CN108017782A - A kind of polyetheramine and preparation method thereof - Google Patents
A kind of polyetheramine and preparation method thereof Download PDFInfo
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- CN108017782A CN108017782A CN201710655283.7A CN201710655283A CN108017782A CN 108017782 A CN108017782 A CN 108017782A CN 201710655283 A CN201710655283 A CN 201710655283A CN 108017782 A CN108017782 A CN 108017782A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/321—Polymers modified by chemical after-treatment with inorganic compounds
- C08G65/325—Polymers modified by chemical after-treatment with inorganic compounds containing nitrogen
- C08G65/3255—Ammonia
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
- C08G65/2603—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen
- C08G65/2606—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups
- C08G65/2609—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups containing aliphatic hydroxyl groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
- C08G65/2603—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen
- C08G65/2606—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups
- C08G65/2612—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups containing aromatic or arylaliphatic hydroxyl groups
Abstract
The invention discloses a kind of polyetheramine and preparation method thereof.The preparation method includes：(1) skeletal nickel catalyst and Mg-Al composite oxide are used as composite catalyst；(2) polyethers, aminated compounds and hydrogen are added, carries out aminating reaction；(3) after gas-liquid separation, liquid material mixes through being dehydrated with after deamination and carries out aminating reaction again reaction product with aminated compounds and hydrogen；(4) reaction product cools down, and after gas-liquid separation, liquid material is dehydrated and deamination, up to target product polyetheramine.Preparation method reaction condition of the invention is relatively mild, high conversion rate, can greatly reduce segment fracture, the narrow molecular weight distribution of obtained polyetheramine.The major constituent that the polyetheramine of the present invention is particularly suitable as gasoline cleaning agent uses, while it can not only efficiently control fuel system, the deposit generation of air inlet system, moreover it is possible to substantially reduce combustion chamber deposit CCD generations.
Description
Technical field
The present invention relates to the preparing technical field of polymer, and in particular to a kind of polyetheramine and preparation method thereof.
Background technology
The unstable components such as some olefin that contains in gasoline, aromatic hydrocarbons are easily in the fuel nozzle, intake valve and combustion of engine
Burn indoor generation deposit：Fuel nozzle carbon distribution (PFIDA), intake valve carbon distribution and combustion-chamber deposit, influence engine performance, lead
Gasoline combustion process deterioration, oil consumption increase, exhaust pollutant discharge increase are caused, this is one that current domestic haze weather produces
Major reason.
Add effective detersive in the oil, be improve automobile engine performance, control pollutant emission has efficacious prescriptions
Method.Forth generation gasoline cleaning agent using polyisobutene amine compound as representative can effectively remove engine nozzle, intake valve
The deposit formed Deng position, but inevitably increase combustion chamber deposit.This is because polyisobutylene group thermostabilization
Property it is high, be not easily decomposed at high temperature, after entering combustion chamber with fuel, the undecomposed detersive in part adsorbs and is gathered in combustion chamber
Inner wall, forms deposit, so as to increase the generation of combustion chamber deposit.
Polyetheramine is a kind of surface reactive material, and nonpolar polyether group and polarity amido base are included in its molecular structure
Group.Its polar group is stretched into gasoline, and the molecule of established deposit is surrounded, and forms oil-soluble micella, point
It is scattered in oil, with oil firing, achievees the purpose that cleaning；Its nonpolar polyether chain is preferentially adsorbed on metal or ion surface, is formed
One layer of molecule protective film, prevents the aggregation of particle from depositing, and plays the role of keeping clean.On the other hand, C-O-C in polyetheramine
Key is easy to Pintsch process, it is while fuel system, the deposit generation of air inlet system is efficiently controlled, moreover it is possible to substantially reduces combustion chamber
Carbon deposit CCD is generated.
The synthetic method of polyetheramine mainly has ammonolysis process, leaving group method, polyethers nitrile alkylation process and amino fourth at present
Four kinds of olefin(e) acid ester process：
(1) ammonolysis process is catalyzed reductive amination method, its essence is polyethers in the same amino of hydroxyl, hydrogen in high-temperature and high-pressure conditions
Ammonolysis reaction is carried out in the presence of lower and Hydro-catalyst.
(2) it is with compound (acid chloride group, benzene sulfo group, halogen with easy leaving group that leaving group method, which prepares polyetheramine,
Deng) with polyether hydroxyl reaction blocked.It is that not only to introduce chlorine, sulphur etc. miscellaneous using the shortcomings that leaving group method synthesizing polyether amine
Matter, and a large amount of inorganic salts are produced during product postprocessing, easily pollute environment.
(3) polyethers and acrylonitrile are carried out addition reaction by polyethers nitrile alkylation in the presence of basic catalyst first, then
Catalytic hydrogenation reaction is carried out up to polyetheramine with hydrogen in autoclave.The shortcomings that this method is of high cost, reaction raw materials propylene
Nitrile has severe toxicity.
(4) amino-butenate method uses dienone or acetoacetic ester and polyether reactant first, is carried out on polyether hydroxyl
End-blocking, then with the further amination of unary primary amine, alkyl alcoholamine or binary primary amine, obtains the polyethers that end group is amino-butenate
Amine compounds.Amido is connected with polyethers by ester bond in the polyetheramine that this method obtains, its stability is poor, it is difficult to clear in gasoline
Application in net agent.
As can be seen that although ammonolysis process synthesizing polyether amine is a kind of high-temperature high-voltage reaction, it is high to equipment requirement, catalyst
Preparation is also complex, but good product quality, high conversion rate, the environmental pollution of the synthesis of this method are few, convenient post-treatment, are mesh
The method of the synthesizing polyether amine of preceding most study, and the main method of industrialized production high activity polyether amine at present.
Patent US3128311 discloses a kind of method for preparing Armeen, and the reaction is using frame special nickel as catalysis
Agent, the fat primary amine of preparation has to be implemented compared with high selectivity, the reaction in intermittent reaction kettle.
Patent CN102336903 disclose it is a kind of in intermittent reaction kettle, using skeleton nickel as catalyst preparation polyethers
The method of amine.
Patent US3654370 discloses the preparation process and its special-purpose catalyst of a kind of polyetheramine, its catalyst is nickel,
Copper, chromium co-precipitation metallic catalyst, the reaction carry out continuous production in fixed-bed tube reactor.
Patent CN104693434 discloses a kind of method of continuity method production polyetheramine, and this method uses immobilized skeleton
Raney nickel, reacts and is carried out in multiple fixed bed type reactors.
In fixed bed reactors, continuous production is easily achieved large-scale production and production cost is low, but initially
Equipment investment is high, production equipment is complicated, technological requirement is high, it is necessary to uses the catalyst especially prepared.Short life, easy in inactivation are urged
Agent is not often suitable for fixed bed reactors.Catalyst cannot be replaced in operation, and the replacement of catalyst is led to
The closing of device often is directed not only to, and further relates to the closing of downstream treatment and finishing section.
CN103012769 discloses the continuous production that a kind of multi-stage batch reaction kettle using series connection realizes polyetheramine.
There is operate loaded down with trivial details, the postprocessing working procedures such as catalyst need to be separated by filtration for this method.
At present, ammonolysis process prepares the working condition harshness of polyetheramine, not only needs the condition of high temperature and pressure, but also it is catalyzed
The preparation of agent is also complex.Fracture commonly also, which occurs, there is polyether segment in the production technology of existing polyetheramine causes polyethers
The average molecular weight of amine reduces, and the phenomenon that molecular weight distribution broadens, this have impact on application of the polyetheramine in gasoline cleaning agent.
The content of the invention
It is proposed in the above background technology to solve it is an object of the invention to provide a kind of polyetheramine and preparation method thereof
Problem.
To achieve the above object, the present invention provides following technical solution：A kind of preparation method of polyetheramine, including following step
Suddenly：
(1) by skeletal nickel catalyst and Mg-Al composite oxide (1-5) in mass ratio:1 is loaded；
(2) polyethers, aminated compounds and hydrogen are added, carries out aminating reaction, reaction temperature is 150-250 DEG C, reaction pressure
Power is 1-20Mpa, when the reaction time is 2-5 small；The general structure of the polyethers shown in formula I, wherein, n be 0-20 it is any
Integer, m are the arbitrary integer of 1-35；R is the straight or branched alkyl of C4-C20, the alkyl phenyl of C4-C20, dialkyl phenyl organic
In one or more；
The aminated compounds is liquefied ammonia, first ammonia, second ammonia or isopropylamine；Mole of the aminated compounds and the polyethers
Than for (1-20):1；The molar ratio of the hydrogen and the polyethers is (0.5-10):1；The polyethers can be this area routine city
Available polyethers is sold, as long as its general structure is Formulas I.The polymerization methods of the segment of the polyethers can be ethylene oxide,
Propylene oxide or their atactic polymerization, homopolymerization or block polymerization；
(3) the reaction product gas-liquid separation that will be obtained in step (2), the liquid material obtained after separation is through dehydration and dehydrogenation
Mixed afterwards with aminated compounds and hydrogen and carry out aminating reaction again, reaction temperature is 150-250 DEG C, reaction pressure 5-
20Mpa, when the reaction time is 2-5 small；Wherein, the aminated compounds is consistent with being used in step (2)；The amine chemical combination
The molar ratio of thing and the polyethers is (1-30): 1；The molar ratio of the hydrogen and the polyethers is (0.5-20):1；
(4) reaction product obtained in step (3) is cooled down, after gas-liquid separation, liquid material is dehydrated and is taken off
Ammonia, that is, obtain target product polyetheramine.
In step (3) and step (4), the method and condition of the gas-liquid separation are the method and bar of this area routine
Part.By common sense in the field, the gas phase after the gas-liquid separation, is unreacted aminated compounds and hydrogen, can pass through ammonia essence
Evaporate tower and carry out recycling；The unreacted material in part passes through lights column, and ground flare is followed by by ammonia recovery unit
Incineration tail gas, to realize the no pollution in terms of environmental protection.
Preferably, for the preparation method of the polyetheramine, in step (1), the component of the skeletal nickel catalyst is pressed
It is specially according to mass percent：Nickel 80-95%, copper 4.5%-15% and lanthanum 0.5-5%, in the Mg-Al composite oxide, aluminium
Molar ratio with magnesium is (1-5):1, the mass ratio of the skeletal nickel catalyst and the Mg-Al composite oxide is preferably (2-
5):1；
Preferably, for the preparation method of the polyetheramine, in step (2), the polyethers is made by following methods：
A. initiator and strong alkali catalyst are added in pressure reaction still, with air in nitrogen displacement kettle 3 times, heating
To 110 DEG C, 30-60min is dehydrated under the following vacuum environment of -0.09MPa；
B. 120 DEG C are warming up to, is passed through ethylene oxide and propylene oxide, is 0.05-0.35MPa, temperature 120-160 in pressure
Polymerisation is carried out under the conditions of DEG C, after charging when pressure no longer declines in 30min in reaction kettle, reaction terminates, raw
Into polyethers crude product；
When reactant c. being cooled to 60-100 DEG C, it is 4.0-5.0 to add phosphoric acid and be neutralized to pH value, adds adsorbent silicic acid
Magnesium is adsorbed, then vacuum distillation dehydration, then after filtering, up to the polyethers, wherein,
The initiator is nonyl phenol, dodecylphenol, ten alcohol of isomery or isomerous tridecanol, the strong alkali catalyst
For KOH, NaOH, KOCH3、NaOCH3In one or more, the strong alkali catalyst dosage be initiator quality 0.05-
1%, the adsorbent amount is the 3-8% of the polyethers crude product weight.
Preferably, for the preparation method of the polyetheramine, in step (2), the aminated compounds and the polyethers
Molar ratio for be preferably (1-10):1, the molar ratio of the hydrogen and the polyethers is preferably (1-5):1.
Preferably, for the preparation method of the polyetheramine, in step (2), the reaction temperature is preferably 180-240
DEG C, the reaction pressure is preferably 5-15MPa.
Preferably, for the preparation method of the polyetheramine, in step (3), the aminated compounds and the polyethers
Molar ratio be preferably (5-15):1, the molar ratio of the hydrogen and the polyethers is preferably (5-15):1.
Preferably, for the preparation method of the polyetheramine, in step (3), the reaction temperature is preferably 180-240
DEG C, the reaction pressure is preferably 5-15MPa.
Preferably, for the preparation method of the polyetheramine, in step (3) and step (4), the dehydration and deamination are equal
Carried out in evaporator, the evaporator can be shell and tube evaporator or scraper film evaporator.
Preferably, for the preparation method of the polyetheramine, in step (4), the target temperature of the cooling is 140-
160 DEG C, be preferably 150 DEG C.
A kind of polyetheramine obtained by preparation method of polyetheramine as mentioned, it is characterised in that the knot of the polyetheramine
Structure general formula as shown in Formula II, wherein, n be 0-20 arbitrary integer, m be 1-35 arbitrary integer, R1For C4-C20 straight chain or
One or more in branched alkyl, the alkyl phenyl of C4-C20, dialkyl phenyl organic, R2For hydrogen, methyl, ethyl or isopropyl,
The molecular weight of the polyetheramine is 200-3000.In the polyetheramine, the polymerization methods of polyether segment can be ethylene oxide,
Propylene oxide or their atactic polymerization, homopolymerization or block polymerization.
Compared with prior art, the beneficial effects of the invention are as follows：
The required pressure of ammonolysis reaction and temperature are low in the preparation method of the present invention, and side reaction is few, and ammonification rate is high, primary amine
High selectivity, reaction conversion ratio >=98%, primary amine selectivity >=96%, obtained polyetheramine narrow molecular weight distribution.The present invention
Processing step is simple, complex catalyst system, effectively increases catalytic activity, and reduce the shadow that water is generated in reaction by being dehydrated
Ring, improve ammonification conversion ratio, reduce the phenomenon of polyethers fracture.
Embodiment
Below in conjunction with specific embodiment, the invention will be further described, in order to which those skilled in the art can be more
Good understanding is of the invention and can be practiced, but cited embodiment is not as limiting to the invention.
In following embodiments, hydroxy value measuring method：With reference to GB/T 12008.3-2009, and extrapolate molecular weight.
Total amine value measurement：Product is titrated using the hydrochloric acid solution of 0.5mol/L, passes through the hydrochloric acid body of consumption
Product can calculate total amine value of product.
Ammonification conversion ratio=total amine value/hydroxyl value × 100%
Secondary/tertiary amine values determination method：By product with etc. quality salicylide be mixed 2h after, using 0.5 mol/L's
Hydrochloric acid solution titrates product, and the sum of secondary amine and the tertiary amine value of product can be calculated by the hydrochloric acid volume number of consumption.
Primary amine selectivity=(total amine value-secondary/tertiary amine value)/total amine value × 100%.
In following embodiments, if without specializing, number used is parts by weight.
Embodiment 1
A) the preparation of polyethers
In pressure reaction still, 100 parts of nonyl phenols and the KOH of nonyl phenol weight 0.2% are added, with sky in nitrogen displacement kettle
Gas 3 times, is warming up to 110 DEG C, is dehydrated 30min under the following vacuum environment of -0.09MPa, then heats to 120 DEG C, slowly logical
Enter propylene oxide, the molar ratio of propylene oxide and nonyl phenol is 17：1, it is 0.25MPa in pressure, is carried out under the conditions of 130 DEG C of temperature
Polymerisation, after charging when pressure no longer declines in 30min in reaction kettle, reaction terminates, and generates polyethers crude product；Will
When reactant is cooled to 90 DEG C, the phosphoric acid for adding 85wt% is neutralized to pH value as 4.0, adds adsorbent magnesium silicate and is adsorbed,
Then vacuum distillation dehydration, obtains refined polyethers after filtering.After chemical analysis, the molecular weight of refined polyethers is measured, as a result
It is listed in table 1.
B) the preparation of polyetheramine
(1) by weight 2 in the reaction kettle with outer circulation and evaporator:1 is packed into skeletal nickel catalyst and magnalium
Composite oxides co-catalyst, the composition of skeletal nickel catalyst are：80wt% nickel, 15wt% copper, 5wt% lanthanums, Mg-Al composite oxygen
Aluminium/magnesium mass ratio is 1 in compound；
(2) add step A in a kettle) made from 100 parts of polyethers, liquefied ammonia and hydrogen, the molar ratio of liquefied ammonia and polyethers
For 3：1, the molar ratio of hydrogen and polyethers is 4：1, aminating reaction is carried out under 180 DEG C of reaction temperature, reaction pressure 13MPa, instead
Between seasonable 3 it is small when；
(3) reactant is after gas-liquid separation, and liquid material is returned in reaction kettle after evaporator dehydration and deamination, weight
The molar ratio of new addition liquefied ammonia and hydrogen, liquefied ammonia and polyethers is 10：1, the molar ratio of hydrogen and polyethers is 5：1, in reaction temperature
240 DEG C, continue aminating reaction under reaction pressure 5MPa, when the reaction time 2 is small；
(4) after reaction, reaction system is cooled to 150 DEG C, and reactant is after gas-liquid separation, and liquid material is through pervaporation
Device is dehydrated with after deamination, that is, polyetheramine is made.
By chemical analysis, the ammonification conversion ratio and primary amine value of product are measured；Product is characterized by GPC exclusion chromatographies
Molecular weight distribution, the results are shown in table 1.
Embodiment 2
A) the preparation of polyethers
In pressure reaction still, 100 parts of dodecylphenols and the NaOH of dodecylphenol weight 0.3% are added, use nitrogen
Air 3 times in kettle are replaced, 110 DEG C is warming up to, is dehydrated 40min under the following vacuum environment of -0.09MPa, then heats to 120
DEG C, it is slowly introducing propylene oxide, the molar ratio of propylene oxide and dodecylphenol is 20：1, it is 0.35MPa in pressure, temperature
Polymerisation is carried out under the conditions of 140 DEG C, after charging when pressure no longer declines in 30min in reaction kettle, reaction terminates,
Generate polyethers crude product；When reactant is cooled to 90 DEG C, the phosphoric acid for adding 85wt% is neutralized to pH value as 5.0, adds adsorbent
Magnesium silicate is adsorbed, then vacuum distillation dehydration, and refined polyethers is obtained after filtering.After chemical analysis, measure refined poly-
The molecular weight of ether, the results are shown in table 1.
B) the preparation of polyetheramine
(1) by weight 3 in the reaction kettle with outer circulation and evaporator:1 is packed into skeletal nickel catalyst and magnalium
Composite oxides co-catalyst, the composition of skeletal nickel catalyst are：90wt% nickel, 8wt% copper, 2wt% lanthanums, Mg-Al composite oxygen
Aluminium/magnesium mass ratio is 3 in compound；
(2) add step A in a kettle) made from 100 parts of polyethers, liquefied ammonia and hydrogen, the molar ratio of liquefied ammonia and polyethers
For 5：1, the molar ratio of hydrogen and polyethers is 4：1, aminating reaction is carried out under 210 DEG C of reaction temperature, reaction pressure 14MPa, instead
Between seasonable 5 it is small when；
(3) reactant is after gas-liquid separation, and liquid material is returned in reaction kettle after evaporator dehydration and deamination, weight
The molar ratio of new addition liquefied ammonia and hydrogen, liquefied ammonia and polyethers is 10：1, the molar ratio of hydrogen and polyethers is 10：1, in reaction temperature
210 DEG C, continue aminating reaction under reaction pressure 10MPa, when the reaction time 4 is small；
(4) after reaction, reaction system is cooled to 140 DEG C, and reactant is after gas-liquid separation, and liquid material is through pervaporation
Device is dehydrated with after deamination, that is, polyetheramine is made.
By chemical analysis, the ammonification conversion ratio and primary amine value of product are measured；Product is characterized by GPC exclusion chromatographies
Molecular weight distribution, the results are shown in table 1.
Embodiment 3
A) the preparation of polyethers
In pressure reaction still, 100 parts of isomerous tridecanols and the NaOCH of isomerous tridecanol weight 0.25% are added3, use
Air 3 times in nitrogen displacement kettle, are warming up to 110 DEG C, are dehydrated 50min under the following vacuum environment of -0.09MPa, then heat up
To 120 DEG C, propylene oxide is slowly introducing, the molar ratio of propylene oxide and isomerous tridecanol is 24：1, it is 0.25MPa in pressure,
Polymerisation is carried out under the conditions of 145 DEG C of temperature, after charging when pressure no longer declines in 30min in reaction kettle, reaction
Terminate, generate polyethers crude product；When reactant is cooled to 80 DEG C, the phosphoric acid for adding 85wt% is neutralized to pH value as 4.5, adds and inhales
Attached dose of magnesium silicate is adsorbed, then vacuum distillation dehydration, and refined polyethers is obtained after filtering.After chemical analysis, essence is measured
The molecular weight of polyethers processed, the results are shown in table 1.
B) the preparation of polyetheramine
(1) by weight 5 in the reaction kettle with outer circulation and evaporator:1 is packed into skeletal nickel catalyst and magnalium
Composite oxides co-catalyst, the composition of skeletal nickel catalyst are：95wt% nickel, 4.5wt% copper, 0.5wt% lanthanums, Mg-Al composite
Aluminium/magnesium mass ratio is 5 in oxide；
(2) add step A in a kettle) made from 100 parts of polyethers, liquefied ammonia and hydrogen, the molar ratio of liquefied ammonia and polyethers
For 8：1, the molar ratio of hydrogen and polyethers is 4：1, aminating reaction is carried out under 240 DEG C of reaction temperature, reaction pressure 15MPa, instead
Answer time 2 h；
(3) reactant is after gas-liquid separation, and liquid material is returned in reaction kettle after evaporator dehydration and deamination, weight
The molar ratio of new addition liquefied ammonia and hydrogen, liquefied ammonia and polyethers is 10：1, the molar ratio of hydrogen and polyethers is 15：1, in reaction temperature
180 DEG C, continue aminating reaction under reaction pressure 15MPa, when the reaction time 5 is small；
(4) after reaction, reaction system is cooled to 150 DEG C, and reactant is after gas-liquid separation, and liquid material is through pervaporation
Device is dehydrated with after deamination, that is, polyetheramine is made.
By chemical analysis, the ammonification conversion ratio and primary amine value of product are measured；Product is characterized by GPC exclusion chromatographies
Molecular weight distribution, the results are shown in table 1.
Embodiment 4
A) the preparation of polyethers
In pressure reaction still, the KOCH of ten alcohol weight 0.4% of 100 parts of ten alcohol of isomery and isomery is added3, use nitrogen displacement
Air 3 times in kettle, are warming up to 110 DEG C, are dehydrated 50min under the following vacuum environment of -0.09MPa, then heat to 120 DEG C,
It is slowly introducing ethylene oxide and propylene oxide, the molar ratio of ethylene oxide and ten alcohol of isomery is 10：1, propylene oxide and isomery ten
The molar ratio of alcohol is 25：1, it is 0.25MPa in pressure, atactic polymerization reaction is carried out under the conditions of 145 DEG C of temperature, after charging
When pressure no longer declines in 30min in reaction kettle, reaction terminates, and generates polyethers crude product；When reactant is cooled to 90 DEG C,
It is 4.0 that the phosphoric acid of addition 85wt%, which is neutralized to pH value, adds adsorbent magnesium silicate and is adsorbed, then vacuum distillation dehydration, mistake
Refined polyethers is obtained after filter.After chemical analysis, the molecular weight of refined polyethers is measured, the results are shown in table 1.
B) the preparation of polyetheramine
(1) by weight 4 in the reaction kettle with outer circulation and evaporator:1 is packed into skeletal nickel catalyst and magnalium
Composite oxides co-catalyst, the composition of skeletal nickel catalyst are：90wt% nickel, 8wt% copper, 2wt% lanthanums, Mg-Al composite oxygen
Aluminium/magnesium mass ratio is 3 in compound；
(2) add step A in a kettle) made from 100 parts of polyethers, liquefied ammonia and hydrogen, the molar ratio of liquefied ammonia and polyethers
For 5：1, the molar ratio of hydrogen and polyethers is 2：1, aminating reaction is carried out under 230 DEG C of reaction temperature, reaction pressure 10MPa, instead
Answer time 2 h；
(3) reactant is after gas-liquid separation, and liquid material is returned in reaction kettle after evaporator dehydration and deamination, weight
The molar ratio of new addition liquefied ammonia and hydrogen, liquefied ammonia and polyethers is 5：1, the molar ratio of hydrogen and polyethers is 10：1, in reaction temperature
230 DEG C, continue aminating reaction under reaction pressure 14MPa, when the reaction time 3 is small；
(4) after reaction, reaction system is cooled to 160 DEG C, and reactant is after gas-liquid separation, and liquid material is through pervaporation
Device is dehydrated with after deamination, that is, polyetheramine is made.
By chemical analysis, the ammonification conversion ratio and primary amine value of product are measured；Product is characterized by GPC exclusion chromatographies
Molecular weight distribution, the results are shown in table 1.
Embodiment 5
A) the preparation of polyethers
In pressure reaction still, 100 parts of nonyl phenols and the KOH of nonyl phenol weight 0.5% are added, with sky in nitrogen displacement kettle
Gas 3 times, is warming up to 110 DEG C, and 50min is dehydrated under vacuum environment under -0.09MPa, then heats to 120 DEG C, is slowly introducing
The molar ratio of ethylene oxide, ethylene oxide and nonyl phenol is 5：1, it is 0.25MPa in pressure, is gathered under the conditions of 130 DEG C of temperature
Reaction is closed, after charging when pressure no longer declines in 30min in reaction kettle, is slowly introducing propylene oxide, propylene oxide
Molar ratio with nonyl phenol is 15：1, it is 0.25MPa in pressure, polymerisation is carried out under the conditions of 130 DEG C of temperature, after charging
When pressure no longer declines in 30min in reaction kettle.Reaction terminates, and generates polyethers crude product；When reactant is cooled to 95 DEG C,
It is 5.0 that the phosphoric acid of addition 85wt%, which is neutralized to pH value, adds adsorbent magnesium silicate and is adsorbed, then vacuum distillation dehydration, mistake
Refined polyethers is obtained after filter.After chemical analysis, the molecular weight of refined polyethers is measured, the results are shown in table 1.
B) the preparation of polyetheramine
(1) by weight 4 in the reaction kettle with outer circulation and evaporator:1 is packed into skeletal nickel catalyst and magnalium
Composite oxides co-catalyst, the composition of skeletal nickel catalyst are：90wt% nickel, 8wt% copper, 2wt% lanthanums, Mg-Al composite oxygen
Aluminium/magnesium mass ratio is 3 in compound；
(2) add step A in a kettle) made from 100 parts of polyethers, liquefied ammonia and hydrogen, the molar ratio of liquefied ammonia and polyethers
For 5：1, the molar ratio of hydrogen and polyethers is 4：1, aminating reaction is carried out under 230 DEG C of reaction temperature, reaction pressure 13MPa, instead
Between seasonable 4 it is small when；
(3) reactant is after gas-liquid separation, and liquid material is returned in reaction kettle after evaporator dehydration and deamination, weight
The molar ratio of new addition liquefied ammonia and hydrogen, liquefied ammonia and polyethers is 10：1, the molar ratio of hydrogen and polyethers is 10：1, in reaction temperature
230 DEG C, continue aminating reaction under reaction pressure 14MPa, when the reaction time 5 is small；
(4) after reaction, reaction system is cooled to 150 DEG C, and reactant is after gas-liquid separation, and liquid material is through pervaporation
Device is dehydrated with after deamination, that is, polyetheramine is made.
By chemical analysis, the ammonification conversion ratio and primary amine value of product are measured；Product is characterized by GPC exclusion chromatographies
Molecular weight distribution, the results are shown in table 1.
Embodiment 6
A) the preparation of polyethers
In pressure reaction still, 100 parts of nonyl phenols and the KOH of nonyl phenol weight 0.2% are added, with sky in nitrogen displacement kettle
Gas 3 times, is warming up to 110 DEG C, is dehydrated 30min under the following vacuum environment of -0.09MPa, then heats to 120 DEG C, slowly logical
Enter propylene oxide, the molar ratio of propylene oxide and nonyl phenol is 10：1, it is 0.25MPa in pressure, is carried out under the conditions of 120 DEG C of temperature
Polymerisation, after charging when pressure no longer declines in 30min in reaction kettle, reaction terminates, and generates polyethers crude product；Will
When reactant is cooled to 90 DEG C, the phosphoric acid for adding 85wt% is neutralized to pH value as 4.5, adds adsorbent magnesium silicate and is adsorbed,
Then vacuum distillation dehydration, obtains refined polyethers after filtering.After chemical analysis, the molecular weight of refined polyethers is measured, as a result
It is listed in table 1.
B) the preparation of polyetheramine
(1) by weight 4 in the reaction kettle with outer circulation and evaporator:1 is packed into skeletal nickel catalyst and magnalium
Composite oxides co-catalyst, the composition of skeletal nickel catalyst are：90wt% nickel, 8wt% copper, 2wt% lanthanums, Mg-Al composite oxygen
Aluminium/magnesium mass ratio is 3 in compound；
(2) add step A in a kettle) made from 100 parts of polyethers, liquefied ammonia and hydrogen, the molar ratio of liquefied ammonia and polyethers
For 5：1, the molar ratio of hydrogen and polyethers is 6：1, aminating reaction is carried out under 230 DEG C of reaction temperature, reaction pressure 14MPa, instead
Between seasonable 4 it is small when；
(3) reactant is after gas-liquid separation, and liquid material is returned in reaction kettle after evaporator dehydration and deamination, weight
The molar ratio of new addition liquefied ammonia and hydrogen, liquefied ammonia and polyethers is 15：1, the molar ratio of hydrogen and polyethers is 10：1, in reaction temperature
230 DEG C, continue aminating reaction under reaction pressure 14MPa, when the reaction time 4 is small；
(4) after reaction, reaction system is cooled to 150 DEG C, and reactant is after gas-liquid separation, and liquid material is through pervaporation
Device is dehydrated with after deamination, that is, polyetheramine is made.
By chemical analysis, the ammonification conversion ratio and primary amine value of product are measured；Product is characterized by GPC exclusion chromatographies
Molecular weight distribution, the results are shown in table 1.
Comparative example 1
A) preparation method of polyethers is the same as embodiment 6.
B) the preparation of polyetheramine
(1) by weight 4 in the reaction kettle with outer circulation and evaporator:1 is packed into skeletal nickel catalyst and magnalium
Composite oxides co-catalyst, the composition of skeletal nickel catalyst are：90wt% nickel, 8wt% copper, 2wt% lanthanums, Mg-Al composite oxidation
Aluminium/magnesium mass ratio is 3 in thing；
(2) add step A in a kettle) made from 100 parts of polyethers, liquefied ammonia and hydrogen, the molar ratio of liquefied ammonia and polyethers
For 15：1, the molar ratio of hydrogen and polyethers is 10：1, aminating reaction is carried out under 230 DEG C of reaction temperature, reaction pressure 14MPa,
When reaction time 8 is small；
(3) after reaction, reaction system is cooled to 150 DEG C, and reactant is after gas-liquid separation, and liquid material is through pervaporation
Device is dehydrated with after deamination, that is, polyetheramine is made.
By chemical analysis, the ammonification conversion ratio and primary amine value of product are measured；Product is characterized by GPC exclusion chromatographies
Molecular weight distribution, the results are shown in table 1.
Comparative example 2
A) preparation method of polyethers is the same as embodiment 6.
B) the preparation of polyetheramine
(1) skeletal nickel catalyst, the group of skeletal nickel catalyst are packed into the reaction kettle with outer circulation and evaporator
Become：90wt% nickel, 8wt% copper, 2wt% lanthanums；
(2) add step A in a kettle) made from 100 parts of polyethers, liquefied ammonia and hydrogen, the molar ratio of liquefied ammonia and polyethers
For 5：1, the molar ratio of hydrogen and polyethers is 6：1, aminating reaction is carried out under 230 DEG C of reaction temperature, reaction pressure 14MPa, instead
Between seasonable 4 it is small when；
(3) reactant is after gas-liquid separation, and liquid material is returned in reaction kettle after evaporator dehydration and deamination, weight
The molar ratio of new addition liquefied ammonia and hydrogen, liquefied ammonia and polyethers is 15：1, the molar ratio of hydrogen and polyethers is 10：1, in reaction temperature
230 DEG C, continue aminating reaction under reaction pressure 14MPa, when the reaction time 4 is small；
(4) after reaction, reaction system is cooled to 150 DEG C, and reactant is after gas-liquid separation, and liquid material is through pervaporation
Device is dehydrated with after deamination, that is, polyetheramine is made.
By chemical analysis, the ammonification conversion ratio and primary amine value of product are measured；Product is characterized by GPC exclusion chromatographies
Molecular weight distribution, the results are shown in table 1.
Comparative example 3
A) preparation method of polyethers is the same as embodiment 6.
B) the preparation of polyetheramine
(1) skeletal nickel catalyst, the group of skeletal nickel catalyst are packed into the reaction kettle with outer circulation and evaporator
Become：90wt% nickel, 8wt% copper, 2wt% lanthanums；
(2) add step A in a kettle) made from 100 parts of polyethers, liquefied ammonia and hydrogen, the molar ratio of liquefied ammonia and polyethers
For 15：1, the molar ratio of hydrogen and polyethers is 10：1, aminating reaction is carried out under 230 DEG C of reaction temperature, reaction pressure 14MPa,
When reaction time 8 is small；
(3) after reaction, reaction system is cooled to 150 DEG C, and reactant is after gas-liquid separation, and liquid material is through pervaporation
Device is dehydrated with after deamination, that is, polyetheramine is made.
By chemical analysis, the ammonification conversion ratio and primary amine value of product are measured；Product is characterized by GPC exclusion chromatographies
Molecular weight distribution, the results are shown in table 1.
As it can be seen from table 1 with regard to embodiment 6, the comparative example 1,2 and 3 prepared using same polyethers sample and
Speech, the conversion ratio and primary amine rate of the sample of embodiment 6 are above comparative example, also, point of the polyetheramine obtained by embodiment 6
Son amount distribution is most narrow, and the decline degree of polyetheramine molecular weight is minimum.As it can be seen that the preparation method of the present invention, employs composite catalyzing
Agent and segmentation Amination Technique, not only amination conversion ratio and primary amine rate are high, but also segment fracture rate substantially reduces, obtained polyethers
Amine molecule amount narrowly distributing.
The sample data of 1 each embodiment of table and comparative example
Effect example
The cleansing performance of polyetheramine is evaluated according to GB/T 19592-2004《Vehicle use gasoline cleansing agent》Appendix B nominative testing
Method carries out.
Polyetheramine made from each embodiment and comparative example and 500SN mineral oils are modulated into gasoline cleaning agent sample,
Wherein polyetheramine accounting 30wt%.Then the gasoline cleaning agent sample of needs assessment is added to composition experiment vapour in base gasoline
The addition of oil, wherein gasoline cleaning agent is 400ppm.
Assessing terms：80 ± 1kPa of air pressure, 700 ± 10L/h of air mass flow, fuel pressure 7.0-8.0 kPa, gasoline
Stability of flow is kept for 173 DEG C in 30-35%, aluminum sediment trap temperature, 70 min of time.
Polyetheramine obtained by selection example 5,6 and comparative example 2,3 carries out simulated experiment for sample, to the clear of polyetheramine
Net performance is evaluated, and the results are shown in table 2.
From table 2 it can be seen that in addition to polyetheramine molecular weight has a direct impact cleansing performance, the molecular weight distribution of polyetheramine
Also there is important influence to cleansing performance.The peace and quiet effect of the polyetheramine prepared using the present invention is far superior to comparative example.
The influence that 2 polyetheramine of table generates deposit is compared
| Additive types | Sediment quality/mg | Deposit slip/% |
| Blank | 13.6 | / |
| Embodiment 5 | 0.7 | 94.8 |
| Embodiment 6 | 1.2 | 91.2 |
| Comparative example 2 | 2.8 | 79.4 |
| Comparative example 3 | 3.6 | 73.5 |
Embodiment described above is only that protection scope of the present invention is not to absolutely prove the preferred embodiment of the invention lifted
It is limited to this.The equivalent substitute or conversion that those skilled in the art are made on the basis of the present invention, the present invention's
Within protection domain.Protection scope of the present invention is subject to claims.
Claims (10)
1. a kind of preparation method of polyetheramine, it is characterised in that comprise the following steps：
(1) by skeletal nickel catalyst and Mg-Al composite oxide (1-5) in mass ratio:1 is loaded；
(2) polyethers, aminated compounds and hydrogen are added, carries out aminating reaction, reaction temperature is 150-250 DEG C, and reaction pressure is
1-20Mpa, when the reaction time is 2-5 small；The general structure of the polyethers shown in formula I, wherein, n be 0-20 arbitrary integer,
M is the arbitrary integer of 1-35；R is one in the straight or branched alkyl of C4-C20, the alkyl phenyl of C4-C20, dialkyl phenyl organic
Kind is a variety of；
The aminated compounds is liquefied ammonia, first ammonia, second ammonia or isopropylamine；The molar ratio of the aminated compounds and the polyethers is
(1-20):1；The molar ratio of the hydrogen and the polyethers is (0.5-10):1；
(3) the reaction product gas-liquid separation that will be obtained in step (2), the liquid material obtained after separation through be dehydrated and dehydrogenation after and
Aminated compounds and hydrogen mixing carry out aminating reaction again, and reaction temperature is 150-250 DEG C, reaction pressure 5-20Mpa, instead
When being 2-5 small between seasonable；Wherein, the aminated compounds is consistent with being used in step (2)；The aminated compounds with it is described
The molar ratio of polyethers is (1-30):1；The molar ratio of the hydrogen and the polyethers is (0.5-20):1；
(4) reaction product obtained in step (3) is cooled down, after gas-liquid separation, liquid material is dehydrated and deamination, i.e.,
Obtain target product polyetheramine.
2. the preparation method of polyetheramine as claimed in claim 1, it is characterised in that in step (1), the skeletal nickel catalyst
Component be specially according to mass percent：Nickel 80-95%, copper 4.5%-15% and lanthanum 0.5-5%, the Mg-Al composite oxidation
In thing, the molar ratio of aluminium and magnesium is (1-5):1, the mass ratio of the skeletal nickel catalyst and the Mg-Al composite oxide is preferred
For (2-5):1.
3. the preparation method of polyetheramine as claimed in claim 1, it is characterised in that in step (2), the polyethers is by following sides
Method is made：
A. initiator and strong alkali catalyst are added in pressure reaction still, with air in nitrogen displacement kettle 3 times, is warming up to 110
DEG C, it is dehydrated 30-60min under the following vacuum environment of -0.09MPa；
B. 120 DEG C are warming up to, is passed through ethylene oxide and propylene oxide, is 0.05-0.35MPa in pressure, 120-160 DEG C of bar of temperature
Polymerisation is carried out under part, after charging when pressure no longer declines in 30min in reaction kettle, reaction terminates, and generation is poly-
Ether crude product；
When reactant c. being cooled to 60-100 DEG C, adding phosphoric acid, to be neutralized to pH value be 4.0-5.0, addition adsorbent magnesium silicate into
Row absorption, then vacuum distillation dehydration, then after filtering, up to the polyethers, wherein,
The initiator is nonyl phenol, dodecylphenol, ten alcohol of isomery or isomerous tridecanol, the strong alkali catalyst are
KOH、NaOH、KOCH3、NaOCH3In one or more, the strong alkali catalyst dosage be initiator quality 0.05-
1%, the adsorbent amount is the 3-8% of the polyethers crude product weight.
4. the preparation method of polyetheramine as claimed in claim 1, it is characterised in that in step (2), the aminated compounds with
The molar ratio of the polyethers is preferably (1-10):1, the molar ratio of the hydrogen and the polyethers is preferably (1-5):1.
5. the preparation method of polyetheramine as claimed in claim 1, it is characterised in that in step (2), the reaction temperature is preferred
For 180-240 DEG C, the reaction pressure is preferably 5-15MPa.
6. the preparation method of polyetheramine as claimed in claim 1, it is characterised in that in step (3), the aminated compounds with
The molar ratio of the polyethers is preferably (5-15):1, the molar ratio of the hydrogen and the polyethers is preferably (5-15):1.
7. the preparation method of polyetheramine as claimed in claim 1, it is characterised in that in step (3), the reaction temperature is preferred
For 180-240 DEG C, the reaction pressure is preferably 5-15MPa.
8. the preparation method of polyetheramine as claimed in claim 1, it is characterised in that described de- in step (3) and step (4)
Water and deamination are carrying out in evaporator.
9. the preparation method of polyetheramine as claimed in claim 1, it is characterised in that in step (4), the target temperature of the cooling
Spend for 140-160 DEG C.
10. the polyetheramine obtained by a kind of preparation method of polyetheramine as described in claim 1-9, it is characterised in that described
The general structure of polyetheramine as shown in Formula II, wherein, n be 0-20 arbitrary integer, m be 1-35 arbitrary integer, R1For C4-
One or more in the straight or branched alkyl of C20, the alkyl phenyl of C4-C20, dialkyl phenyl organic, R2For hydrogen, methyl, second
Base or isopropyl, the molecular weight of the polyetheramine is 200-3000.In the polyetheramine, the polymerization methods of polyether segment can be
Ethylene oxide, propylene oxide or their atactic polymerization, homopolymerization or block polymerization.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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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 |
| CN109627149A (en) * | 2018-12-14 | 2019-04-16 | 药大制药有限公司 | A method of preparing the nonoxinol without ethylene oxide |
| CN111440308A (en) * | 2020-04-29 | 2020-07-24 | 浙江皇马科技股份有限公司 | Polyether amine synthesis process for gasoline detergent |
| CN112521595A (en) * | 2020-12-04 | 2021-03-19 | 淄博正大聚氨酯有限公司 | Synthetic method for preparing amino-terminated polyether polyol through hydrogen catalytic amination |
| CN114437334A (en) * | 2020-10-20 | 2022-05-06 | 中国石油化工股份有限公司 | Polyether amine compound and preparation method and application thereof |
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2017
- 2017-08-03 CN CN201710655283.7A patent/CN108017782A/en active Pending
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109627149A (en) * | 2018-12-14 | 2019-04-16 | 药大制药有限公司 | A method of preparing the nonoxinol without ethylene oxide |
| 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 |
| 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 |
| CN111440308A (en) * | 2020-04-29 | 2020-07-24 | 浙江皇马科技股份有限公司 | Polyether amine synthesis process for gasoline detergent |
| CN111440308B (en) * | 2020-04-29 | 2023-04-14 | 浙江皇马科技股份有限公司 | Polyether amine synthesis process for gasoline detergent |
| CN114437334A (en) * | 2020-10-20 | 2022-05-06 | 中国石油化工股份有限公司 | Polyether amine compound and preparation method and application thereof |
| CN114437334B (en) * | 2020-10-20 | 2023-07-14 | 中国石油化工股份有限公司 | Polyether amine compound, preparation method and application thereof |
| CN112521595A (en) * | 2020-12-04 | 2021-03-19 | 淄博正大聚氨酯有限公司 | Synthetic method for preparing amino-terminated polyether polyol through hydrogen catalytic amination |
| CN112521595B (en) * | 2020-12-04 | 2022-08-12 | 淄博正大聚氨酯有限公司 | Synthetic method for preparing amino-terminated polyether polyol through hydrogen catalytic amination |
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