CN102336903A - Production process of aliphatic polyetheramine - Google Patents
Production process of aliphatic polyetheramine Download PDFInfo
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- CN102336903A CN102336903A CN2011101887767A CN201110188776A CN102336903A CN 102336903 A CN102336903 A CN 102336903A CN 2011101887767 A CN2011101887767 A CN 2011101887767A CN 201110188776 A CN201110188776 A CN 201110188776A CN 102336903 A CN102336903 A CN 102336903A
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Abstract
The invention belongs to the technical field of high molecular materials and provides a production process of aliphatic polyetheramine. In the process, aliphatic polyetheramine is prepared by catalyzing, reducing and aminating polyether polyol of which the number-average molecular weight is over 100 and which serves as a raw material in the presence of hydrogen gas, an aminating agent and a framework nickel catalyst. The framework nickel catalyst consists of 85-95 percent by mass of metal nickel and 15-5 percent of metal aluminum. The framework nickel catalyst and the aminating agent are circularly applied mechanically after being treated. The entire process has the advantages of high route selectivity, high transformation ratio, low environmental pollution and convenience for post-treatment.
Description
Technical field
The invention belongs to polymeric material field, relate to a kind of polymkeric substance, is a kind of production technique of aliphatic polyether amine specifically.
Background technology
Polyetheramine is one type and has soft polyether skeleton, and terminal compound with amino or amine-terminated, these compounds are to be raw material with corresponding polyether glycol mostly, obtain through terminal hydroxyl is carried out chemical treatment.Difference according to the amino alkyl radical structure that links to each other of end can be divided into two types of aromatic series and aliphatics again.Aliphatic polyether amine is widely used in epoxy resin, urethane and spraying Spray Polyurea Elastomer (Spray Polyurea Elastomer is called for short SPUA) field at present.About 1.13 ten thousand tons of the output of global SPUA material in 2002, the field has obtained widespread use in that chemical anticorrosion, pipeline, building, naval vessel, water conservancy, traffic, machinery, mine be wear-resisting etc.The SPUA technology of China has also been moved towards the practical stage; The output of spray polyurea material develops several kilotons rapidly from annual tens tons; The SPUA series material of exploitation in Beijing, city and regional successful Application such as Qingdao, Shanghai, Wuxi; Wherein the application in Beijing-Tianjin high-speed railway subgrade and the protection of bridge face is especially noticeable, and being applied to Beijing-Shanghai express railway becomes the maximum up to now polyurea water-proof project in the whole world.
The present compound method of polyetheramine mainly contains three kinds: catalytic reduction amination method, leavings group method and Qing Wanji method.
The Study on Catalytic Amination of Alcohols method is set about from the terminal hydroxyl of polyether glycol, replaces its terminal hydroxyl through ammonolysis reaction with amino.The Study on Catalytic Amination of Alcohols method needs high-temperature high-voltage reaction, and facility investment and running cost are higher, and the Preparation of catalysts complicated steps.External suitability for industrialized production mainly adopts the high pressure reductive amination method.
The leavings group method; This method generally was divided into for two steps; The first step is an esterification, sets about from the reactive hydrogen of polyether glycol terminal hydroxyl, carries out end-blocking with having the compound (acid chloride group, halogen, carboxyl, aldehyde radical etc.) that is prone to leavings group or unsaturated group with the reactive hydrogen effect; Second step was amination reaction, and product and amine (monoamine or diamine) that the first step is obtained react.The inside and outside compound method of leavings group France has: phosgenation, SULPHURYL CHLORIDE method, halo method etc.The synthetic Amino Terminated polyether(ATPE) of leavings group method exist that raw material is difficult for purchasing and easily contaminate environment, particularly reaction to generate by product many.In the acid that product postprocessing needs a large amount of alkali neutralization reactions to produce, produce a large amount of inorganic salt, separate difficulty.
The Qing Wanji method is set about from the reactive hydrogen of polyether glycol terminal hydroxyl, carries out end-blocking with the compound and the reactive hydrogen effect of band unsaturated group (NCO ,-CN etc.), then through obtaining Amino Terminated polyether(ATPE) after the corresponding processing.The Qing Wanji method is to carry out addition reaction with polyether glycol with propylene cyanogen, and is simple to producing this method operational path again, but in the reaction process of polyether glycol and vinyl cyanide; Side reaction is many; And the easy autohemagglutination of vinyl cyanide, therefore strict to reaction conditions, the actually operating difficulty.
CN200310112615.5 has described and used molecular weight is 5000 three-functionality-degree polyethers and molecular weight is the method that 2000 difunctionality polyethers neighbour hydrogen amination prepares polyetheramine.This catalyzer is a skeletal nickel catalyst, and metallic nickel accounts for 60～80%, metallic aluminium accounts for 10～35%, chromium metal accounts for 2～10%.
CN101982482A provides a kind of and has prepared the method for polyetheramine with amorphous alloy catalyst, and the staple of the amorphous alloy catalyst of employing is nickel and aluminium, and promoter elements M, and M is one or more among Mo, La, Cr and the Mn.The quality group of described amorphous alloy powder becomes: nickel 40～50%, and aluminium 40～50%, M content is not higher than 10%.
CN101001902A discloses a kind of polyetheramine and preparation method thereof, at first generates terminal chlorine adducts by the reaction of oligomeric hydroxy compound (molecular weight is more than or equal to 92) and Epicholorohydrin, again with terminal chlorine adducts and fatty oligomeric amine react polyetheramine.
CN101522607A discloses a kind of preparation method of polyetheramine, and its molecular formula is R
2(NR
1R
3) n, wherein n is the integer of 1-20, R
1Be the organic group of 2-600 oxyalkylene, and R
1, R
3Can be identical or different, represent the carbon atom organic group of Wasserstoffatoms or 1-400.This catalyzer be comprise 80wt% cobalt metal catalyst or comprise being selected from cobalt and aluminium and comprising the Raney catalyzer that is lower than 5wt% copper of 80wt%.
CN101921392A has introduced a kind of compound method of polyetheramine, becomes the polyethers of different molecular weight in the patent with oxyethane or propylene oxide or its polymerization of mixtures, and then obtains the polyethers nitrile with acrylonitrile reactor, and then shortening gets polyetheramine.
US4618717 has described the method for preparing primary amine from oxygen ethylidene glycol monoalky lether, and this catalyzer is 50-90% nickel, 10-15 % copper, 0.5-5% chromium, iron, titanium, zirconium, thorium, magnesium, manganese or zinc by mass ratio.
US5352835 has described a kind of carried catalyst of ammonification, is used for alcohol or polymeric alcohol are changed into corresponding amine.This catalyzer is that the θ-aluminum oxide of 15～30% nickel, 1～20 % copper, 0.5～1% molybdenum or chromium and at least 50% constitutes by mass ratio, and θ-aluminum oxide is as solid support material.
This patent of US4766245 discloses a kind of compound method of ending amino polyether, and in the presence of anhydrous, RANEY nickel/Al catalysts, with hydrogen, ammonia react preparation, reaction has very high productive rate and selectivity by end hydroxy polyether (molecular weight is greater than 500).Said catalyzer is made up of the metallic aluminium of 60～75% metallic nickels and 40～25%, in the continous way pipeline reactor, is used for molecular weight with such catalyzer and separates greater than the ammonia of 500 Aethoxy Sklerols, and this temperature of reaction is at 235～250 ℃, and pressure is at 140kg/cm
3～190kg/cm
3
The open method of synthesizing polyoxy butylene diamines through reduction amination by polyoxy butylene glycol and ammonia, hydrogen of US5003107, it is 70～75 wt% nickel, 20～25 wt% copper, 0.5～5 wt% chromium, 1～5 wt% molybdenum that catalyzer is formed.Temperature of reaction: 150～220 ℃, pressure is 100～10000 psig, ammonia: Aethoxy Sklerol=10-150:1; Hydrogen: Aethoxy Sklerol=0.5-80:1, post reaction mixture is separated through fractionated mode, uses the serialization tubular reactor; In the THF homopolymer polyethers ammonifying process to molecular weight 1000 and 2000; Transformation efficiency is 91～96%, and in batch reactor, 2000 molecular weight THF polyethers transformation efficiencys are merely 76%.
US0139289 has described the method for preparing amine from alcohol, aldehyde or ketone, and this catalyzer is made up of nickel, copper, tin.
US3236895 has described and has a kind ofly made solvent with absolute ethyl alcohol or hexanaphthene, separates the method that the polyethers divalent alcohol prepares polyetheramine with Raney's nickel catalyst ammonia, and this temperature of reaction is at 235～255 ℃, and pressure is at 140kg/cm
3～170kg/cm
3, the Aethoxy Sklerol transformation efficiency is 40%～70%.
US3654370 has described with hexanaphthene and has made solvent; Use the serialization tubular reactor; The polyether Glycols of molecular weight 1000 and molecular weight are the method for 1500 polyether-tribasic alcohol Study on Catalytic Amination of Alcohols, and this ammonia is separated catalyzer and prepared with coprecipitation method, contain 75 wt% nickel, 23 wt% copper, 2 wt% chromium; This temperature of reaction is at 235～246 ℃, and pressure is at 210kg/cm
3
DE1643426 has described the method for preparing polyoxy alkylidene amine from corresponding alcohol use nickel-copper-chromium catalyst, and this catalyzer comprises the nickel of 60～85 moles of %, the chromium of 14～37 moles of % copper and 1～5 mole of %.
DE3608716 has described from corresponding alcohol use nickel-aluminium-molybdenum catalyst and has prepared the method for polyoxy alkylidene amine, and this catalyzer comprises 0.2～5% molybdenum.
DE4428004 has described the method for preparing amine from corresponding alcohol, and this catalyzer comprises 20～85% Zr, 1～30% Cu, 30～70% Ni, 0.1～5% Mo, 0～10% Al or Mn, calculates as oxide compound under every kind of situation.
DE1953263 has described the method for preparing amine from corresponding alcohol, and this catalyzer comprises 70～95% Co and Ni, 5～30% Cu, and the weight ratio of Co and Ni is 4:1 to 4:1.
DE10211101 has described the method for preparing amine from alcohol or aldehyde, and this catalyzer is made up of nickel, copper, tin, and this catalyzer comprises 22～40% Zr, 1～30% Cu, 15～50% Ni, 15～50% Co, calculates as oxide compound under every kind of situation.
Summary of the invention
The present invention provide a kind of in stirring reactor the applied catalysis reductive amination method prepare the technology of aliphatic polyether amine.
The object of the invention is realized through following technical scheme: a kind of aliphatic polyether amine production technique; Be to be raw material with the polyether glycol; In the presence of hydrogen, aminating agent and catalyzer, prepare the technology of polyetheramine through the catalytic reduction amination, it comprises the following step:
A) select special-purpose skeletal nickel catalyst for use, its composition is metallic nickel and metallic aluminium, and metallic nickel quality percentage composition accounts for 85～95%, and metallic aluminium quality percentage composition accounts for 15～5%, catalyst seal is preserved subsequent use;
B) in reactor drum, adopt the catalyzer described in the step a), carry out the catalytic reduction amination reaction, raw materials used is the polyether glycol of number-average molecular weight more than 100; The catalyzer add-on is 2 ~ 15% of a raw material polyether glycol quality; The aminating agent add-on is 1.5 ~ 20 times of raw material polyether glycol hydroxyl mole number, and the hydrogen add-on is 0.4 ~ 15 times of raw material polyether glycol hydroxyl mole number, and temperature of reaction is 120 ~ 250 ℃; Reaction pressure is 8 ~ 35MPa, and the reaction times is 1.5 ~ 8h.
C) reaction solution in the step b) is cooled to 25 ~ 60 ℃, get rid of unreacted gas, discharging, reaction product is sloughed moisture, aminating agent and other low-boiling by-products through underpressure distillation and is promptly got the aliphatic polyether amine product.
Usually, in the above-mentioned aliphatic polyether amine production technique, the preparation method of special-purpose skeletal nickel catalyst may further comprise the steps:
A) metallic nickel quality percentage composition is accounted for 85～95%; Metallic aluminium quality percentage composition accounts for 15～5% binary Nickel Aluminium Alloy Powder and under vigorous stirring, adds in the sodium hydroxide solution and dissolve; The sodium hydroxide mass percent concentration is 10～40%, and sodium hydroxide concentration is 1～3 times of alloy powder quality, and solvent temperature is at 45～85 ℃; Dissolution time is 0.5～5h, and dissolving finishes continued at 50～100 ℃ of priming reaction 0.5～5h;
B) tell the reaction product of upper strata white cotton fiber shape after static, repeatedly wash sedimentary black Raney's nickel catalyst water to neutrality, wash 2～5 times with ethanol solution again, be kept at catalyzer in the ethanol solution then.
Above-mentioned aliphatic polyether amine production technique, described raw material polyether glycol have following general structure a) or b):
a）
R wherein
1, R
2And R
3Be independently selectable side chain or the straight chain aliphatics C of comprising
2~ C
4Group; M:0 ~ 115; N:0 ~ 115; M+n:1 ~ 115.
b)
Wherein R is hydrogen or the aliphatics organic group with 1 to 6 carbon atom, R
2And R
3Be independently selectable side chain or the straight chain aliphatics C of comprising
2~ C
4Group; M:0 ~ 40; N:0 ~ 40; M+n:1 ~ 115.
The production technique of above-mentioned aliphatic polyether amine, said aminating agent can be ammonia, methylamine, n n dimetylaniline, ethamine, diethylamine, Tri N-Propyl Amine, di-n-propylamine, Isopropylamine, Diisopropylamine, hexylamine or hexahydroaniline.
The production technique of above-mentioned aliphatic polyether amine, said aliphatic polyether amine have following general structure a) or b):
a）
R wherein
1, R
2And R
3Be independently selectable side chain or the straight chain aliphatics C of comprising
2~ C
4Group; M:0 ~ 115; N:0 ~ 115; M+n:1 ~ 115; R
4And R
5Be identical or different and be hydrogen or aliphatics organic group with 1 to 6 carbon atom.
b)
R wherein
2And R
3Be independently selectable side chain or the straight chain aliphatics C of comprising
2~ C
4Group; M:0 ~ 40; N:0 ~ 40; M+n:1 ~ 115; R, R
4And R
5Be identical or different and be hydrogen or aliphatics organic group with 1 to 6 carbon atom.
In the above-mentioned aliphatic polyether amine technology, the hydrogen add-on generally is to control through the pressure that adjustment hydrogen charges into reactor drum, and pressure control range is 1.5 ~ 8MPa.
In the production technique of said aliphatic polyether amine, vacuum distillation temperature is controlled at 100～120 ℃, vacuum degree control-0.08～-0.1MPa, slough moisture, aminating agent and other low-boiling by-products.
Reactor drum is stirring reactor or annular reactor in the production technique of said aliphatic polyether amine.
Technology of the present invention, skeletal nickel catalyst and aminating agent are all carried out recycled after treatment, and whole technological process route selection property is good, transformation efficiency is high, environmental pollution is few, convenient post-treatment.
Embodiment
Below in conjunction with embodiment technology of the present invention is described.
Embodiment 1
1.3 ~ 1.5 times NaOH are configured to 20% the aqueous solution, put into TM and stainless there-necked flask are housed, be cooled to 50 ℃ with flowing water, under high degree of agitation, the Ni-Al alloy is added wherein in batches on a small quantity (each 2 ~ 4g), add in 25 ~ 30min.Regulate the speed that adds alloy, so that the liquid temperature is remained on about in the of 50 ℃.Feeding intake finishes is afterwards reacting about 90min about 80 ℃ when stirring.Treat that hydrogen gas production finishes and treat to tell after static the reaction product of upper strata white cotton fiber shape, move to sedimentary black Raney's nickel catalyst in the beaker, with washing till washing lotion presents neutrality to reindeer moss.Wash respectively 2～3 times with 95% ethanol and absolute ethyl alcohol, the band that is placed on absolute ethyl alcohol at last seals in the container of stopper again.
Embodiment 2
Adding 100g number-average molecular weight 230.8 functionality are 2 terminal hydroxy group polyethenoxy ether (Plant of Tianjin Petrochemical Company polyethers portion) in the 0.5L autoclave, special-purpose skeletal nickel catalyst 10g.Use 0.4MPa nitrogen and hydrogen exchange reaction kettle 2～3 times respectively; In whipped state downhill reaction still, pour ammonia and be about 43L (under the standard state), adjustment hydrogen gas cylinder top hole pressure 4.0MPa fills hydrogen to pressure equilibrium in reaction kettle; Heat temperature raising; Control reaction temperature is 200 ℃, and the reaction times is 4h, and highest response pressure is 13.0MPa.It is 50 ℃ that reaction finishes logical water coolant to the temperature of reaction kettle in back, slowly exhaust, and gas absorbs through secondary water, discharging.
With reacting liquor while hot filtering separation catalyzer and reaction product, reaction product is carried out underpressure distillation in being transferred to there-necked flask, temperature is 105 ℃, vacuum tightness is that distillation time is 2h, promptly gets the polyetheramine product.Adopt GB GB12008.3-89 test lead hydroxy polyethers OH value, measure total amine value and primary, the second month in a season, uncle's content of polyetheramine with USS ASTM2074 method.The Aethoxy Sklerol transformation efficiency is 70.6%, and primary amine purity is 97.3%.
Embodiment 3
Adding 100g number-average molecular weight 230.8 functionality are 2 terminal hydroxy group polyethenoxy ether (Plant of Tianjin Petrochemical Company polyethers portion) in the 0.5L autoclave, special-purpose skeletal nickel catalyst 15g.Use 0.4MPa nitrogen and hydrogen exchange reaction kettle 2～3 times respectively; In whipped state downhill reaction still, pour ammonia and be about 43L (under the standard state), adjustment hydrogen gas cylinder top hole pressure 4.0MPa fills hydrogen to pressure equilibrium in reaction kettle; Heat temperature raising; Control reaction temperature is 200 ℃, and the reaction times is 4h, and highest response pressure is 12.5MPa.It is 50 ℃ that reaction finishes logical water coolant to the temperature of reaction kettle in back, slowly exhaust, and gas absorbs through secondary water, discharging.
With reacting liquor while hot filtering separation catalyzer and reaction product, reaction product is carried out underpressure distillation in being transferred to there-necked flask, temperature is 120 ℃, vacuum tightness is that distillation time is 1h, promptly gets the polyetheramine product.Adopt GB GB12008.3-89 test lead hydroxy polyethers OH value, measure total amine value and primary, the second month in a season, uncle's content of polyetheramine with USS ASTM2074 method.The Aethoxy Sklerol transformation efficiency is 92.6%, and primary amine purity is 93.2%.
Embodiment 4
Adding 100g number-average molecular weight 230.8 functionality are 2 terminal hydroxy group polyethenoxy ether (Plant of Tianjin Petrochemical Company polyethers portion) in the 0.5L autoclave, special-purpose skeletal nickel catalyst 10g.Use 0.4MPa nitrogen and hydrogen exchange reaction kettle 2～3 times respectively; In whipped state downhill reaction still, pour ammonia and be about 50.2L (under the standard state), adjustment hydrogen gas cylinder top hole pressure 2.5MPa fills hydrogen to pressure equilibrium in reaction kettle; Heat temperature raising; Control reaction temperature is 210 ℃, and the reaction times is 4h, and highest response pressure is 14.5MPa.It is 50 ℃ that reaction finishes logical water coolant to the temperature of reaction kettle in back, slowly exhaust, and gas absorbs through secondary water, discharging.
With reacting liquor while hot filtering separation catalyzer and reaction product, reaction product is carried out underpressure distillation in being transferred to there-necked flask, temperature is 105 ℃, vacuum tightness is-0.08MPa that distillation time is 2h, promptly gets the polyetheramine product.Adopt GB GB12008.3-89 test lead hydroxy polyethers OH value, measure total amine value and primary, the second month in a season, uncle's content of polyetheramine with USS ASTM2074 method.The Aethoxy Sklerol transformation efficiency is 87.7%, and primary amine purity is 94.6%.
Embodiment 5
Adding 100g number-average molecular weight 431.5 functionality are 2 terminal hydroxy group polyethenoxy ether (Plant of Tianjin Petrochemical Company polyethers portion) in the 0.5L autoclave, special-purpose skeletal nickel catalyst 15g.Use 0.4MPa nitrogen and hydrogen exchange reaction kettle 2～3 times respectively; In whipped state downhill reaction still, pour ammonia and be about 60.3L (under the standard state), adjustment hydrogen gas cylinder top hole pressure 4.0MPa fills hydrogen to pressure equilibrium in reaction kettle; Heat temperature raising; Control reaction temperature is 200 ℃, and the reaction times is 4h, and highest response pressure is 9.8MPa.It is 50 ℃ that reaction finishes logical water coolant to the temperature of reaction kettle in back, slowly exhaust, and gas absorbs through secondary water, discharging.
With reacting liquor while hot filtering separation catalyzer and reaction product, reaction product is carried out underpressure distillation in being transferred to there-necked flask, temperature is 105 ℃, vacuum tightness is-0.09MPa that distillation time is 2h, promptly gets the polyetheramine product.Adopt GB GB12008.3-89 test lead hydroxy polyethers OH value, measure total amine value and primary, the second month in a season, uncle's content of polyetheramine with USS ASTM2074 method.The Aethoxy Sklerol transformation efficiency is 80.6%, and primary amine purity is 90.2%.
Embodiment 6
Adding 100g number-average molecular weight 800.0 functionality are 2 terminal hydroxy group polyethenoxy ether (Plant of Tianjin Petrochemical Company polyethers portion) in the 0.5L autoclave, special-purpose skeletal nickel catalyst 14g.Use 0.4MPa nitrogen and hydrogen exchange reaction kettle 2～3 times respectively; In whipped state downhill reaction still, pour ammonia and be about 70.2L (under the standard state), adjustment hydrogen gas cylinder top hole pressure 3.5MPa fills hydrogen to pressure equilibrium in reaction kettle; Heat temperature raising; Control reaction temperature is 200 ℃, and the reaction times is 4h, and highest response pressure is 13.8Pa.It is 50 ℃ that reaction finishes logical water coolant to the temperature of reaction kettle in back, slowly exhaust, and gas absorbs through secondary water, discharging.
With reacting liquor while hot filtering separation catalyzer and reaction product, reaction product is carried out underpressure distillation in being transferred to there-necked flask, temperature is 105 ℃, vacuum tightness is that distillation time is 2h, promptly gets the polyetheramine product.Adopt GB GB12008.3-89 test lead hydroxy polyethers OH value, measure total amine value and primary, the second month in a season, uncle's content of polyetheramine with USS ASTM2074 method.The Aethoxy Sklerol transformation efficiency is 86.9%, and primary amine purity is 95.7%.
Embodiment 7
Adding 100g number-average molecular weight 983.0 functionality are 2 terminal hydroxy group polyethenoxy ether (Plant of Tianjin Petrochemical Company polyethers portion) in the 0.5L autoclave, special-purpose skeletal nickel catalyst 10g.Use 0.4MPa nitrogen and hydrogen exchange reaction kettle 2～3 times respectively; In whipped state downhill reaction still, pour ammonia and be about 40.2L (under the standard state), adjustment hydrogen gas cylinder top hole pressure 2.5MPa fills hydrogen to pressure equilibrium in reaction kettle; Heat temperature raising; Control reaction temperature is 200 ℃, and the reaction times is 4h, and highest response pressure is Pa.It is 50 ℃ that reaction finishes logical water coolant to the temperature of reaction kettle in back, slowly exhaust, and gas absorbs through secondary water, discharging.
With reacting liquor while hot filtering separation catalyzer and reaction product, reaction product is carried out underpressure distillation in being transferred to there-necked flask, temperature is 105 ℃, vacuum tightness is-0.08MPa that distillation time is 2h, promptly gets the polyetheramine product.Adopt GB GB12008.3-89 test lead hydroxy polyethers OH value, measure total amine value and primary, the second month in a season, uncle's content of polyetheramine with USS ASTM2074 method.The Aethoxy Sklerol transformation efficiency is 98.47%, and primary amine purity is 96.5%.
Embodiment 8
Adding 100g number-average molecular weight 983.0 functionality are 2 terminal hydroxy group polyethenoxy ether (Plant of Tianjin Petrochemical Company polyethers portion) in the 0.5L autoclave, special-purpose skeletal nickel catalyst 5g.Use 0.4MPa nitrogen and hydrogen exchange reaction kettle 2～3 times respectively; In whipped state downhill reaction still, pour ammonia and be about 40.2L (under the standard state), adjustment hydrogen gas cylinder top hole pressure 3.5MPa fills hydrogen to pressure equilibrium in reaction kettle; Heat temperature raising; Control reaction temperature is 200 ℃, and the reaction times is 3h, and highest response pressure is 14.4Pa.It is 50 ℃ that reaction finishes logical water coolant to the temperature of reaction kettle in back, slowly exhaust, and gas absorbs through secondary water, discharging.
With reacting liquor while hot filtering separation catalyzer and reaction product, reaction product is carried out underpressure distillation in being transferred to there-necked flask, temperature is 105 ℃, vacuum tightness is-0.08MPa that distillation time is 2h, promptly gets the polyetheramine product.Adopt GB GB12008.3-89 test lead hydroxy polyethers OH value, measure total amine value and primary, the second month in a season, uncle's content of polyetheramine with USS ASTM2074 method.The Aethoxy Sklerol transformation efficiency is 100.0%, and primary amine purity is 96.4%.
Embodiment 9
Adding 100g number-average molecular weight 983.0 functionality are 2 terminal hydroxy group polyethenoxy ether (Plant of Tianjin Petrochemical Company polyethers portion) in the 0.5L autoclave, special-purpose skeletal nickel catalyst 5g.Use 0.4MPa nitrogen and hydrogen exchange reaction kettle 2～3 times respectively; In whipped state downhill reaction still, pour ammonia and be about 40.2L (under the standard state), adjustment hydrogen gas cylinder top hole pressure 2.5MPa fills hydrogen to pressure equilibrium in reaction kettle; Heat temperature raising; Control reaction temperature is 180 ℃, and the reaction times is 4h, and highest response pressure is 12.6MPa.It is 50 ℃ that reaction finishes logical water coolant to the temperature of reaction kettle in back, slowly exhaust, and gas absorbs through secondary water, discharging.
With reacting liquor while hot filtering separation catalyzer and reaction product, reaction product is carried out underpressure distillation in being transferred to there-necked flask, temperature is 105 ℃, vacuum tightness is-0.08MPa that distillation time is 2h, promptly gets the polyetheramine product.Adopt GB GB12008.3-89 test lead hydroxy polyethers OH value, measure total amine value and primary, the second month in a season, uncle's content of polyetheramine with USS ASTM2074 method.The Aethoxy Sklerol transformation efficiency is 90.3%, and primary amine purity is 97.2%.
Embodiment 10
Adding 100g number-average molecular weight 983.0 functionality are 2 terminal hydroxy group polyethenoxy ether (Plant of Tianjin Petrochemical Company polyethers portion) in the 0.5L autoclave, special-purpose skeletal nickel catalyst 5g.Use 0.4MPa nitrogen and hydrogen exchange reaction kettle 2～3 times respectively; In whipped state downhill reaction still, pour ammonia and be about 20.2L (under the standard state), adjustment hydrogen gas cylinder top hole pressure 2.5MPa fills hydrogen to pressure equilibrium in reaction kettle; Heat temperature raising; Control reaction temperature is 180 ℃, and the reaction times is 4h, and highest response pressure is 9.8MPa.It is 50 ℃ that reaction finishes logical water coolant to the temperature of reaction kettle in back, slowly exhaust, and gas absorbs through secondary water, discharging.
With reacting liquor while hot filtering separation catalyzer and reaction product, reaction product is carried out underpressure distillation in being transferred to there-necked flask, temperature is 105 ℃, vacuum tightness is-0.08MPa that distillation time is 2h, promptly gets the polyetheramine product.Adopt GB GB12008.3-89 test lead hydroxy polyethers OH value, measure total amine value and primary, the second month in a season, uncle's content of polyetheramine with USS ASTM2074 method.The Aethoxy Sklerol transformation efficiency is 82.9%, and primary amine purity is 89.5%.
Embodiment 11
Adding 100g number-average molecular weight 983.0 functionality are 2 terminal hydroxy group polyethenoxy ether (Plant of Tianjin Petrochemical Company polyethers portion) in the 0.5L autoclave, special-purpose skeletal nickel catalyst 3.0g.Use 0.4MPa nitrogen and hydrogen exchange reaction kettle 2～3 times respectively; In whipped state downhill reaction still, pour ammonia and be about 40.2L (under the standard state), adjustment hydrogen gas cylinder top hole pressure 3.0MPa fills hydrogen to pressure equilibrium in reaction kettle; Heat temperature raising; Control reaction temperature is 200 ℃, and the reaction times is 4h, and highest response pressure is 12.2MPa.It is 50 ℃ that reaction finishes logical water coolant to the temperature of reaction kettle in back, slowly exhaust, and gas absorbs through secondary water, discharging.
With reacting liquor while hot filtering separation catalyzer and reaction product, reaction product is carried out underpressure distillation in being transferred to there-necked flask, temperature is 105 ℃, vacuum tightness is-0.08MPa that distillation time is 2h, promptly gets the polyetheramine product.Adopt GB GB12008.3-89 test lead hydroxy polyethers OH value, measure total amine value and primary, the second month in a season, uncle's content of polyetheramine with USS ASTM2074 method.The Aethoxy Sklerol transformation efficiency is 97.5%, and primary amine purity is 97.5%.
Embodiment 12
Adding 100g number-average molecular weight 2000.0 functionality are 2 terminal hydroxy group polyethenoxy ether in the 0.5L autoclave, special-purpose skeletal nickel catalyst 3.0g.Use 0.4MPa nitrogen and hydrogen exchange reaction kettle 2～3 times respectively; In whipped state downhill reaction still, pour ammonia and be about 20.2L (under the standard state), adjustment hydrogen gas cylinder top hole pressure 3.0MPa fills hydrogen to pressure equilibrium in reaction kettle; Heat temperature raising; Control reaction temperature is 200 ℃, and the reaction times is 4h, and highest response pressure is 10.2MPa.It is 50 ℃ that reaction finishes logical water coolant to the temperature of reaction kettle in back, slowly exhaust, and gas absorbs through secondary water, discharging.
With reacting liquor while hot filtering separation catalyzer and reaction product, reaction product is carried out underpressure distillation in being transferred to there-necked flask, temperature is 105 ℃, vacuum tightness is-0.09MPa that distillation time is 2h, promptly gets the polyetheramine product.Adopt GB GB12008.3-89 test lead hydroxy polyethers OH value, measure total amine value and primary, the second month in a season, uncle's content of polyetheramine with USS ASTM2074 method.The Aethoxy Sklerol transformation efficiency is 96.5%, and primary amine purity is 93.5%.
Embodiment 13
Adding 100g number-average molecular weight 5000.0 functionality are 3 terminal hydroxy group polyethenoxy ether in the 0.5L autoclave, special-purpose skeletal nickel catalyst 5.0g.Use 0.4MPa nitrogen and hydrogen exchange reaction kettle 2～3 times respectively; In whipped state downhill reaction still, pour ammonia and be about 15.2L (under the standard state), adjustment hydrogen gas cylinder top hole pressure 3.0MPa fills hydrogen to pressure equilibrium in reaction kettle; Heat temperature raising; Control reaction temperature is 200 ℃, and the reaction times is 4h, and highest response pressure is 8.9MPa.It is 50 ℃ that reaction finishes logical water coolant to the temperature of reaction kettle in back, slowly exhaust, and gas absorbs through secondary water, discharging.
With reacting liquor while hot filtering separation catalyzer and reaction product, reaction product is carried out underpressure distillation in being transferred to there-necked flask, temperature is 105 ℃, vacuum tightness is-0.08MPa that distillation time is 2h, promptly gets the polyetheramine product.Adopt GB GB12008.3-89 test lead hydroxy polyethers OH value, measure total amine value and primary, the second month in a season, uncle's content of polyetheramine with USS ASTM2074 method.The Aethoxy Sklerol transformation efficiency is 97.5%, and primary amine purity is 95.5%.
Embodiment 14
Adding 100g number-average molecular weight 1000.0 functionality are 2 terminal hydroxy group Soxylat A 25-7 in the 0.5L autoclave, special-purpose skeletal nickel catalyst 5.0g.Use 0.4MPa nitrogen and hydrogen exchange reaction kettle 2～3 times respectively; In whipped state downhill reaction still, pour ammonia and be about 50.2L (under the standard state), adjustment hydrogen gas cylinder top hole pressure 3.0MPa fills hydrogen to pressure equilibrium in reaction kettle; Heat temperature raising; Control reaction temperature is 198 ℃, and the reaction times is 4h, and highest response pressure is 13.2MPa.It is 50 ℃ that reaction finishes logical water coolant to the temperature of reaction kettle in back, slowly exhaust, and gas absorbs through secondary water, discharging.
With reacting liquor while hot filtering separation catalyzer and reaction product, reaction product is carried out underpressure distillation in being transferred to there-necked flask, temperature is 115 ℃, vacuum tightness is-0.08MPa that distillation time is 1h, promptly gets the polyetheramine product.Adopt GB GB12008.3-89 test lead hydroxy polyethers OH value, measure total amine value and primary, the second month in a season, uncle's content of polyetheramine with USS ASTM2074 method.The Aethoxy Sklerol transformation efficiency is 98.5%, and primary amine purity is 94.5%.
Embodiment 15
The polyoxypropylene, the Vinyl Ether copolymerization glycol that in the 0.5L autoclave, add 100g number-average molecular weight 238.0, special-purpose skeletal nickel catalyst 10.0g.Use 0.4MPa nitrogen and hydrogen exchange reaction kettle 2～3 times respectively; In whipped state downhill reaction still, pour ammonia and be about 55.2L (under the standard state), adjustment hydrogen gas cylinder top hole pressure 2.5MPa fills hydrogen to pressure equilibrium in reaction kettle; Heat temperature raising; Control reaction temperature is 200 ℃, and the reaction times is 4h, and highest response pressure is 12.8MPa.It is 50 ℃ that reaction finishes logical water coolant to the temperature of reaction kettle in back, slowly exhaust, and gas absorbs through secondary water, discharging.
With reacting liquor while hot filtering separation catalyzer and reaction product, reaction product is carried out underpressure distillation in being transferred to there-necked flask, temperature is 120 ℃, vacuum tightness is-0.09MPa that distillation time is 1h, promptly gets the polyetheramine product.Adopt GB GB12008.3-89 test lead hydroxy polyethers OH value, measure total amine value and primary, the second month in a season, uncle's content of polyetheramine with USS ASTM2074 method.The Aethoxy Sklerol transformation efficiency is 88.5%, and primary amine purity is 95.5%.
Claims (9)
1. an aliphatic polyether amine production technique is to be raw material with the polyether glycol, in the presence of hydrogen, aminating agent and catalyzer, prepares the technology of polyetheramine through the catalytic reduction amination, and its characteristic comprises following step:
A) select special-purpose skeletal nickel catalyst for use, its composition is metallic nickel and metallic aluminium, and metallic nickel quality percentage composition accounts for 85～95%, and metallic aluminium quality percentage composition accounts for 15～5%, catalyst seal is preserved subsequent use;
B) in reactor drum, adopt the catalyzer described in the step a), carry out the catalytic reduction amination reaction, raw materials used is the polyether glycol of number-average molecular weight more than 100; The catalyzer add-on is 2 ~ 15% of a raw material polyether glycol quality; The aminating agent add-on is 1.5 ~ 20 times of raw material polyether glycol hydroxyl mole number, and the hydrogen add-on is 0.4 ~ 15 times of raw material polyether glycol hydroxyl mole number, and temperature of reaction is 120 ~ 250 ℃; Reaction pressure is 8 ~ 35MPa, and the reaction times is 1.5 ~ 8h;
C) reaction solution in the step b) is cooled to 25 ~ 60 ℃, get rid of unreacted gas, discharging, reaction product is sloughed moisture, aminating agent and other low-boiling by-products through underpressure distillation and is promptly got the aliphatic polyether amine product.
2. according to the production technique of the said aliphatic polyether amine of claim 1, it is characterized in that: described raw material polyether glycol have following general structure a) or b):
a）
R wherein
1, R
2And R
3Be independently selectable side chain or the straight chain aliphatics C of comprising
2~ C
4Group; M:0 ~ 115; N:0 ~ 115; M+n:1 ~ 115;
b)
Wherein R is hydrogen or the aliphatics organic group with 1 to 6 carbon atom, R
2And R
3Be independently selectable side chain or the straight chain aliphatics C of comprising
2~ C
4Group; M:0 ~ 40; N:0 ~ 40; M+n:1 ~ 115.
3. according to the production technique of the said aliphatic polyether amine of claim 1, it is characterized in that prepared aliphatic polyether amine have following general structure a) or b):
a）
R wherein
1, R
2And R
3Be independently selectable side chain or the straight chain aliphatics C of comprising
2~ C
4Group; M:0 ~ 115; N:0 ~ 115; M+n:1 ~ 115; R
4And R
5Be identical or different and be hydrogen or aliphatics organic group with 1 to 6 carbon atom;
b)
R wherein
2And R
3Be independently selectable side chain or the straight chain aliphatics C of comprising
2~ C
4Group; M:0 ~ 40; N:0 ~ 40; M+n:1 ~ 115; R, R
4And R
5Be identical or different and be hydrogen or aliphatics organic group with 1 to 6 carbon atom.
4. according to the production technique of the said aliphatic polyether amine of claim 1, it is characterized in that the preparation method of said special-purpose skeletal nickel catalyst comprises following steps:
A) metallic nickel quality percentage composition is accounted for 85～95%; Metallic aluminium quality percentage composition accounts for 15～5% binary Nickel Aluminium Alloy Powder and under vigorous stirring, adds in the sodium hydroxide solution and dissolve; The sodium hydroxide mass percent concentration is 10～40%, and sodium hydroxide concentration is 1～3 times of alloy powder quality, and solvent temperature is at 45～85 ℃; Dissolution time is 0.5～5h, and dissolving finishes continued at 50～100 ℃ of priming reaction 0.5～5h;
B) tell the reaction product of upper strata white cotton fiber shape after static, repeatedly wash sedimentary black Raney's nickel catalyst water to neutrality, wash 2～5 times with ethanol solution again, be kept at catalyzer in the ethanol solution then.
5. according to the production technique of the said aliphatic polyether amine of claim 1, it is characterized in that said aminating agent is ammonia, methylamine, n n dimetylaniline, ethamine, diethylamine, Tri N-Propyl Amine, di-n-propylamine, Isopropylamine, Diisopropylamine, hexylamine or hexahydroaniline.
6. according to the production technique of the said aliphatic polyether amine of claim 1, it is characterized in that the hydrogen add-on is to control through the pressure that adjustment hydrogen charges into reactor drum, pressure control range is 1.5 ~ 8MPa.
7. according to the production technique of the said aliphatic polyether amine of claim 1, it is characterized in that vacuum distillation temperature is controlled at 100～120 ℃, vacuum degree control-0.08～-0.1MPa, slough moisture, aminating agent and other low-boiling by-products.
8. according to the production technique of the said aliphatic polyether amine of claim 1, it is characterized in that reactor drum is a stirring reactor.
9. according to the production technique of the said aliphatic polyether amine of claim 1, it is characterized in that reactor drum is an annular reactor.
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| CN102604072A (en) * | 2012-03-02 | 2012-07-25 | 无锡阿科力化工有限公司 | Preparation method of polyether amine |
| CN102964586A (en) * | 2012-12-06 | 2013-03-13 | 盘锦科隆精细化工股份有限公司 | Preparation method of catalyst used for polyether amine |
| CN104119239A (en) * | 2014-08-12 | 2014-10-29 | 无锡阿科力科技股份有限公司 | Process of producing small molecular weight polyether amine by continuous method |
| CN104419002A (en) * | 2013-08-20 | 2015-03-18 | 中国石油化工股份有限公司 | Producing method of amine-terminated polyether |
| CN105542146A (en) * | 2015-12-10 | 2016-05-04 | 浙江皇马科技股份有限公司 | Continuous production process for polyetheramine |
| CN107915836A (en) * | 2016-10-11 | 2018-04-17 | 上海东大化学有限公司 | Polyetheramine and preparation method thereof |
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| CN115926140A (en) * | 2022-12-24 | 2023-04-07 | 江南大学 | N, N-dibutyl polyetheramine nonionic surfactant, preparation thereof, tetrabutyl ammonium hydroxide developer based on N, N-dibutyl polyetheramine nonionic surfactant and preparation |
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| CN102604072A (en) * | 2012-03-02 | 2012-07-25 | 无锡阿科力化工有限公司 | Preparation method of polyether amine |
| CN102604072B (en) * | 2012-03-02 | 2013-09-18 | 无锡阿科力化工有限公司 | Preparation method of polyether amine |
| CN102964586A (en) * | 2012-12-06 | 2013-03-13 | 盘锦科隆精细化工股份有限公司 | Preparation method of catalyst used for polyether amine |
| CN104419002B (en) * | 2013-08-20 | 2017-12-01 | 中国石油化工股份有限公司 | A kind of production method of amine terminated polyether |
| CN104419002A (en) * | 2013-08-20 | 2015-03-18 | 中国石油化工股份有限公司 | Producing method of amine-terminated polyether |
| CN104119239B (en) * | 2014-08-12 | 2016-08-17 | 无锡阿科力科技股份有限公司 | The technique that continuity method produces small-molecular-weight polyetheramine |
| CN104119239A (en) * | 2014-08-12 | 2014-10-29 | 无锡阿科力科技股份有限公司 | Process of producing small molecular weight polyether amine by continuous method |
| US10814314B2 (en) | 2015-11-09 | 2020-10-27 | Wanhua Chemical Group Co., Ltd. | Catalyst for aminating polyether polyol and preparation method thereof and method of preparing polyetheramines using catalyst thereof |
| CN105542146A (en) * | 2015-12-10 | 2016-05-04 | 浙江皇马科技股份有限公司 | Continuous production process for polyetheramine |
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| CN107915836A (en) * | 2016-10-11 | 2018-04-17 | 上海东大化学有限公司 | Polyetheramine and preparation method thereof |
| CN107915836B (en) * | 2016-10-11 | 2020-02-07 | 上海东大化学有限公司 | Polyether amine and preparation method thereof |
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