 1.5, and the maintenance temperature is 60 ℃, reacts 2 hours, to slough tertbutyloxycarbonyl (BOC) group;
(6) temperature that keeps the product that step (5) obtains is greater than 70 ℃, vacuumizes to make pressure less than 500Pa, and, after forming without water droplet to the return line tube wall, continue to keep 1 hour; Filter; Add the 5g hexa-magnesium silicate, keeping temperature in the adsorption process is 110 ℃, and adsorption time is 3 hours; Be cooled to 30 ℃, filter, namely obtain described polyetheramine product, 993g.
Embodiment 7: a kind of preparation method of polyetheramine, adopt following processing step:
(1) 200g α-amino isopropyl alcohol (2.67mol) and 610g tert-Butyl dicarbonate (2.80mol) are dissolved in the 1600ml water, are cooled to 0 ℃, with the 636g Na of 213g
2CO
3(6.0mol) be dissolved in 2000ml water, stir lower slowly being added drop-wise in the α-amino isopropyl alcohol, be added dropwise to complete 2 ℃ of dropping temperatures in 3 hours; After being added dropwise to complete, keep 2 ℃ to continue reaction 10 hours, the pH value that reaction finishes the afterreaction system is 10;
(2) add the 1000ml ethyl acetate in the compound that obtains to step (1) and extract, obtain water layer and organic layer; After extracting again once with the 500ml ethyl acetate water layer, organic phase and the organic layer that obtains merged; Organic layer with the water washing of 600ml saturated common salt, was added anhydrous sodium sulfate drying 3 hours, and the underpressure distillation control pressure is less than 500Pa, and slowly be warming up to 100 ℃, remove ethyl acetate, obtain the α-amino isopropyl alcohol BOC-IPA by tertbutyloxycarbonyl (BOC) protection, 442.8g;
(3) the α-amino isopropyl alcohol BOC-IPA by tertbutyloxycarbonyl (BOC) protection with 200g puts into autoclave pressure, the NaOH that adds 5g, be warming up to 100 ℃, be evacuated to pressure less than 500Pa, kept 2 hours, remove the water in the reaction system, after the reaction, the water content of reaction system is less than 0.5%;
(4) close vacuum, add 700g oxyethane in the product that obtains to step (3) and react, temperature of reaction is 120 ℃, and the control reaction pressure is no more than 0.6MPa, and question response Pressure Drop to normal pressure afterreaction finishes;
(5) add the hydrochloric acid of 5mol/L in the product that obtains to step (4), regulating pH value is 1, and the maintenance temperature is 50 ℃, reacts 1 hour, to slough tertbutyloxycarbonyl (BOC) group;
(6) keeping the temperature of the product that step (5) obtains is 80 ℃, vacuumize to make pressure less than 500Pa, and, after forming without water droplet to the return line tube wall, continue to keep 0.5 hour; Filter; Add the 12g hexa-magnesium silicate and adsorb, keeping temperature in the adsorption process is 100 ℃, and adsorption time is 3 hours; Be cooled to 40 ℃, filter, namely obtain described polyetheramine product, 815.4g.
Claims (6)
1. the preparation method of a polyetheramine is characterized in that, adopts following processing step:
(1) will have general formula H
2The N-R-OH(I) in the mixed solvent of water-soluble or water and organic solvent of the alcamine compound of structure, concentration is 10～60%; Described organic solvent is tetrahydrofuran (THF) or dioxane, and the ratio of organic solvent and water is 5:95～40:60 in the mixed solvent;
Wherein R is the C of straight or branched
nH
2n, n=2～18 or
X=0～10, y=0～10 or
, x=0～10, y=0～10 or
N=0～10;
(2) drip catalyzer and tert-Butyl dicarbonate in the compound that obtains to step (1), the temperature during dropping is-10～40 ℃, is added dropwise to complete in 1～6 hour; After being added dropwise to complete, reacted 4～48 hours under-10～40 ℃ the condition in temperature, the pH value after reaction finishes is 10～14; Described catalyzer is NaOH, Na
2CO
3Perhaps triethylamine, the mol ratio of catalyzer and alcamine compound is 0.5～3:1, the mol ratio of tert-Butyl dicarbonate and alcamine compound is 1～1.1:1, described tert-Butyl dicarbonate is pure tert-Butyl dicarbonate or the mixing solutions of tert-Butyl dicarbonate and organic solvent, the concentration of the mixing solutions of described tert-Butyl dicarbonate and organic solvent is 10～60%, and described organic solvent is acetone, tetrahydrofuran (THF) or dioxane;
(3) compound that step (2) is obtained carries out underpressure distillation, and to remove the organic solvent in the compound, vacuum pressure is less than 500Pa, and distillation temperature is 40～100 ℃;
(4) add organic solvent in the compound that obtains to step (3) and extract, obtain water layer and organic layer; After extracting again once with organic solvent water layer, the organic layer that obtains is merged; With organic layer saturated common salt water washing, added anhydrous sodium sulfate drying 2～6 hours, organic solvent is removed in underpressure distillation, obtains the alcamine compound BOC-NH-R-OH by tertbutyloxycarbonyl (BOC) protection; Described organic solvent is ethyl acetate, benzene, toluene, hexanaphthene, methylene dichloride or chloroform;
(5) to oxide compound or oxyhydroxide or double metal cyanide by adding basic metal or alkaline-earth metal among the alcamine compound BOC-NH-R-OH of tertbutyloxycarbonyl (BOC) protection, the add-on of the oxide compound of basic metal or alkaline-earth metal or oxyhydroxide or double metal cyanide is 0.1～5%wt by the alcamine compound BOC-NH-R-OH of tertbutyloxycarbonyl (BOC) protection, inflated with nitrogen is to remove oxygen in the reaction system, be warming up to 50～100 ℃, be evacuated to pressure less than 500Pa, kept 0.5～2 hour, and removed the water in the reaction system;
(6) add monomer in the product that obtains to step (5) and react, temperature of reaction is 80～120 ℃, and reaction pressure is 0.1～0.6MPa, adds a kind of monomer at every turn, and the question response Pressure Drop adds lower a kind of monomer to the normal pressure or reaction finishes; The add-on of described monomer and the mol ratio of BOC-NH-R-OH are 5～100:1, and described monomer is one or more in oxyethane, propylene oxide or the tetrahydrofuran (THF);
(7) hydrochloric acid that adds 0.5～5mol/L in the product that obtains to step (6), regulating pH value is 1～2, the maintenance temperature is 50～80 ℃, reacts 1～4 hour, to slough tertbutyloxycarbonyl (BOC) group;
(8) keeping the temperature of the product that step (7) obtains is 40～100 ℃, vacuumizes to make pressure less than 500Pa, after forming without water droplet to the return line tube wall, keeps 0.5～1 hour again; Filter; Add sorbent material and adsorb, keeping temperature in the adsorption process is 100～120 ℃, and adsorption time is 1～3 hour; Be cooled to 30～50 ℃, filter, namely obtain described polyetheramine product.
2. the preparation method of polyetheramine as claimed in claim 1, it is characterized in that: the oxide compound of described basic metal or alkaline-earth metal or oxyhydroxide are sodium hydroxide, potassium hydroxide, strontium oxide, barium oxide, strontium hydroxide or hydrated barta.
3. the preparation method of polyetheramine as claimed in claim 1 is characterized in that: after step (5) was processed, the water content of reaction system was less than 0.5%.
4. the preparation method of polyetheramine as claimed in claim 1, it is characterized in that: described sorbent material is hexa-magnesium silicate or six pure aluminium silicate.
5. the preparation method of polyetheramine as claimed in claim 1 is characterized in that: the add-on of described sorbent material is 0.1～5% of the product total amount that obtains of step (7).
6. the preparation method of polyetheramine as claimed in claim 1 is characterized in that: in the step (2), the adding mode of catalyzer and tert-Butyl dicarbonate adds first catalyzer for (1), tert-Butyl dicarbonate is dissolved in dripping behind the organic solvent again adding; Or (2) add first tert-Butyl dicarbonate, drips to add catalyzer again; Or (3) drip adding catalyzer and tert-Butyl dicarbonate simultaneously.
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| CN102746510B (en) * | 2012-07-31 | 2013-12-25 | 无锡阿科力化工有限公司 | Method for preparing polyether amide material |
| CN103214667B (en) * | 2013-03-14 | 2015-07-08 | 杭州三隆新材料有限公司 | Polymerization method of polytetrahydrofuran single alcohol and diol mixture |
| CN103131002A (en) * | 2013-03-25 | 2013-06-05 | 福州百盛精细化学品有限公司 | Polyether amine and preparation method thereof |
| CN104140454B (en) * | 2013-10-29 | 2017-06-30 | 中国石油化工股份有限公司 | A kind of drilling fluid polyethers amido APG and preparation method thereof |
| CN104387578B (en) * | 2014-12-08 | 2016-07-13 | 广州腾威科技有限公司 | Polyetheramine compositions, preparation method and its usage |
| CN108003041A (en) * | 2016-10-28 | 2018-05-08 | 中国石油化工股份有限公司 | A kind of method for separating Aethoxy Sklerol and polyetheramine |
| CN110483758A (en) * | 2019-08-26 | 2019-11-22 | 浙江皇马科技股份有限公司 | A kind of preparation method of monoamine base polyoxyethylene ether |
| CN111072954B (en) * | 2019-12-27 | 2021-01-08 | 浙江大学 | Polytetrahydrofuran-polyamino acid block copolymer and synthetic method thereof |
| CN111171672B (en) * | 2019-12-31 | 2022-04-05 | 鲁东大学 | Preparation method of water-based anticorrosive epoxy coating |
| CN114539105B (en) * | 2020-01-20 | 2023-04-18 | 山东建科建筑材料有限公司 | Gemini type concrete air entraining agent and preparation method thereof |
| CN114687216A (en) * | 2022-01-11 | 2022-07-01 | 浙江科峰新材料有限公司 | Soft and smooth block silicone oil for cotton and preparation method thereof |
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