CN102408559A - Preparation process of amine terminated polyether - Google Patents
Preparation process of amine terminated polyether Download PDFInfo
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- CN102408559A CN102408559A CN2011101887678A CN201110188767A CN102408559A CN 102408559 A CN102408559 A CN 102408559A CN 2011101887678 A CN2011101887678 A CN 2011101887678A CN 201110188767 A CN201110188767 A CN 201110188767A CN 102408559 A CN102408559 A CN 102408559A
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Abstract
The invention belongs to the technical field of polymer materials and provides a preparation process of amine terminated polyether. In the process, polyether polyol with a number-average molecular weight of more than 100 is used as a raw material, and polyetheramine is prepared by catalytic reduction and amination in the presence of hydrogen, an aminating agent and a skeleton nickel catalyst, wherein the skeleton nickel catalyst comprises the following components by mass percent: 80-95% of metal nickel, 5-20% of metal aluminum and 0.5-5% of one, two or three of chromium, iron, copper or zinc; and the skeleton nickel catalyst and the aminating agent can be circularly applied after being processed. The whole preparation process has the advantages of good route selectivity, high conversion rate, low environmental pollution, and convenience in posttreatment.
Description
Technical field
The invention belongs to polymeric material field, relate to a kind of preparation technology of polymer ends amino-polyether.
Background technology
Amino Terminated polyether(ATPE) 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.Amino Terminated polyether(ATPE) is as solidifying agent, tackiness agent, urethane and spraying Spray Polyurea Elastomer (the Spray Polyurea Elastomer of epoxy resin resin at present; Be called for short SPUA) starting material, on anticorrosion, pipeline, building, naval vessel, water conservancy, traffic, machinery, mine be wear-resisting etc., and the field has obtained widespread use.The present compound method of Amino Terminated polyether(ATPE) 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 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.This method operational path is simple, but in the reaction process of polyether glycol and vinyl cyanide, side reaction is many, and the easy autohemagglutination of vinyl cyanide, and is therefore strict to reaction conditions, the actually operating difficulty.
The compound method of existing disclosed relevant Amino Terminated polyether(ATPE):
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 %, 14～37 moles of % copper and 1～5 mole of % chromium.
DE3608716 has described from corresponding alcohol use nickel-aluminium-molybdenum catalyst and has prepared the method for polyoxy alkylidene amine, and this catalyzer comprises 0.2～5wt% molybdenum, 0～40wt% aluminium.
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 Amino Terminated polyether(ATPE).
The object of the invention is realized through following technical scheme: a kind of Amino Terminated polyether(ATPE) preparation technology; Be to be raw material with the polyether glycol; In the presence of hydrogen, aminating agent and catalyzer, prepare the technology of Amino Terminated polyether(ATPE) through the catalytic reduction amination, it comprises the following step:
A) select special-purpose skeletal nickel catalyst for use, its mass percent consists of: 80～95% metallic nickels, 5～20% metallic aluminiums, in 0.5～5% chromium, iron, copper or the zinc a kind of, two or three, catalyst seal is preserved subsequent use;
B) in stirring reactor, 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 Amino Terminated polyether(ATPE) product.
Usually, the preparation method of special-purpose skeletal nickel catalyst may further comprise the steps in the Amino Terminated polyether(ATPE) production technique of the present invention:
Ternary, quaternary or the quinary alloy powder that a) will contain different components join in the sodium hydroxide solution under vigorous stirring and dissolve; The sodium hydroxide mass percent concentration is 10～40%; Sodium hydroxide concentration is 1～3 times of alloy powder quality; Solvent temperature is at 45～100 ℃, and 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 skeletal nickel catalyst to neutrality with warm water, wash 2～5 times with ethanol solution again, be kept at catalyzer in the ethanol solution then.
The production technique of above-mentioned Amino Terminated polyether(ATPE), 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 Amino Terminated polyether(ATPE), 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 Amino Terminated polyether(ATPE), the prepared following general structure of Amino Terminated polyether(ATPE) tool 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.
Among the said Amino Terminated polyether(ATPE) preparation technology, aminating agent is ammonia, methylamine, n n dimetylaniline, ethamine, diethylamine, Tri N-Propyl Amine, di-n-propylamine, Isopropylamine, Diisopropylamine, hexylamine or hexahydroaniline.
Said Amino Terminated polyether(ATPE) preparation technology is that the hydrogen add-on is to control through the pressure that adjustment hydrogen charges into reactor drum in the actually operating, and pressure control range is 1.5 ~ 8MPa.
Among the said Amino Terminated polyether(ATPE) preparation technology, 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 a stirring reactor among the said Amino Terminated polyether(ATPE) preparation technology.
In the technology of the present invention, skeletal nickel catalyst and aminating agent all carry out recycled after treatment, and whole preparation 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
2 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, the Ni-Al alloy powder of under high degree of agitation, extra fine quality being formed add wherein on a small quantity in batches (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, quaternary 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 50L (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 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 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 Amino Terminated polyether(ATPE) with USS ASTM2074 method.Total amine value of product is 6.80mmoL/g, and the Aethoxy Sklerol transformation efficiency is 81.1%, and primary amine purity is 96.7%.
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, quaternary 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 50L (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 3h, and highest response pressure is 13.6MPa.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 120 ℃, vacuum tightness is that distillation time is 1h, promptly gets the Amino Terminated polyether(ATPE) 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.Total amine value of product is 7.25mmoL/g, and the Aethoxy Sklerol transformation efficiency is 87.7%, and primary amine purity is 95.0%.
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, ternary 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 43.2L (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 190 ℃, 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 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.Total amine value of product is 4.83mmoL/g, and the Aethoxy Sklerol transformation efficiency is 58.4%, and primary amine purity is 94.9%.
Embodiment 5
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, quaternary 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 43.2L (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 220 ℃, and the reaction times is 4h, and highest response pressure is 12.3MPa.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 Amino Terminated polyether(ATPE) 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.Total amine value of product is 6.72mmoL/g, and the Aethoxy Sklerol transformation efficiency is 85.9%, and primary amine purity is 92.4%.
Embodiment 6
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 28.6L (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 8.9Pa.It is 60 ℃ 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 1h, promptly gets the Amino Terminated polyether(ATPE) 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.Total amine value of product is 1.71mmoL/g, and the Aethoxy Sklerol transformation efficiency is 86.3%, and primary amine purity is 97.6%.
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, the special-purpose skeletal nickel catalyst 2g of quaternary.Use 0.4MPa nitrogen and hydrogen exchange reaction kettle 2～3 times respectively; In whipped state downhill reaction still, pour ammonia and be about 30.2L (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 11.2MPa.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.Total amine value of product is 1.72mmoL/g, and the Aethoxy Sklerol transformation efficiency is 88.3%, and primary amine purity is 96.4%.
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, the special-purpose skeletal nickel catalyst 5g of quaternary.Use 0.4MPa nitrogen and hydrogen exchange reaction kettle 2～3 times respectively; In whipped state downhill reaction still, pour ammonia and be about 43.0L (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 60 ℃ 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 Amino Terminated polyether(ATPE) 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.Total amine value of product is 1.89mmoL/g, and the Aethoxy Sklerol transformation efficiency is 96.2%, and primary amine purity is 98.6%.
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, quaternary 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 28.2L (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 2h, and highest response pressure is 9.2MPa.It is 60 ℃ 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 1h, promptly gets the Amino Terminated polyether(ATPE) 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.Total amine value of product is 1.89mmoL/g, and the Aethoxy Sklerol transformation efficiency is 96.4%, and primary amine purity is 96.3%.
Embodiment 10
Adding 100g number-average molecular weight 2000.0 functionality are 2 terminal hydroxy group polyethenoxy ether in the 0.5L autoclave, the special-purpose skeletal nickel catalyst 3.5g of quaternary.Use 0.4MPa nitrogen and hydrogen exchange reaction kettle 2～3 times respectively; In whipped state downhill reaction still, pour ammonia and be about 18.2L (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 195 ℃, and the reaction times is 3h, and highest response pressure is 9.2MPa.It is 60 ℃ 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.Total amine value of product is 0.92mmoL/g, and the Aethoxy Sklerol transformation efficiency is 96.4%, and primary amine purity is 96.3%.
Embodiment 11
Adding 100g number-average molecular weight 2000.0 functionality are 2 terminal hydroxy group polyethenoxy ether in the 0.5L autoclave, the special-purpose skeletal nickel catalyst 4.0g of quaternary.Use 0.4MPa nitrogen and hydrogen exchange reaction kettle 2～3 times respectively; In whipped state downhill reaction still, pour ammonia and be about 22.2L (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 9.2MPa.It is 60 ℃ 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.Total amine value of product is 1.02mmoL/g, and the Aethoxy Sklerol transformation efficiency is 100.0%, and primary amine purity is 97.3%.
Embodiment 12
Adding 100g number-average molecular weight 5000.0 functionality are 3 terminal hydroxy group polyethenoxy ether in the 0.5L autoclave, the special-purpose skeletal nickel catalyst 5.0g of quaternary.Use 0.4MPa nitrogen and hydrogen exchange reaction kettle 2～3 times respectively; In whipped state downhill reaction still, pour ammonia and be about 10.2L (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 3h, and highest response pressure is 8.5MPa.It is 60 ℃ 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 98.5%, and primary amine purity is 96.5%.
Claims (8)
1. an Amino Terminated polyether(ATPE) preparation technology is to be raw material with the polyether glycol, in the presence of hydrogen, aminating agent and catalyzer, prepares the technology of Amino Terminated polyether(ATPE) through the catalytic reduction amination, and its characteristic comprises following step:
A) select special-purpose skeletal nickel catalyst for use, its mass percent consists of: 80～95% metallic nickels, 5～20% metallic aluminiums, in 0.5～5% chromium, iron, copper or the zinc a kind of, two or three, 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 Amino Terminated polyether(ATPE) product.
2. according to the said Amino Terminated polyether(ATPE) preparation technology 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 said Amino Terminated polyether(ATPE) preparation technology of claim 1, it is characterized in that prepared Amino Terminated polyether(ATPE) 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 said Amino Terminated polyether(ATPE) preparation technology of claim 1, it is characterized in that said special-purpose skeletal nickel catalyst preparation method comprises following step:
The alloy powder that a) will contain ternary, quaternary or five yuan of different components joins in the sodium hydroxide solution under vigorous stirring and dissolves; The sodium hydroxide mass percent concentration is 10～40%; Sodium hydroxide concentration is 1～3 times of alloy powder quality; Solvent temperature is at 45～100 ℃, and 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 skeletal 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 said Amino Terminated polyether(ATPE) preparation technology of claim 1, it is characterized in that 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 said Amino Terminated polyether(ATPE) preparation technology 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 said Amino Terminated polyether(ATPE) preparation technology 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 said Amino Terminated polyether(ATPE) preparation technology of claim 1, it is characterized in that said reactor drum is a stirring reactor.
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|---|---|---|---|
| CN2011101887678A CN102408559A (en) | 2011-07-07 | 2011-07-07 | Preparation process of amine terminated polyether |
| SG2012050605A SG187335A1 (en) | 2011-07-07 | 2012-07-06 | Method for preparing amino-terminated polyether |
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|---|---|---|---|
| CN2011101887678A CN102408559A (en) | 2011-07-07 | 2011-07-07 | Preparation process of amine terminated polyether |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
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| 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 |
| CN103342808A (en) * | 2013-07-04 | 2013-10-09 | 中国石油化工股份有限公司 | Synthesis method of aliphatic amine-terminated polyether |
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| 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 |
| CN107964094A (en) * | 2017-11-28 | 2018-04-27 | 中国科学院长春应用化学研究所 | A kind of catalyst, its preparation method and application for being used to synthesize end primary amino radical polyethers |
| 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 |
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| CN109503389A (en) * | 2019-01-14 | 2019-03-22 | 南京师范大学 | The method that primary amine in No. 200 polyetheramines is extracted using unilateral line rectification under vacuum and column chromatography |
| CN109569441A (en) * | 2018-12-14 | 2019-04-05 | 南京红宝丽聚氨酯有限公司 | A kind of method of reactor and serialization preparation small molecule polyetheramine |
| CN109880111A (en) * | 2017-12-06 | 2019-06-14 | 中国石油化工股份有限公司 | A kind of catalyst and preparation method thereof for synthesizing polyether amine |
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| 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 |
| CN104099069A (en) * | 2013-04-12 | 2014-10-15 | 中国石油化工股份有限公司 | Anti-temperature clay anti-swelling agent and preparation method thereof |
| CN104099069B (en) * | 2013-04-12 | 2017-02-08 | 中国石油化工股份有限公司 | Anti-temperature clay anti-swelling agent and preparation method thereof |
| CN103342808A (en) * | 2013-07-04 | 2013-10-09 | 中国石油化工股份有限公司 | Synthesis method of aliphatic amine-terminated polyether |
| CN108191675A (en) * | 2014-06-11 | 2018-06-22 | 宁夏中盛新科技有限公司 | The method that paraphenetidine is prepared with the device catalytic hydrogenation of industrially scalable |
| 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 |
| 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 |
| CN107964094A (en) * | 2017-11-28 | 2018-04-27 | 中国科学院长春应用化学研究所 | A kind of catalyst, its preparation method and application for being used to synthesize end primary amino radical polyethers |
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| CN109503389B (en) * | 2019-01-14 | 2021-08-31 | 南京师范大学 | Method for extracting primary amine in No. 200 polyetheramine by adopting single-side-line reduced pressure rectification and column chromatography |
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Application publication date: 20120411 |