CN103613506A - Preparation method of bis(fatty alcohol polyoxyalkene ether) secondary amine - Google Patents
Preparation method of bis(fatty alcohol polyoxyalkene ether) secondary amine Download PDFInfo
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Abstract
The invention discloses a preparation method of bis(fatty alcohol polyoxyalkene ether) secondary amine, belonging to the technical field of organic chemical industry. The method comprises the following step of: preparing the bis(fatty alcohol polyoxyalkene ether) secondary amine through condensation-deamination coupling reaction of two-molecule primary amine under normal-pressure condition by taking primary amine-terminated fatty alcohol polyoxyalkene ether as a raw material and taking raney nickel as a catalyst. Ammoniation rate of the primary amine-terminated fatty alcohol polyoxyalkene ether is 40%-100%; dosage of the catalyst is 0-20% of the mass of the primary amine-terminated fatty alcohol polyoxyalkene ether; hydrogen gas flow velocity is 0 ml/minute-1000ml/minute for every 100g of the primary amine-terminated fatty alcohol polyoxyalkene ether; reaction temperature is 150 DEG C-250 DEG C; reaction time is 2 hours-20 hours. According to the preparation method disclosed by the invention, on the condition of improving content of secondary amine, process flow is simplified, and cost is lowered, so that the preparation method can be used for large-scale production in the industrial field.
Description
Technical field
The preparation method who the present invention relates to a kind of two (fatty alcohol polyoxy alkane alkene ether) secondary amine, belongs to field of chemical technology.
Background technology
Amidogen ether compounds (etheramine) is in molecule, to have the compound of amido and ehter bond simultaneously, and its special construction has determined that it has unique performance.Therefore as a class Functional Chemicals, amidogen ether compounds plays an important role in a plurality of fields such as chemical industry, medicine, over nearly 30 years, amidogen ether is that huge contribution has been made in the development of global chemical industry, especially the polyetheramine (polyetheramine) in this compounds, is widely used in a plurality of fields of epoxy material, concrete additive, pigment dyestuff, fuel, lubricating oil additive, plastics, medical material, matrix material, weedicide and agrochemical.
The report of comprehensive at present relevant Amino Terminated polyether(ATPE) synthetic method, its Research Thinking mainly contains two kinds:
The first is set about from the terminal hydroxyl of polyether glycol, by ammonolysis reaction ammonia (amine) base, replaces its terminal hydroxyl, and this is also the synthetic main method of current Amino Terminated polyether(ATPE) industry;
From the reactive hydrogen of polyether glycol terminal hydroxyl, set about in addition, use with easy leavings group or unsaturated group (NCO ,-NO
2,-CN etc.) end-blocking is carried out in compound and reactive hydrogen effect, and then by obtaining Amino Terminated polyether(ATPE) after corresponding processing, these class methods comprise hydrolysis method, leavings group method, ammonia phenoxy group method, amino-butenate method, ω-cyanoalkyl method etc.
US Patent No. 2888439 proposes, by amine and the polyether reactant that contains leavings group (leaving groups), can obtain ATPE, and cost to be lower.Its step is first by polyether glycol and phosgene reaction, introduces chloroformate group at polyethers two ends, then with diamine, reacts with polyethers chloro-formic ester.The mol ratio of amido and chloroformate group is 3, just can obtain the ATPE being connected by amino-formate bond that viscosity pole is low.Excessive diamine can be used as the absorption agent of HCl.
It is worthy of note, in the forming process of the first step chloro-formic ester, likely exist the nucleophilic substitution side reaction of hydroxyl and chlorine, while particularly containing dimethyl formamide (DMF) in reactant, side reaction will become main reaction and generate end chloro alkyl, polyether.
Under HCl absorption agent exists, end chloro alkyl, polyether can react with aliphatic unary primary amine, obtains the polyethers by secondary amine end-blocking.
Somebody found afterwards, and methylsulfonyl group is than the more effective leavings group of chlorine, utilize methylsulfonyl chloride can easily methylsulfonyl be introduced to the two ends of polyethers, and the nucleophilic substitution reaction of methylsulfonyl group and amine also can carry out well.Document polyoxytrimethylene polyamines synthetic, characterize and the toughening effect of epoxy resin barked Polyoxypropylene diol, tetrahydrochysene to be muttered and Tosyl chloride drops in four-hole boiling flask, after stirring and dissolving, splash into pyridine.Stirring reaction 24h when lower than 30 ℃, obtains two sulfonylation polyethers.Then under nitrogen protection, two sulfonylation polyethers are splashed in the four-hole boiling flask that includes quadrol and toluene, at 110 ℃, carry out aminolysis reaction, obtain lurid polyoxytrimethylene polyamines.
Chinese patent CN1092786 propose to take end hydroxy polyether as raw material through over-churning, amination reaction the Amino Terminated polyether(ATPE) for the preparation of urethane and epoxy resin.In its patent, first end hydroxy polyether is reacted with Acetyl Chloride 98Min., phenmethyl chlorine or Butyltriphenylphosphonium chloride and generate corresponding ester, then the ester of producing is reacted with primary amine, quadrol or trientine etc., generate corresponding Amino Terminated polyether(ATPE).
Step of esterification is used the polyethers of polyether glycol and the synthetic end of halogenating agent reaction chlorine, then adds ammoniation agent to carry out ammonification.The study on the synthesis of document W Amino Polyoxyalkylene reacts and obtains after the polyoxyethylene glycol of bromo in tetracol phenixin liquid with phosphorus tribromide, heats the synthetic ATPE of ammonification in strong aqua, and by Infrared spectroscopy, determines the ammonification degree of polyoxyethylene glycol.
The people such as Rasschover of nineteen eighty-two Bayer company have proposed the TDI prepolymer of polyethers or polyester polyol by reacting with alkaline aqueous solution, generate containing carbamic intermediate, and then obtain the method for aminocompound.The key of this method is that the first step reaction must carry out under low temperature (18-20 ℃), and to guarantee carbamic whole formation, second step, by rising temperature, makes to hold carboxylamine group to decompose, and forms amino, and discharges C02.
US Patent No. 5091582 has proposed the method for ammonia phenoxy group (aminophenooy) legal system ATPE.Chloronitrobenzene is under the effect of highly basic (as NaOH powder) and polar solvent (as dimethyl sulfoxide (DMSO)), react with polyether glycol, obtain polyethers by the intermediate product of nitre phenoxy group end-blocking, and then by hydrogenation reaction, make nitre phenoxy compounds be reduced to phenalgin oxycompound.
US Patent No. 3691112 proposes to utilize amino-butenate (aminocrotonates) legal system for ATPE, can select very neatly the amino kind at polyethers two ends.First use dienone (diketen) or by the transesterification reaction of methyl aceto acetate and polyether glycol, two ends at polyethers connect acetoacetate groups, then will be carried out amination by the polyethers of acetoacetate groups end-blocking and unary primary amine, alkyl alcoholamine or binary primary amine, obtaining end group is the group with imine moiety that amino-butenate, viscosity are very low.
US Patent No. 4061678 use polyether glycols carry out addition reaction with propylene cyanogen, then product hydrogenating reduction is obtained to Amino Terminated polyether(ATPE).
According to molecular weight, number of functional groups, polyether units structure etc., amidogen ether compounds can be divided into multiple series product:
From functional group, see and can be divided into M-, D-, T-series, and titled with molecular weight; According to the type of terminal amido, have and derive the product that end is secondary amine, in original series name above titled with S; According to polyether units structure, also derive the ED product line that contains ethylene oxide structure in chain.
Existing product also comprises that some end alkyls are some product lines of long-chain fat hydrocarbon or aromatic hydrocarbons:
But above-mentioned secondary amine constructional feature is a section of amido is connected with polyethers, the other end small molecules alkyl of ining succession, this is to be determined by the method for preparing at present amidogen ether.According to current existing amidogen ether preparation method, can not prepare that secondary amine content is high, two (fatty alcohol polyoxy alkane alkene ether) secondary amine of constant product quality, therefore in current product line, lack two (fatty alcohol polyoxy alkane alkene ether) secondary amine.
Chinese patent CN1629132 provides a kind of and take aniline as raw material, utilizes the method that condensation reaction and deamination are coupled to produce pentanoic, take beta-zeolite molecular sieve as catalyzer, reaction pressure 1.5～3.0MPa, 260～400 ℃ of temperature of reaction.
It is raw material that end primary amino fatty alcohol polyoxy alkane alkene ether is take in the present invention, condensation-denitrification coupling reaction by two molecule primary amine makes two (fatty alcohol polyoxy alkane alkene ether) secondary amine, but different is that the present invention uses hydrogenation/dehydrogenation class catalyzer Raney's nickel, reaction conditions is normal pressure, only 150～250 ℃ of temperature of reaction, improving under the condition of secondary amine content, simplification of flowsheet, reducing costs, enabling for industrial circle scale operation.
Summary of the invention
The present invention be exploitation a kind of to take end primary amino fatty alcohol polyoxy alkane alkene ether be raw material, Raney's nickel is catalyzer, makes the method for two (fatty alcohol polyoxy alkane alkene ether) secondary amine under condition of normal pressure by condensation-denitrification coupling reaction of two molecule primary amine.
Technical scheme of the present invention is:
The preparation method of two (fatty alcohol polyoxy alkane alkene ether) secondary amine, is characterized in that:
In end primary amino fatty alcohol polyoxy alkane alkene ether, add a certain amount of catalyzer, this catalyzer is Raney's nickel, described catalyst levels is 0～20% of end primary amino fatty alcohol polyoxy alkane alkene ether quality, speed with every 100g end primary amino fatty alcohol polyoxy alkane alkene ether 0～1000 ml/min passes to hydrogen, be warming up to 150～250 ℃, after reaction 2～20 h, be down to room temperature, filter to obtain two (the fatty alcohol polyoxy alkane alkene ether) secondary amine of product, the ammonification rate of described end primary amino fatty alcohol polyoxy alkane alkene ether is 40～100%.
Described end primary amino fatty alcohol polyoxy alkane alkene ether molecular-weight average is 200～1000, and its structure is as follows:
Wherein R is the alkyl of carbon number 8～18; R1 is H or CH
3, its polyether segment is the single polymers of oxyethane, propylene oxide, or both mixed polymers, block polymer;
2. the preparation method of two (fatty alcohol polyoxy alkane alkene ether) secondary amine according to claim 1, is characterized in that: the ammonification rate of end primary amino fatty alcohol polyoxy alkane alkene ether is 40～90%.When ammonification rate is lower, the amine value of product secondary amine can be on the low side, when ammonification rate is higher, can cause the increase of raw materials cost, and by selecting rational ammonification rate, the product quality index making is stable, and cost is suitable.
3. the preparation method of two (fatty alcohol polyoxy alkane alkene ether) secondary amine according to claim 1, is characterized in that: catalyzer is hydrogenation/dehydrogenation class catalyzer Raney's nickel, and catalyst levels is 0～10% of end primary amino fatty alcohol polyoxy alkane alkene ether quality.When catalytic amount is not enough, speed of reaction is slower, and catalyst excess easily causes waste, and brings pressure can to follow-up filtration.
4. the preparation method of two (fatty alcohol polyoxy alkane alkene ether) secondary amine according to claim 1, is characterized in that: temperature of reaction is 180～220 ℃.Temperature is too low, and speed of response is slower, is unfavorable for the carrying out of reaction, during excess Temperature, can accelerate the speed that the further condensation of secondary amine generates tertiary amine, and tertiary amine content in product is raise.
5. the preparation method of two (fatty alcohol polyoxy alkane alkene ether) secondary amine according to claim 1, is characterized in that: in reaction process, continue to pass to a certain amount of hydrogen, hydrogen flow rate is every 100g end primary amino fatty alcohol polyoxy alkane alkene ether 0～200ml/min.When amounts of hydrogen is not enough, can cause product colour darker
6. the preparation method of two (fatty alcohol polyoxy alkane alkene ether) secondary amine according to claim 1, is characterized in that: the reaction times is 4～10h.Reaction times is too short, and in product, primary amine content is higher, and the reaction times is long, can be that in product, tertiary amine content raises, and therefore need to select the suitable reaction times.
Products obtained therefrom also can carry out aftertreatment, separating catalyst by the mode of suction filtration.
Beneficial effect:
The present invention adopts the denitrification coupling reaction of primary amine to prepare secondary amine, and this reaction mechanism is similar to faces hydrogen aminating reaction, therefore has advantages of that side reaction is few, and this reaction conditions is normal pressure simultaneously, has overcome again the shortcoming of its severe reaction conditions; It is raw material that single reactant end primary amino fatty alcohol polyoxy alkane alkene ether is take in the present invention, feeds intake conveniently while operating in the production making, and has simplified technical process.
Therefore the present invention is improving under the condition of secondary amine content, simplification of flowsheet, reduces costs, and enables for industrial circle scale operation.
Embodiment
Below in conjunction with specific embodiment, further set forth the present invention.
The invention is further illustrated by the following examples, but be not limited to lifted embodiment.
In an embodiment, the ratio value representation secondary amine content (S%) with total amine value with secondary amine value:
In examination: S% is secondary amine content, %; A
sfor the secondary amine value of product, mg KOH/g; A is total amine value of product, mg KOH/g;
End primary amino fatty alcohol polyoxy alkane alkene ether raw material used herein is provided by Yangzhou Chen Hua novel material limited-liability company, and catalyzer Raney's nickel is buied from Jiangsu You Lian metal products company limited.
Example 1:
500g is held to primary amino C
12～14alcohol polyoxyethylene ether, 15g catalyzer Raney's nickel join with agitator, thermometer, ventilation body canal, in the 1000ml four-hole boiling flask of condenser west tube, and end primary amino C
12～14the molecular weight of alcohol polyoxyethylene ether is 390, ammonification rate 46%.Flow velocity with 100ml/min passes to hydrogen, is warming up to 200 ℃, and reacts 5h under the stirring velocity of 300r/min.
After reaction finishes, be cooled to below 100 ℃, stop logical hydrogen, by suction filtration, remove two (C that catalyzer is
12～14alcohol polyoxyethylene groups) secondary amine, secondary amine content (S%) is 92%.
Example 2:
200g is held to primary amino C
12～14alcohol polyoxyethylene ether, 10g catalyzer Raney's nickel join with agitator, thermometer, ventilation body canal, in the 500ml four-hole boiling flask of condenser west tube, and end primary amino C
12～14the molecular weight of alcohol polyoxyethylene ether is 390, ammonification rate 63%.Flow velocity with 100ml/min passes to hydrogen, is warming up to 200 ℃, and reacts 5h under the stirring velocity of 300r/min.
After reaction finishes, be cooled to below 100 ℃, stop logical hydrogen, by suction filtration, remove two (C that catalyzer is
12～14alcohol polyoxyethylene groups) secondary amine, secondary amine content (S%) is 89%.
Example 3:
400g is held to primary amino C
12～14alcohol polyoxypropylene base ether, 20g catalyzer Raney's nickel join with agitator, thermometer, ventilation body canal, in the 1000ml four-hole boiling flask of condenser west tube, and end primary amino C
12～14the molecular weight of alcohol polyoxypropylene base ether is 476, ammonification rate 61%.Flow velocity with 200ml/min passes to hydrogen, is warming up to 200 ℃, and reacts 5h under the stirring velocity of 300r/min.
After reaction finishes, be cooled to below 100 ℃, stop logical hydrogen, by suction filtration, remove two (C that catalyzer is
12～14alcohol polyoxypropylene base) secondary amine, secondary amine content (S%) is 43%.
Example 4:
2500g is held to primary amino C
12～14alcohol polyoxyethylene ether, 50g catalyzer Raney's nickel join with agitator, thermometer, ventilation body canal, in the 5000ml four-hole boiling flask of condenser west tube, and end primary amino C
12～14the molecular weight of alcohol polyoxyethylene ether is 425, ammonification rate 73%.Flow velocity with 300ml/min passes to hydrogen, is warming up to 200 ℃, and reacts 6h under the stirring velocity of 400r/min.
After reaction finishes, be cooled to below 100 ℃, stop logical hydrogen, by suction filtration, remove two (C that catalyzer is
12～14alcohol polyoxyethylene groups) secondary amine, secondary amine content (S%) is 81%.
Example 5:
200g is held to primary amino C
12～14alcohol polyoxyethylene ether, 4g catalyzer Raney's nickel join with agitator, thermometer, ventilation body canal, in the 500ml four-hole boiling flask of condenser west tube, and end primary amino C
12～14the molecular weight of alcohol polyoxyethylene ether is 425, ammonification rate 66%.Flow velocity with 100ml/min passes to hydrogen, is warming up to 200 ℃, and reacts 6h under the stirring velocity of 300r/min.
After reaction finishes, be cooled to below 100 ℃, stop logical hydrogen, by suction filtration, remove two (C12～14 alcohol polyoxyethylene groups) secondary amine that catalyzer is, secondary amine content (S%) is 97%.
Example 6:
200g is held to primary amino C
12～14alcohol polyoxyethylene ether, 4g catalyzer Raney's nickel join with agitator, thermometer, ventilation body canal, in the 500ml four-hole boiling flask of condenser west tube, and end primary amino C
12～14the molecular weight of alcohol polyoxyethylene ether is 416, ammonification rate 74%.Flow velocity with 100ml/min passes to hydrogen, is warming up to 200 ℃, and reacts 6h under the stirring velocity of 300r/min.
After reaction finishes, be cooled to below 100 ℃, stop logical hydrogen, by suction filtration, remove two (C that catalyzer is
12～14alcohol polyoxyethylene groups) secondary amine, secondary amine content (S%) is 96%.
Example 7:
200g is held to primary amino C
8～12alcohol polyoxyethylene ether, 4g catalyzer Raney's nickel join with agitator, thermometer, ventilation body canal, in the 500ml four-hole boiling flask of condenser west tube, and end primary amino C
8～12the molecular weight of alcohol polyoxyethylene ether is 320, ammonification rate 56%.Flow velocity with 100ml/min passes to hydrogen, is warming up to 200 ℃, and reacts 6h under the stirring velocity of 300r/min.
After reaction finishes, be cooled to below 100 ℃, stop logical hydrogen, by suction filtration, remove two (C that catalyzer is
8～12alcohol polyoxyethylene groups) secondary amine, secondary amine content (S%) is 86%.
Example 8:
200g is held to primary amino C
16～18alcohol polyoxyethylene ether, 4g catalyzer Raney's nickel join with agitator, thermometer, ventilation body canal, in the 500ml four-hole boiling flask of condenser west tube, and end primary amino C
16～18the molecular weight of alcohol polyoxyethylene ether is 516, ammonification rate 84%.Flow velocity with 100ml/min passes to hydrogen, is warming up to 200 ℃, and reacts 6h under the stirring velocity of 300r/min.
After reaction finishes, be cooled to below 100 ℃, stop logical hydrogen, by suction filtration, remove two (C that catalyzer is
16～18alcohol polyoxyethylene groups) secondary amine, secondary amine content (S%) is 82%.
Example 9:
200g is held to primary amino C
14alcohol polyoxypropylene base ether, 4g catalyzer Raney's nickel join with agitator, thermometer, ventilation body canal, in the 500ml four-hole boiling flask of condenser west tube, and end primary amino C
14the molecular weight of alcohol polyoxypropylene base ether is 475, ammonification rate 79%.Flow velocity with 100ml/min passes to hydrogen, is warming up to 200 ℃, and reacts 6h under the stirring velocity of 300r/min.
After reaction finishes, be cooled to below 100 ℃, stop logical hydrogen, by suction filtration, remove two (C that catalyzer is
14alcohol polyoxypropylene base) secondary amine, secondary amine content (S%) is 91%.
Should be understood that these embodiment are only not used in and limit the scope of the invention for the present invention is described.In addition should be understood that those skilled in the art can make various changes or modifications the present invention after having read the content of the present invention's instruction, these equivalent form of values fall within the application's appended claims limited range equally.
Claims (7)
1. the preparation method of two (fatty alcohol polyoxy alkane alkene ether) secondary amine, is characterized in that:
In end primary amino fatty alcohol polyoxy alkane alkene ether, add a certain amount of catalyzer, this catalyzer is Raney's nickel, described catalyst levels is 0～20% of end primary amino fatty alcohol polyoxy alkane alkene ether quality, speed with every 100g end primary amino fatty alcohol polyoxy alkane alkene ether 0～1000ml/min passes to hydrogen, be warming up to 150～250 ℃, after reaction 2～20h, be down to room temperature, filter to obtain two (the fatty alcohol polyoxy alkane alkene ether) secondary amine of product, the ammonification rate of described end primary amino fatty alcohol polyoxy alkane alkene ether is 40～100%;
Described end primary amino fatty alcohol polyoxy alkane alkene ether molecular-weight average is+200～1000, and its structure is as follows:
Wherein R is the alkyl of carbon number 8～18; R1 is H or CH
3, its polyether segment is the single polymers of oxyethane, propylene oxide, or both mixed polymers, block polymer.
2. the preparation method of two (fatty alcohol polyoxy alkane alkene ether) secondary amine according to claim 1, is characterized in that: the ammonification rate of end primary amino fatty alcohol polyoxy alkane alkene ether is 40～90%.
3. the preparation method of two (fatty alcohol polyoxy alkane alkene ether) secondary amine according to claim 1, is characterized in that: catalyzer is hydrogenation/dehydrogenation class catalyzer Raney's nickel, and catalyst levels is 0～10% of end primary amino fatty alcohol polyoxy alkane alkene ether quality.
4. the preparation method of two (fatty alcohol polyoxy alkane alkene ether) secondary amine according to claim 1, is characterized in that: temperature of reaction is 160～220 ℃.
5. the preparation method of two (fatty alcohol polyoxy alkane alkene ether) secondary amine according to claim 1, is characterized in that: in reaction process, continue to pass to a certain amount of hydrogen, hydrogen flow rate is every 100g end primary amino fatty alcohol polyoxy alkane alkene ether 0～200ml/min.
6. the preparation method of two (fatty alcohol polyoxy alkane alkene ether) secondary amine according to claim 1, is characterized in that: the reaction times is 4～10h.
7. the preparation method of two (fatty alcohol polyoxy alkane alkene ether) secondary amine according to claim 1, is characterized in that: products obtained therefrom also can carry out aftertreatment, separating catalyst by the mode of suction filtration.
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| CN113277952A (en) * | 2021-04-23 | 2021-08-20 | 岳阳昌德新材料有限公司 | Preparation method of bis (C12-14 alkyl polyoxyethylene) secondary amine |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1092786A (en) * | 1994-01-11 | 1994-09-28 | 青岛化工学院 | The preparation method of polyether polyamine curing agent |
| CN102002158A (en) * | 2010-11-10 | 2011-04-06 | 扬州晨化科技集团有限公司 | Preparation method of alkyl amino terminated polyether |
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- 2013-11-26 CN CN201310603107.0A patent/CN103613506B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1092786A (en) * | 1994-01-11 | 1994-09-28 | 青岛化工学院 | The preparation method of polyether polyamine curing agent |
| CN102002158A (en) * | 2010-11-10 | 2011-04-06 | 扬州晨化科技集团有限公司 | Preparation method of alkyl amino terminated polyether |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113277952A (en) * | 2021-04-23 | 2021-08-20 | 岳阳昌德新材料有限公司 | Preparation method of bis (C12-14 alkyl polyoxyethylene) secondary amine |
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