CN102604072A - Preparation method of polyether amine - Google Patents
Preparation method of polyether amine Download PDFInfo
- Publication number
- CN102604072A CN102604072A CN2012100523880A CN201210052388A CN102604072A CN 102604072 A CN102604072 A CN 102604072A CN 2012100523880 A CN2012100523880 A CN 2012100523880A CN 201210052388 A CN201210052388 A CN 201210052388A CN 102604072 A CN102604072 A CN 102604072A
- Authority
- CN
- China
- Prior art keywords
- boc
- obtains
- polyetheramine
- compound
- organic solvent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Polyethers (AREA)
- Polyesters Or Polycarbonates (AREA)
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 one type of main chain contains the polyoxygenated alkyl structure, and active function groups is the compound of amido.Through selecting different polyoxygenated alkyl structures, a series of performances such as the toughness of adjustable polyetheramine, viscosity and wetting ability, and amido offers the possibility of polyetheramine and the reaction of multiple compound.Because of its particular structural, polyetheramine shows particular performances in numerous Application Areass, and its range of application is also more and more wider.
Disclosed at present compound method, the terminal method of introducing amido of polyethers mainly comprises three kinds: (1) polyethers terminal hydroxyl utilizes the direct amination of ammonia/hydrogen under catalyst action; (2) through introducing cyanic acid, obtain amido behind the shortening; (3), introduce amido through amine group containing and polyether reactant.Wherein preceding two kinds of methods are higher to equipment and processing requirement, and by comparison, the third technology 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, be difficult to guarantee that an aminated compounds only connects a polyether backbone with polyether chain; 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, through 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 through 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 compound 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, utilizes aliphatic amide to react with it then, and amido is linked to each other with polyether chain.
Because show stronger wetting ability after the ionize of polyetheramine amido; And the polyether structure main chain can be selected through 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.Through 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 deficiency that exists 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 said polyetheramine is polypropyleneoxide, polyethylene oxide, THF homopolymer or three's a multipolymer, and the polymerization degree is 5～100, and an end of main chain is a 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 characteristic is to adopt following process 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%; Said organic solvent is THF or dioxane, and the ratio of organic solvent and water is 5: 95～40: 60 in the mixed solvent;
(2) in the compound that step (1) obtains, drip catalyzer and tert-Butyl dicarbonate, 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; Said 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; Said tert-Butyl dicarbonate is the pure tert-Butyl dicarbonate or the mixing solutions of tert-Butyl dicarbonate and organic solvent, and the concentration of the mixing solutions of said tert-Butyl dicarbonate and organic solvent is 10～60%, and said organic solvent is acetone, 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) in the compound that step (3) obtains, add organic solvent and extract, obtain water layer and organic layer; After extracting once again with organic solvent water layer, organic phase that obtains and organic layer are merged; Organic layer is used the 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; Said organic solvent is ETHYLE ACETATE, benzene, toluene, hexanaphthene, methylene dichloride or chloroform;
(5) oxide compound or the oxyhydroxide or the double metal cyanide of adding basic metal or earth alkali metal in by the alcamine compound BOC-NH-R-OH of tertbutyloxycarbonyl (BOC) protection; The add-on of the oxide compound of basic metal or earth alkali 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 towards nitrogen to remove oxygen; Be warming up to 50～100 ℃; Be evacuated to pressure less than 500Pa, kept 0.5～2 hour, remove the water in the reaction system;
(6) in the product that step (5) obtains, add monomer 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 question response pressure adds a kind of monomer or reaction end down after reducing to normal pressure; The mol ratio of said monomeric add-on and BOC-NH-R-OH is 5～100: 1, and said monomer is one or more in oxyethane, propylene oxide or the THF;
(7) in the product that step (6) obtains, add the hydrochloric acid of 0.5～5mol/L, regulating pH value is 1～2, and 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 no water droplet forms 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, promptly obtain described polyetheramine product.
The oxide compound of said basic metal or earth alkali metal or oxyhydroxide are sodium hydroxide, Pottasium Hydroxide, strontium oxide, barium oxide, strontium hydroxide or hydrated barta.
After step (5) was handled, the water cut of reaction system was less than 0.5%.
Said sorbent material is hexa-magnesium silicate or six pure aluminium silicate.
The add-on of said 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 is that (1) adds earlier catalyzer, again tert-Butyl dicarbonate is dissolved in dripping behind the organic solvent adding; Or (2) elder generation adding tert-Butyl dicarbonate, drip the adding catalyzer again; Or (3) drip adding catalyzer and tert-Butyl dicarbonate simultaneously.
With existing single-ended be amido the polyetheramine compound method relatively, the present invention has realized the synthetic of title product under normal condition, avoided the high requirement of the direct amination of hydroxyl for conversion unit and reaction conditions; Adopt the BOC group to protect simultaneously, effectively reduced the side reaction when aminated compounds links to each other with polyether chain, obtain the polyetheramine product of compound with regular structure for amido.Product can be applicable to fields such as tensio-active agent, flocculation agent, dyeing and finishing auxiliaries and electrocoating paint.
Embodiment
Below in conjunction with specific embodiment the present invention is described further.
The main chain of polyetheramine of the present invention is polypropyleneoxide, polyethylene oxide, THF homopolymer or three's a multipolymer, and the polymerization degree is 5～100, and an end of main chain is a 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 through 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, 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 said polyetheramine.The polyetheramine that adopts this method to obtain; Through regulating the ratio of propylene oxide, oxyethane and THF in the polyether chain; Can get the polyether backbone of different hydrophilic property; One end of polyether chain contains amido, after the acidifying stronger wetting ability can be provided, and can be applicable to 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 process step:
(1) 100g thanomin (1.64mol) and 131gNaOH (3.28mol) are dissolved in the 500ml water, are cooled to 0 ℃, 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) in the product that step (2) obtains, add 500ml ETHYLE ACETATE and extract, obtain water layer and organic layer; After extracting once again with 250ml ETHYLE ACETATE water layer, organic phase that obtains and organic layer are 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 ETHYLE 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, adds the KOH of 3g, is warming up to 80 ℃; In reaction system towards 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 cut of reaction system is less than 0.5%;
(5) close vacuum, in the product that step (4) obtains, add 440g oxyethane and react, temperature of reaction is 100 ℃, and the control reaction pressure is 0.6MPa, and question response pressure is reduced to the normal pressure afterreaction and finished;
(6) hydrochloric acid of adding 0.5mol/L in the product that step (5) obtains, regulating the pH value is 2, keeping 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 no water droplet forms to the return line tube wall, continue maintenance 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, promptly obtain described polyetheramine product, 489g.
Embodiment 2: a kind of preparation method of polyetheramine, adopt following process 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; The NaOH aqueous solution under agitation slowly is added drop-wise in the thanomin, was added dropwise to complete in 2 hours, dropping temperature is-5 ℃; Be added dropwise to complete the back and keep-5 ℃, continue reaction 6 hours, after the reaction knot was whole, the pH value of reaction system was 10;
(2) in the compound that step (1) obtains, add 500ml ETHYLE ACETATE and extract, obtain water layer and organic layer; After extracting once again with 250ml ETHYLE ACETATE water layer, organic phase that obtains and organic layer are 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 ETHYLE ACETATE; Obtain thanomin BOC-MEA, 240.3g by tertbutyloxycarbonyl (BOC) protection;
(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 cut of reaction system is less than 0.5%;
(4) close vacuum, in the product that step (3) obtains, add 300g oxyethane, keeping temperature of reaction is 80 ℃; Reaction pressure is 0.5MPa, after question response pressure is reduced to normal pressure, adds the 640g propylene oxide; Keeping temperature of reaction is 100 ℃, reduces to the normal pressure afterreaction until reaction pressure and finishes;
(5) hydrochloric acid of adding 5mol/L in the product that step (4) obtains, regulating the pH value is 1, keeping 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 no water droplet forms to the return line tube wall, continue maintenance 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, promptly obtain described polyetheramine product, 990g.
Embodiment 3: a kind of preparation method of polyetheramine, adopt following process 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; The NaOH aqueous solution and 375g tert-Butyl dicarbonate (1.72mol) under agitation slowly are added drop-wise in the thanomin simultaneously, were added dropwise to complete in 3 hours, dropping temperature is 5 ℃; Be added dropwise to complete the back and keep 5 ℃, continue reaction 6 hours, after the reaction knot was whole, the pH value of reaction system was 11;
(2) in the compound that step (1) obtains, add 500ml toluene and extract, obtain water layer and organic layer; After extracting once again with 250ml toluene water layer, organic phase that obtains and organic layer are 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 thanomin BOC-MEA, 240.3g by tertbutyloxycarbonyl (BOC) protection;
(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 cut of reaction system is less than 0.5%;
(4) close vacuum, in the product that step (3) obtains, add the 940g propylene oxide, keeping temperature of reaction is 100 ℃, and reaction pressure is reduced to the normal pressure afterreaction until reaction pressure and finished less than 0.6MPa;
(5) hydrochloric acid of adding 5mol/L in the product that step (4) obtains, regulating the pH value is 1, keeping 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 no water droplet forms to the return line tube wall, continue maintenance 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, promptly obtain described polyetheramine product, 992g.
Embodiment 4: a kind of preparation method of polyetheramine, adopt following process 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; The NaOH aqueous solution under agitation slowly is added drop-wise in the polyetheramine, was added dropwise to complete in 2 hours, dropping temperature is 0 ℃; Be added dropwise to complete the back and keep 0 ℃, continue reaction 8 hours;
(2) in the compound that step (1) obtains, add 1000ml ETHYLE ACETATE and extract, obtain water layer and organic layer; After extracting once again with 500ml ETHYLE ACETATE water layer, organic phase that obtains and organic layer are 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 ETHYLE ACETATE; Obtain polyetheramine BOC-PEA, 274.4g by tertbutyloxycarbonyl (BOC) protection;
(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 towards nitrogen to remove oxygen; Be evacuated to pressure less than 500Pa; Kept 1 hour, and removed the water in the reaction system, the water cut of reaction afterreaction system is less than 0.5%;
(4) close vacuum, in the product that step (3) obtains, add the 200g propylene oxide and react, temperature of reaction is 80 ℃, and reaction pressure is less than 0.6MPa, and question response pressure is reduced to the normal pressure afterreaction and finished;
(5) hydrochloric acid of adding 2mol/L in the product that step (4) obtains, regulating the pH value is 1, keeping 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 no water droplet forms to the return line tube wall, continue maintenance 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, promptly obtain described polyetheramine product, 396g.
Embodiment 5: a kind of preparation method of polyetheramine, adopt following process step:
(1) 123g Yi Bingchunan (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, stir and slowly is added drop-wise in the Yi Bingchunan down; 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) in the compound that step (1) obtains, add 500ml ETHYLE ACETATE and extract, obtain water layer and organic layer; After extracting once again with 250ml ETHYLE ACETATE water layer, organic phase that obtains and organic layer are 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 ETHYLE ACETATE, obtain Yi Bingchunan BOC-IPA, 272.3g by tertbutyloxycarbonyl (BOC) protection;
(3) the Yi Bingchunan 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 cut of reaction system is less than 0.5%;
(4) close vacuum, in the product that step (3) obtains, add 440g oxyethane and react, temperature of reaction is 100 ℃, and the control reaction pressure is no more than 0.6MPa, and question response pressure is reduced to the normal pressure afterreaction and finished;
(5) hydrochloric acid of adding 0.5mol/L in the product that step (4) obtains, regulating the pH value is 2, keeping 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 no water droplet forms to the return line tube wall, continue maintenance 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, promptly obtain described polyetheramine product, 501.5g.
Embodiment 6: a kind of preparation method of polyetheramine, adopt following process step:
(1) 146.1g 4-amido-1-butanols (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; The NaOH aqueous solution and 370.6g tert-Butyl dicarbonate (1.70mol) under agitation slowly are added drop-wise in the thanomin simultaneously, were added dropwise to complete in 4 hours, dropping temperature is 10～20 ℃; Be added dropwise to complete the back and keep 10～20 ℃, continue reaction 8 hours, after the reaction knot was whole, the pH value of reaction system was 10～11;
(2) in the compound that step (1) obtains, add 500ml benzene and extract, obtain water layer and organic layer; After extracting once again with 250ml benzene water layer, organic phase that obtains and organic layer are 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 4-amido-1-butanols BOC-BA, 240.3g by tertbutyloxycarbonyl (BOC) protection;
(3) the 4-amido-1-butanols BOC-BA that 189g is protected by tertbutyloxycarbonyl (BOC) puts into autoclave pressure, adds the KOH of 4.5g, is 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 cut of reaction system is less than 0.5%;
(4) close vacuum, in the product that step (3) obtains, add 912g oxyethane, keeping temperature of reaction is 105 ℃, and reaction pressure is reduced to the normal pressure afterreaction until reaction pressure and finished less than 0.6MPa;
(5) hydrochloric acid of adding 3mol/L in the product that step (4) obtains, regulating the pH value is 1.5, keeping 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 no water droplet forms to the return line tube wall, continue maintenance 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, promptly obtain described polyetheramine product, 993g.
Embodiment 7: a kind of preparation method of polyetheramine, adopt following process step:
(1) 200g Yi Bingchunan (2.67mol) and 610g tert-Butyl dicarbonate (2.80mol) are dissolved in the 1600ml water, are cooled to 0 ℃, the 636g Na of 213g
2CO
3(6.0mol) be dissolved in 2000ml water, slowly be added drop-wise in the Yi Bingchunan under stirring, 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) in the compound that step (1) obtains, add 1000ml ETHYLE ACETATE and extract, obtain water layer and organic layer; After extracting once again with 500ml ETHYLE ACETATE water layer, organic phase that obtains and organic layer are 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 ETHYLE ACETATE, obtain Yi Bingchunan BOC-IPA, 442.8g by tertbutyloxycarbonyl (BOC) protection;
(3) the Yi Bingchunan BOC-IPA by tertbutyloxycarbonyl (BOC) protection with 200g puts into autoclave pressure, adds the NaOH of 5g, is 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 cut of reaction system is less than 0.5%;
(4) close vacuum, in the product that step (3) obtains, add 700g oxyethane and react, temperature of reaction is 120 ℃, and the control reaction pressure is no more than 0.6MPa, and question response pressure is reduced to the normal pressure afterreaction and finished;
(5) hydrochloric acid of adding 5mol/L in the product that step (4) obtains, regulating the pH value is 1, keeping 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 no water droplet forms to the return line tube wall, continue maintenance 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, promptly obtain described polyetheramine product, 815.4g.
Claims (7)
1. polyetheramine, it is characterized in that: the main chain of said polyetheramine is polypropyleneoxide, polyethylene oxide, THF homopolymer or three's a multipolymer, and the polymerization degree is 5～100, and an end of main chain is a 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.
2. the preparation method of a polyetheramine is characterized in that, adopts following process 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%; Said organic solvent is THF or dioxane, and the ratio of organic solvent and water is 5: 95～40: 60 in the mixed solvent;
(2) in the compound that step (1) obtains, drip catalyzer and tert-Butyl dicarbonate, 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; Said 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; Said tert-Butyl dicarbonate is the pure tert-Butyl dicarbonate or the mixing solutions of tert-Butyl dicarbonate and organic solvent, and the concentration of the mixing solutions of said tert-Butyl dicarbonate and organic solvent is 10～60%, and said organic solvent is acetone, 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) in the compound that step (3) obtains, add organic solvent and extract, obtain water layer and organic layer; After extracting once again with organic solvent water layer, the organic layer that obtains is merged; Organic layer is used the 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; Said organic solvent is ETHYLE ACETATE, benzene, toluene, hexanaphthene, methylene dichloride or chloroform;
(5) oxide compound or the oxyhydroxide or the double metal cyanide of adding basic metal or earth alkali metal in by the alcamine compound BOC-HRA of tertbutyloxycarbonyl (BOC) protection; The add-on of the oxide compound of basic metal or earth alkali 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 towards nitrogen to remove oxygen; Be warming up to 50～100 ℃; Be evacuated to pressure less than 500Pa, kept 0.5～2 hour, remove the water in the reaction system;
(6) in the product that step (5) obtains, add monomer 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 question response pressure adds a kind of monomer or reaction end down after reducing to normal pressure; The mol ratio of said monomeric add-on and BOC-NH-R-OH is 5～100: 1, and said monomer is one or more in oxyethane, propylene oxide or the THF;
(7) in the product that step (6) obtains, add the hydrochloric acid of 0.5～5mol/L, regulating pH value is 1～2, and 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 no water droplet forms 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, promptly obtain described polyetheramine product.
3. the preparation method of polyetheramine as claimed in claim 2, it is characterized in that: the oxide compound of said basic metal or earth alkali metal or oxyhydroxide are sodium hydroxide, Pottasium Hydroxide, strontium oxide, barium oxide, strontium hydroxide or hydrated barta.
4. the preparation method of polyetheramine as claimed in claim 2 is characterized in that: after step (5) was handled, the water cut of reaction system was less than 0.5%.
5. the preparation method of polyetheramine as claimed in claim 2, it is characterized in that: said sorbent material is hexa-magnesium silicate or six pure aluminium silicate.
6. the preparation method of polyetheramine as claimed in claim 2 is characterized in that: the add-on of said sorbent material is 0.1～5% of the product total amount that obtains of step (7).
7. the preparation method of polyetheramine as claimed in claim 2 is characterized in that: in the step (2), the adding mode of catalyzer and tert-Butyl dicarbonate is that (1) adds catalyzer earlier, again tert-Butyl dicarbonate is dissolved in dripping behind the organic solvent adding; Or (2) elder generation adding tert-Butyl dicarbonate, drip the adding catalyzer again; Or (3) drip adding catalyzer and tert-Butyl dicarbonate simultaneously.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201210052388 CN102604072B (en) | 2012-03-02 | 2012-03-02 | Preparation method of polyether amine |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201210052388 CN102604072B (en) | 2012-03-02 | 2012-03-02 | Preparation method of polyether amine |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102604072A true CN102604072A (en) | 2012-07-25 |
| CN102604072B CN102604072B (en) | 2013-09-18 |
Family
ID=46521884
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201210052388 Active CN102604072B (en) | 2012-03-02 | 2012-03-02 | Preparation method of polyether amine |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102604072B (en) |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102746510A (en) * | 2012-07-31 | 2012-10-24 | 无锡阿科力化工有限公司 | Method for preparing polyether amide material |
| 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 |
| CN103214667A (en) * | 2013-03-14 | 2013-07-24 | 杭州三隆新材料有限公司 | Polymerization method of polytetrahydrofuran single alcohol and diol mixture |
| CN104140454A (en) * | 2013-10-29 | 2014-11-12 | 中国石油化工股份有限公司 | Polyether amine based alkyl glycoside for drilling fluid and preparation method thereof |
| CN104387578A (en) * | 2014-12-08 | 2015-03-04 | 广州腾威科技有限公司 | Polyether amine composition and preparation method and application thereof |
| 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 |
| CN111072954A (en) * | 2019-12-27 | 2020-04-28 | 浙江大学 | Polytetrahydrofuran-polyamino acid block copolymer and synthetic method thereof |
| CN111170903A (en) * | 2020-01-20 | 2020-05-19 | 山东建科建筑材料有限公司 | Gemini type concrete air entraining agent and preparation method thereof |
| CN111171672A (en) * | 2019-12-31 | 2020-05-19 | 鲁东大学 | Preparation method of water-based anticorrosive epoxy coating |
| 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 |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3231619A (en) * | 1959-12-18 | 1966-01-25 | Jefferson Chem Co Inc | Basic primary amino polyether compositions |
| WO1998002490A1 (en) * | 1996-07-12 | 1998-01-22 | Huntsman Petrochemical Corporation | Polyether amine modification of polypropylene |
| CN101921392A (en) * | 2010-09-29 | 2010-12-22 | 岳阳市金茂泰科技有限公司 | Method for synthesizing polyether amine |
| CN102336903A (en) * | 2011-07-07 | 2012-02-01 | 中国石油化工集团公司 | Production process of aliphatic polyetheramine |
-
2012
- 2012-03-02 CN CN 201210052388 patent/CN102604072B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3231619A (en) * | 1959-12-18 | 1966-01-25 | Jefferson Chem Co Inc | Basic primary amino polyether compositions |
| WO1998002490A1 (en) * | 1996-07-12 | 1998-01-22 | Huntsman Petrochemical Corporation | Polyether amine modification of polypropylene |
| CN101921392A (en) * | 2010-09-29 | 2010-12-22 | 岳阳市金茂泰科技有限公司 | Method for synthesizing polyether amine |
| CN102336903A (en) * | 2011-07-07 | 2012-02-01 | 中国石油化工集团公司 | Production process of aliphatic polyetheramine |
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102746510A (en) * | 2012-07-31 | 2012-10-24 | 无锡阿科力化工有限公司 | Method for preparing polyether amide material |
| CN103214667A (en) * | 2013-03-14 | 2013-07-24 | 杭州三隆新材料有限公司 | Polymerization method of polytetrahydrofuran single alcohol and diol mixture |
| 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 |
| CN104140454A (en) * | 2013-10-29 | 2014-11-12 | 中国石油化工股份有限公司 | Polyether amine based alkyl glycoside for drilling fluid 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 |
| CN104387578A (en) * | 2014-12-08 | 2015-03-04 | 广州腾威科技有限公司 | Polyether amine composition and preparation method and application thereof |
| 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 |
| CN111072954A (en) * | 2019-12-27 | 2020-04-28 | 浙江大学 | Polytetrahydrofuran-polyamino acid block copolymer and synthetic method thereof |
| CN111171672A (en) * | 2019-12-31 | 2020-05-19 | 鲁东大学 | Preparation method of water-based anticorrosive epoxy coating |
| CN111170903A (en) * | 2020-01-20 | 2020-05-19 | 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102604072B (en) | 2013-09-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102604072B (en) | Preparation method of polyether amine | |
| CN102643452B (en) | Method for improving aziridine cross-linking agent stability | |
| CN102741326A (en) | Novel organomodified siloxanes having primary amino functions, novel organomodified siloxanes having quaternary ammonium functions and the method for the production thereof | |
| CN104479125A (en) | Synthesis method and application of oleic acid-polyethylene polyamine polyether | |
| CN102911365A (en) | Method for preparing modified block polyether amino silicone oil | |
| CN102408559A (en) | Preparation process of amine terminated polyether | |
| CN102336903A (en) | Production process of aliphatic polyetheramine | |
| CN105601904B (en) | A kind of preparation method of hydroxylamino polyethers | |
| CN101880362B (en) | Preparation method of aqueous polyamide resin emulsion | |
| CN116515367A (en) | Anticorrosive water-based paint and preparation process thereof | |
| CN101072748B (en) | Method for the production of n,n-dimethylacetamide (DMAC) | |
| CN102432863B (en) | A kind of quaternary ammonium salt type hyperbranched negative-ion exchange resin and preparation method thereof | |
| CN110302813B (en) | Catalyst for synthesizing cyclic carbonate and preparation method and application thereof | |
| CN103483577B (en) | A kind of preparation method of glycidyl capped allyl alcohol polyethenoxy ether | |
| CN103657512B (en) | One class perfluor ene-type anionic gemini surfactant and preparation method thereof | |
| CN113957721B (en) | Anti-wrinkle elastic silicone oil and preparation method thereof | |
| CN102060989A (en) | Preparation method of glycidol ether base allyl alcohol polyoxyethylene ether | |
| CN105693926B (en) | A kind of high-performance environment protection type dynamic hydrate inhibitor and its synthetic method | |
| US10377775B2 (en) | Method for producing polyalkylene glycol derivative having amino group at end | |
| KR20160067752A (en) | Method for producing polyalkylene glycol derivative having amino group at end | |
| CN104084092A (en) | Trisiloxane gemini surfactant containing glucosamide group and preparation method of surfactant | |
| CN104760939B (en) | A kind of synthesis technique of the sodium azide aqueous phase of n-butanol recycled | |
| KR20160013721A (en) | Method for preparation of five-membered cyclic carbonate from carbon dioxide and epoxide by using alkanolamine as catalyst | |
| CN109678774A (en) | A kind of storage method of ethylene imide class compound | |
| CN109607504A (en) | A kind of preparation method of II type ammonium polyphosphate |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C56 | Change in the name or address of the patentee |
Owner name: WUXI ACRYL TECHNOLOGY CO., LTD. Free format text: FORMER NAME: AKELI CHEMICAL CO., LTD. WUXI |
|
| CP03 | Change of name, title or address |
Address after: 214196 No. 29, Xiang Xiang Road, Donggang new material industrial zone, Xishan District, Jiangsu, Wuxi Patentee after: Wuxi Acryl Technology Co., Ltd. Address before: 214101, No. 10, C District, Dongting science and Technology Industrial Park, Wuxi, Jiangsu, Xishan Patentee before: Akeli Chemical Co., Ltd. Wuxi |