CN105693537A - N-alkyl acrylamide intermediate and preparation method thereof and preparation method of N-alkyl acrylamide - Google Patents
N-alkyl acrylamide intermediate and preparation method thereof and preparation method of N-alkyl acrylamide Download PDFInfo
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- CN105693537A CN105693537A CN201511019469.0A CN201511019469A CN105693537A CN 105693537 A CN105693537 A CN 105693537A CN 201511019469 A CN201511019469 A CN 201511019469A CN 105693537 A CN105693537 A CN 105693537A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C231/00—Preparation of carboxylic acid amides
- C07C231/02—Preparation of carboxylic acid amides from carboxylic acids or from esters, anhydrides, or halides thereof by reaction with ammonia or amines
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C231/00—Preparation of carboxylic acid amides
- C07C231/12—Preparation of carboxylic acid amides by reactions not involving the formation of carboxamide groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C237/00—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by amino groups
- C07C237/02—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by amino groups having the carbon atoms of the carboxamide groups bound to acyclic carbon atoms of the carbon skeleton
- C07C237/04—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by amino groups having the carbon atoms of the carboxamide groups bound to acyclic carbon atoms of the carbon skeleton the carbon skeleton being acyclic and saturated
- C07C237/06—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by amino groups having the carbon atoms of the carboxamide groups bound to acyclic carbon atoms of the carbon skeleton the carbon skeleton being acyclic and saturated having the nitrogen atoms of the carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C237/00—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by amino groups
- C07C237/02—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by amino groups having the carbon atoms of the carboxamide groups bound to acyclic carbon atoms of the carbon skeleton
- C07C237/16—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by amino groups having the carbon atoms of the carboxamide groups bound to acyclic carbon atoms of the carbon skeleton the carbon skeleton being acyclic and unsaturated
Abstract
The invention belongs to the field of acrylamide, and particularly relates to an N-alkyl acrylamide intermediate and a preparation method thereof and a preparation method of N-alkyl acrylamide.The preparation method of N-alkyl acrylamide comprises the following steps that a cracking reaction is conducted on a compound with the structure of a formula (I) in the presence of a cracking catalyst, and N-alkyl acrylamide with the structure of a formula (VII) is obtained, wherein R1 and R2 are independently selected from alkyl, and n is larger than or equal to 0 and smaller than or equal to 30.The yield of N-alkyl acrylamide prepared through the method is high.It is indicated through experimental results that the total yield of N-alkyl acrylamide prepared through the method is larger than 85%.Please see the formulas in the description.
Description
Technical field
The invention belongs to acrylamide field, the preparation method particularly relating to a kind of N-alkyl acrylamide intermediate and preparation method thereof and N-alkyl acrylamide。
Background technology
N-alkyl acrylamide is the function monomer that a class is important, and its structure is as follows:
N-alkyl acrylamide has good polymerization activity and excellent hydrolytic resistance, its multiple copolymer has a wide range of applications at oil recovery, sewage disposal, cosmetic and coating industry, and its temperature sensitive performance makes it have huge potential using value in bio-separation engineering, drug release material and sensor material field。
At present, the method for synthesis N-alkyl acrylamide has a lot, and wherein most widely used is acrylonitrile alcoholysis method。Acrylonitrile alcoholysis method refers to using acrylonitrile and alcohol as reaction raw materials, and by the method that alcoholysis reaction prepares into N-alkyl acrylamide, but it is relatively low to adopt acrylonitrile alcoholysis method to prepare the yield of obtained final products during N-alkyl acrylamide。
Summary of the invention
In view of this, the preparation method that it is an object of the invention to provide a kind of N-alkyl acrylamide intermediate and preparation method thereof and N-alkyl acrylamide, adopt method provided by the invention to prepare the yield of N-alkyl acrylamide higher。
The invention provides a kind of N-alkyl acrylamide intermediate, there is formula (I) structure:
Formula (I)；
In formula (I), R1And R2Independently selected from alkyl, 0≤n≤30。
Preferably, described R1And R2Independently selected from C1～C10Alkyl。
Preferably, 4≤n≤20。
Preferably, described N-alkyl acrylamide intermediate has formula (II) structure:
Formula (II)；
In formula (II), n=8,11,15 or 17。
The preparation method that the invention provides a kind of N-alkyl acrylamide intermediate, comprises the following steps:
Formula (III) structural compounds carries out aminolysis reaction with formula (IV) structural compounds under ammonolysis catalyst exists, and obtains formula (I) structural compounds；
Formula (I)；
Formula (III)；Formula (IV)；
Wherein, R1And R2Independently selected from alkyl, 0≤m≤10,0≤n≤30。
Preferably, described formula (III) structural compounds is prepared in accordance with the following methods:
Formula (V) structural compounds and formula (VI) structural compounds carry out additive reaction, obtain formula (III) structural compounds；
Formula (V)；Formula (VI)；
Wherein, 0≤m≤10, R1And R2Independently selected from alkyl。
The preparation method that the invention provides a kind of N-alkyl acrylamide, comprises the following steps:
Formula (I) structural compounds carries out cracking reaction under catalyst for cracking exists, and obtains the N-alkyl acrylamide with formula (VII) structure；
Formula (I)；Formula (VII)；
Wherein, R1And R2Independently selected from alkyl, 0≤n≤30。
Preferably, described catalyst for cracking is tetrabutyl ammonium bromide, MgO, Ca (OH)2With Ba (OH)2In one or more。
Preferably, described cracking reaction carries out under polymerization inhibitor exists。
Preferably, the reaction pressure of described cracking reaction is 0.01～0.1MPa；The reaction temperature of described cracking reaction is 150～170 DEG C；The response time of described cracking reaction is 3～5h。
Compared with prior art, the preparation method that the invention provides a kind of N-alkyl acrylamide intermediate and preparation method thereof and N-alkyl acrylamide。Method provided by the invention comprises the following steps: formula (I) structural compounds carries out cracking reaction under catalyst for cracking exists, and obtains the N-alkyl acrylamide with formula (VII) structure；Wherein, R1And R2Independently selected from alkyl, 0≤n≤30。Method provided by the invention is adopted to prepare the yield of N-alkyl acrylamide higher。Test result indicate that, adopt method provided by the invention to prepare the total recovery of N-alkyl acrylamide more than 85%。
Detailed description of the invention
Below the technical scheme in the embodiment of the present invention is clearly and completely described, it is clear that described embodiment is only a part of embodiment of the present invention, rather than whole embodiments。Based on the embodiment in the present invention, the every other embodiment that those of ordinary skill in the art obtain under not making creative work premise, broadly fall into the scope of protection of the invention。
The invention provides a kind of N-alkyl acrylamide intermediate, there is formula (I) structure:
Formula (I)；
In formula (I), 0≤n≤30。
N-alkyl acrylamide intermediate provided by the invention has formula (I) structure, in formula (I), and R1And R2Independently selected from alkyl, it is preferable that from C1～C10Alkyl, more preferably from methyl, ethyl, propyl group, butyl or amyl group；0≤n≤30, it is preferred to 2≤n≤25, more preferably 4≤n≤20, it is most preferred that for n=8,11,15 or 17。
In an embodiment provided by the invention, described N-alkyl acrylamide intermediate has formula (II) structure:
Formula (II)；
In formula (II), n=8,11,15 or 17。
In the present invention, there is the concrete structure of N-alkyl acrylamide intermediate of formula (II) structure described in respectively as shown in (II-1), formula (II-2), formula (II-3) or formula (II-4):
Formula (II-1)；
Formula (II-2)；
Formula (II-3)；
Formula (II-4)。
The N-alkyl acrylamide intermediate with formula (I) structure provided by the invention can pass through a step cracking reaction and prepare N-alkyl acrylamide, adopts the yield that this intermediate prepares N-alkyl acrylamide by a step cracking reaction higher。
The preparation method that the invention provides a kind of N-alkyl acrylamide intermediate, comprises the following steps:
Formula (III) structural compounds carries out aminolysis reaction with formula (IV) structural compounds under ammonolysis catalyst exists, and obtains formula (I) structural compounds；
Formula (I)；
Formula (III)；Formula (IV)；
Wherein, R1And R2Independently selected from alkyl, 0≤m≤10,0≤n≤30。
In the preparation method of N-alkyl acrylamide intermediate provided by the invention, under ammonolysis catalyst exists, directly formula (III) structural compounds and formula (IV) structural compounds are carried out aminolysis reaction, formula (I) structural compounds can be obtained, this process particularly as follows:
First formula (III) structural compounds, formula (IV) structural compounds and ammonolysis catalyst are mixed。Wherein, the concrete structure of described formula (III) structural compounds is as follows:
Formula (III)；
In formula (III), R1And R2Independently selected from alkyl, it is preferable that from C1～C10Alkyl, more preferably from methyl, ethyl, propyl group, butyl or amyl group；0≤m≤10, it is preferred to 0≤m≤5, more preferably m=0,1 or 3。In an embodiment provided by the invention, described formula (III) structural compounds is specially the compound with formula (III-1), formula (III-2) or formula (III-3) structure:
Formula (III-1)；
Formula (III-2)
Formula (III-3)；
The source of described formula (III) structural compounds is not particularly limited by the present invention, it is possible to adopt commercial goods, it is also possible to be prepared according to method well known to those skilled in the art。In an embodiment provided by the invention, described formula (III) structural compounds is prepared in accordance with the following methods:
Formula (V) structural compounds and formula (VI) structural compounds carry out additive reaction, obtain formula (III) structural compounds；
Formula (V)；Formula (VI)；
Wherein, 0≤m≤10, R1And R2Independently selected from alkyl。
In the preparation method of formula provided by the invention (III) structural compounds, directly formula (V) structural compounds and formula (VI) structural compounds are carried out additive reaction, formula (III) structural compounds can be obtained, this process particularly as follows:
First formula (V) structural compounds is mixed with formula (VI) structural compounds。Wherein, the concrete structure of described formula (III) structural compounds is as follows:
Formula (V)；
In formula (V), 0≤m≤10, it is preferred to 0≤m≤5, more preferably m=0,1 or 3。In an embodiment provided by the invention, described formula (V) structural compounds is specially the compound with formula (V-1), formula (V-2) or formula (V-3) structure:
Formula (V-1)；
Formula (V-2)；
Formula (V-3)。
The source of described formula (V) structural compounds is not particularly limited by the present invention, it is possible to adopt commercial goods, it is also possible to be prepared according to method well known to those skilled in the art。
In the present invention, in described (V) structural compounds with (VI) structural compounds mixed process, the structure of described (VI) structural compounds is as follows:
Formula (VI)；
In formula (VI), R1And R2Independently selected from alkyl, it is preferable that from C1～C10Alkyl, more preferably from methyl, ethyl, propyl group, butyl or amyl group。In an embodiment provided by the invention, described formula (VI) structural compounds is specially the compound with formula (VI-1) structure:
Formula (VI-1)。
The source of described formula (VI) structural compounds is not particularly limited by the present invention, it is possible to adopt commercial goods, it is also possible to be prepared according to method well known to those skilled in the art。
In the present invention, in described (V) structural compounds with (VI) structural compounds mixed process, the mol ratio of described (V) structural compounds and (VI) structural compounds is preferably 1:(1～2), it is more preferably 1:(1.2～1.5), it is most preferred that for 1:(1.3～1.4)。Described (V) structural compounds carries out additive reaction after mixing with (VI) structural compounds。The temperature of described additive reaction is preferably 60～90 DEG C, more preferably 70～80 DEG C。The time of described additive reaction is preferably 2～8h, more preferably 4～5h。Reaction obtains containing reaction product solution after terminating, and the described solution containing product carries out post processing, obtains formula (III) structural compounds。In the present invention, the mode of described post processing is preferably distillation of reducing pressure。
In the present invention, described formula (III) structural compounds, formula (IV) structural compounds are with ammonolysis catalyst mixed process, and the concrete structure of described formula (IV) structural compounds is as follows:
Formula (IV)；
In formula (IV), 0≤n≤30, it is preferred to 2≤n≤25, more preferably 4≤n≤20, it is most preferred that for n=8,11,15 or 17。In an embodiment provided by the invention, described formula (IV) structural compounds specifically has formula (IV-1), formula (IV-2), formula (IV-3) or formula (IV-4) structure:
Formula (IV-1)；Formula (IV-2)；Formula (IV-3)；Formula (IV-4)。
The source of formula (IV) structural compounds is not particularly limited by the present invention, it is possible to adopt commercial goods, it is also possible to be prepared according to method well known to those skilled in the art。
In the present invention, described formula (III) structural compounds, formula (IV) structural compounds are with ammonolysis catalyst mixed process, and described ammonolysis catalyst is preferably Feldalat NM or organotin catalysts。The mol ratio of described formula (III) structural compounds and formula (IV) structural compounds is preferably 1:(0.5～4), more preferably 1:(1～3), it is most preferred that for 1:(1.2～2.6)。Described ammonolysis catalyst is preferably 1～10wt% at described formula (III) structural compounds, formula (IV) structural compounds with the content in the mixed system of ammonolysis catalyst composition, more preferably 2～5wt%。Described formula (III) structural compounds, formula (IV) structural compounds carry out aminolysis reaction after mixing with ammonolysis catalyst。In the present invention, the pressure of described aminolysis reaction is preferably 2～10MPa, more preferably 4～6MPa。The reaction temperature of described aminolysis reaction is preferably 120～180 DEG C, more preferably 130～180 DEG C。The response time of described aminolysis reaction is preferably 5～10h, more preferably 7～9h。After aminolysis reaction terminates, obtaining the solution containing product, the described solution containing product carries out post processing, obtains formula (I) structural compounds。In the present invention, the mode of described post processing is preferably distillation of reducing pressure。
Method provided by the invention can prepare the N-alkyl acrylamide intermediate with formula (I) structure, this intermediate can pass through a step cracking reaction and prepare N-alkyl acrylamide, this intermediate the yield preparing N-alkyl acrylamide by a step cracking reaction is higher。
The preparation method that the invention provides a kind of N-alkyl acrylamide, comprises the following steps:
Formula (I) structural compounds carries out cracking reaction under tetrabutyl ammonium bromide catalytic condition, obtains the N-alkyl acrylamide with formula (VII) structure；
Formula (I)；Formula (VII)；
Wherein, R1And R2Independently selected from alkyl, 0≤n≤30。
In the preparation method of N-alkyl acrylamide provided by the invention, directly formula (I) structural compounds is carried out cracking reaction under catalyst for cracking exists, the N-alkyl acrylamide with formula (VII) structure can be obtained, this process particularly as follows:
First formula (I) structural compounds and catalyst for cracking are mixed in a solvent。Wherein, the concrete structure of described formula (I) structural compounds is as follows:
Formula (I)；
In formula (I), 0≤n≤30, it is preferred to 2≤n≤25, more preferably 4≤n≤20, it is most preferred that for n=8,11,15 or 17。
In an embodiment provided by the invention, described N-alkyl acrylamide intermediate has (II) structure:
Formula (II)；
In formula (II), n=8,11,15 or 17。
In the present invention, there is the concrete structure of N-alkyl acrylamide intermediate of formula (II) structure described in respectively as shown in (II-1), formula (II-2), formula (II-3) or formula (II-4):
Formula (II-1)；
Formula (II-2)；
Formula (II-3)；
Formula (II-4)。
The source of described formula (I) structural compounds is not particularly limited by the present invention, it is possible to adopt commercial goods, it is also possible to be prepared according to method well known to those skilled in the art。In an embodiment provided by the invention, described formula (I) structural compounds is prepared in accordance with the following methods:
Formula (III) structural compounds carries out aminolysis reaction with formula (IV) structural compounds under ammonolysis catalyst exists, and obtains formula (I) structural compounds；
Formula (III)；Formula (IV)；
Wherein, R1And R2Independently selected from alkyl, 0≤m≤10,0≤n≤30。
In the preparation method of N-alkyl acrylamide intermediate provided by the invention, under ammonolysis catalyst exists, directly formula (III) structural compounds and formula (IV) structural compounds are carried out aminolysis reaction, formula (I) structural compounds can be obtained, this process particularly as follows:
First formula (III) structural compounds, formula (IV) structural compounds and ammonolysis catalyst are mixed。Wherein, the concrete structure of described formula (III) structural compounds is as follows:
Formula (III)；
In formula (III), R1And R2Independently selected from alkyl, it is preferable that from C1～C10Alkyl, more preferably from methyl, ethyl, propyl group, butyl or amyl group；0≤m≤10, it is preferred to 0≤m≤5, more preferably m=0,1 or 3。In an embodiment provided by the invention, described formula (III) structural compounds is specially the compound with formula (III-1), formula (III-2) or formula (III-3) structure:
Formula (III-1)；
Formula (III-2)；
Formula (III-3)；
The source of described formula (III) structural compounds is not particularly limited by the present invention, commercial goods can be adopted, can also be prepared according to method well known to those skilled in the art, in an embodiment provided by the invention, described formula (III) structural compounds is prepared in accordance with the following methods:
Formula (V) structural compounds and formula (VI) structural compounds carry out additive reaction, obtain formula (III) structural compounds；
Formula (V)；Formula (VI)；
Wherein, 0≤m≤10, R1And R2Independently selected from alkyl。
In the preparation method of formula provided by the invention (III) structural compounds, directly formula (V) structural compounds and formula (VI) structural compounds are carried out additive reaction, formula (III) structural compounds can be obtained, this process particularly as follows:
First formula (V) structural compounds is mixed with formula (VI) structural compounds。Wherein, the concrete structure of described formula (III) structural compounds is as follows:
Formula (V)；
In formula (V), 0≤m≤10, it is preferred to 0≤m≤5, more preferably m=0,1 or 3。In an embodiment provided by the invention, described formula (V) structural compounds is specially the compound with formula (V-1), formula (V-2) or formula (V-3) structure:
Formula (V-1)；
Formula (V-2)；
Formula (V-3)。
The source of described formula (V) structural compounds is not particularly limited by the present invention, it is possible to adopt commercial goods, it is also possible to be prepared according to method well known to those skilled in the art。
In the present invention, in described (V) structural compounds with (VI) structural compounds mixed process, the structure of described (VI) structural compounds is as follows:
Formula (VI)；
In formula (VI), R1And R2Independently selected from alkyl, it is preferable that from C1～C10Alkyl, more preferably from methyl, ethyl, propyl group, butyl or amyl group。In an embodiment provided by the invention, described formula (VI) structural compounds is specially the compound with formula (VI-1) structure:
Formula (VI-1)。
The source of described formula (VI) structural compounds is not particularly limited by the present invention, it is possible to adopt commercial goods, it is also possible to be prepared according to method well known to those skilled in the art。
In the present invention, in described (V) structural compounds with (VI) structural compounds mixed process, the mol ratio of described (V) structural compounds and (VI) structural compounds is preferably 1:(1～2), it is more preferably 1:(1.2～1.5), it is most preferred that for 1:(1.3～1.4)。Described (V) structural compounds carries out additive reaction after mixing with (VI) structural compounds。The temperature of described additive reaction is preferably 60～90 DEG C, more preferably 70～80 DEG C。The time of described methanol reaction is preferably 2～8h, more preferably 4～5h。Reaction obtains containing reaction product solution after terminating, and the described solution containing product carries out post processing, obtains formula (III) structural compounds。In the present invention, the mode of described post processing is preferably distillation of reducing pressure。
In the present invention, described formula (III) structural compounds, formula (IV) structural compounds are with ammonolysis catalyst mixed process, and the concrete structure of described formula (IV) structural compounds is as follows:
Formula (IV)；
In formula (IV), 0≤n≤30, it is preferred to 2≤n≤25, more preferably 4≤n≤20, it is most preferred that for n=8,11,15 or 17。In an embodiment provided by the invention, described formula (IV) structural compounds specifically has formula (IV-1), formula (IV-2), formula (IV-3) or formula (IV-4) structure:
Formula (IV-1)；Formula (IV-2)；Formula (IV-3)；Formula (IV-4)。
The source of formula (IV) structural compounds is not particularly limited by the present invention, it is possible to adopt commercial goods, it is also possible to be prepared according to method well known to those skilled in the art。
In the present invention, described formula (III) structural compounds, formula (IV) structural compounds are with ammonolysis catalyst mixed process, and described ammonolysis catalyst is preferably Feldalat NM or organotin catalysts。The mol ratio of described formula (III) structural compounds and formula (IV) structural compounds is preferably 1:(0.5～4), more preferably 1:(1～3), it is most preferred that for 1:(1.2～2.6)。Described ammonolysis catalyst is preferably 1～10wt% at described formula (III) structural compounds, formula (IV) structural compounds with the content in the mixed system of ammonolysis catalyst composition, more preferably 2～5wt%。Described formula (III) structural compounds, formula (IV) structural compounds carry out aminolysis reaction after mixing with ammonolysis catalyst。In the present invention, the reaction pressure of described aminolysis reaction is preferably 2～10MPa, more preferably 4～6MPa。The reaction temperature of described aminolysis reaction is preferably 120～180 DEG C, more preferably 130～180 DEG C。The response time of described aminolysis reaction is preferably 5～10h, more preferably 7～9h。After aminolysis reaction terminates, obtaining the solution containing product, the described solution containing product carries out post processing, obtains formula (I) structural compounds。In the present invention, the mode of described post processing is preferably distillation of reducing pressure。
In the present invention, described formula (I) structural compounds and in catalyst for cracking mixed process in a solvent, described catalyst for cracking is preferably tetrabutyl ammonium bromide, MgO, Ca (OH)2With Ba (OH)2In one or more；Described solvent is preferably toluene or dimethylbenzene。The mass ratio of described formula (I) structural compounds and catalyst for cracking is preferably (20～50): 1, more preferably (30～35): 1, it is most preferred that for (32～35): 1。After described formula (I) structural compounds and catalyst for cracking mixing, carry out cracking reaction。In the present invention, described cracking reaction carries out under existing preferably in polymerization inhibitor。Described polymerization inhibitor is preferably the one in benzoquinone, hydroquinone, phenothiazine and MEHQ。The mass ratio of described formula (I) structural compounds and polymerization inhibitor is preferably (80～120): 1, more preferably (90～110): 1, it is most preferred that for (100～105): 1。In the present invention, the reaction pressure of described cracking reaction is preferably 0.01～0.1MPa, more preferably 0.07～0.08MPa。The reaction temperature of described cracking reaction is 150～170 DEG C。The response time of described cracking reaction is 3～5h。After cracking reaction terminates, obtaining the solution containing product, the described solution containing product carries out post processing, obtains the N-alkyl acrylamide with formula (VII) structure。In the present invention, the mode of described post processing is preferably distillation of reducing pressure。
Method provided by the invention is adopted to prepare the yield of N-alkyl acrylamide higher。Test result indicate that, adopt method provided by the invention to prepare the total recovery of N-alkyl acrylamide more than 85%。
In preferred implementation provided by the invention, employing formula (V) structural compounds and formula (VI) structural compounds are as the initiation material preparing N-alkyl acrylamide, these raw materials cheap, it is possible to reduce the production cost of N-alkyl acrylamide。
For the purpose of becoming apparent from, it is described in detail below by following example。
Embodiment 1
Preparing the dry four-hole boiling flask being furnished with stirring paddle, reflux condensing tube, thermometer, by 110g acrylic acid methyl ester., 126g diethylamine joins in reaction bulb, mix homogeneously, is warming up to 75 DEG C of reaction 4h, and decompression distillation obtains addition compound product diethylin propionic ester 142g。
Above-mentioned diethylin acrylate, 205g lauryl amine, 6.5g Feldalat NM are joined in autoclave, reaction pressure be 5MPa, aminolysis reaction 8h at 130 DEG C, taking after aminolysis reaction and proceed in there-necked flask by above-mentioned mixed liquor, decompression distillation obtains amidated products 263g。
Above-mentioned prepared amidated products is carried out Infrared Characterization, and result is as shown in table 1:
The Infrared Characterization data of the amidated products that table 1 embodiment 1 prepares
The data in kind and table 1 are added it can be concluded that above-mentioned prepared amidated products has formula (II-2) structure by raw material。
Take above-mentioned amidated products and 1000g toluene, 7.8g tetrabutyl ammonium bromide, 2.6g benzoquinone and join in reactor, be warming up to 150 DEG C, catalytic pyrolysis 5h under 0.0747MPa pressure, distillation of finally reducing pressure, obtain long-chain N-alkyl-substituted acrylamide product。
Above-mentioned prepared long-chain N-alkyl-substituted acrylamide product is carried out Infrared Characterization, and result is as shown in table 2:
The Infrared Characterization data of the long-chain N-alkyl-substituted acrylamide product that table 2 embodiment 1 prepares
The data in kind and table 2 are added it can be concluded that above-mentioned prepared long-chain N-alkyl-substituted acrylamide product has formula (VII) structure by raw material, in formula (VII), n=11。
Adopting liquid-phase chromatographic analysis to calculate the purity of above-mentioned prepared long-chain N-alkyl-substituted acrylamide product, the actual conditions of described liquid-phase chromatographic analysis test is: ZorbaxSAX chromatographic column, mobile phase is 0.1mol/LKH2PO4Solution, flow rate of mobile phase is 1.0ml/min, UV-detector, and result is: purity is 96.8%。
The total recovery of the long-chain N-alkyl-substituted acrylamide product obtained is calculated, and result is: total yield of products is 85.7%。
In the present invention, described total yield of products refers to according to initiation material (in the present embodiment, initiation material refers to acrylic acid methyl ester. and diethylamine) calculated yield, formula is: total recovery=purpose product amount of actually generating/according to calculated purpose product theory growing amount × 100% of initiation material。
Embodiment 2
Preparing the dry four-hole boiling flask being furnished with stirring paddle, reflux condensing tube, thermometer, by 110g acrylic acid methyl ester., 126g diethylamine joins in reaction bulb, mix homogeneously, is warming up to 75 DEG C of reaction 4h, and decompression distillation obtains addition compound product diethylin propionic ester 158g。
Above-mentioned diethylin acrylate, 456g lauryl amine, 12g Feldalat NM are joined in autoclave, reaction pressure be 5MPa, aminolysis reaction 8h at 130 DEG C, taking after aminolysis reaction and proceed in there-necked flask by above-mentioned mixed liquor, decompression distillation obtains amidated products 308g。
Take above-mentioned amidated products and 1200g toluene, 9.4g tetrabutyl ammonium bromide, 3g benzoquinone and join in reactor, be warming up to 150 DEG C, catalytic pyrolysis 5h under 0.0747MPa pressure, distillation of finally reducing pressure, obtain long-chain N-alkyl-substituted acrylamide product。
The long-chain N-alkyl-substituted acrylamide product obtained is carried out infrared analysis by the method adopting embodiment 1, it is shown that this product is the long-chain N-alkyl-substituted acrylamide with formula (VII) structure, in formula (VII), and n=11。
Purity and the total recovery of the method for the employing embodiment 1 long-chain N-alkyl-substituted acrylamide product to obtaining are calculated, and result is: purity is 98.6%, and total yield of products is 90.4%。
Embodiment 3
Preparing the dry four-hole boiling flask being furnished with stirring paddle, reflux condensing tube, thermometer, by 110g acrylic acid methyl ester., 126g diethylamine joins in reaction bulb, mix homogeneously, is warming up to 75 DEG C of reaction 4h, and decompression distillation obtains addition compound product diethylin propionic ester 163g。
Above-mentioned diethylin acrylate, 542g 18-amine., 14g Feldalat NM are joined in autoclave, reaction pressure be 5MPa, aminolysis reaction 8h at 130 DEG C, taking after aminolysis reaction and proceed in there-necked flask by above-mentioned mixed liquor, decompression distillation obtains amidated products 452g。
Above-mentioned prepared amidated products is carried out Infrared Characterization, and result is as shown in table 3:
The Infrared Characterization data of the amidated products that table 3 embodiment 3 prepares
The data in kind and table 3 are added it can be concluded that above-mentioned prepared amidated products has formula (II-4) structure by raw material。
Take above-mentioned amidated products and 1500g toluene, 13g tetrabutyl ammonium bromide, 4.5g benzoquinone and join in reactor, be warming up to 150 DEG C, catalytic pyrolysis 5h under 0.0747MPa pressure, distillation of finally reducing pressure, obtain long-chain N-alkyl-substituted acrylamide product。
Above-mentioned prepared long-chain N-alkyl-substituted acrylamide product is carried out Infrared Characterization, and result is as shown in table 4:
The Infrared Characterization data of the long-chain N-alkyl-substituted acrylamide product that table 4 embodiment 3 prepares
The data in kind and table 4 are added it can be concluded that above-mentioned prepared long-chain N-alkyl-substituted acrylamide product has formula (VII) structure by raw material, in formula (VII), n=17。
Purity and the total recovery of the method for the employing embodiment 1 long-chain N-alkyl-substituted acrylamide product to obtaining are calculated, and result is: purity is 97.1%, and total yield of products is 89.3%。
Embodiment 4:
Preparing the dry four-hole boiling flask being furnished with stirring paddle, reflux condensing tube, thermometer, by 110g acrylic acid methyl ester., 126g diethylamine joins in reaction bulb, mix homogeneously, is warming up to 75 DEG C of reaction 4h, and decompression distillation obtains addition compound product diethylin propionic ester 153g。
Above-mentioned diethylin acrylate, 456g lauryl amine, 12g Feldalat NM are joined in autoclave, reaction pressure be 5MPa, aminolysis reaction 8h at 180 DEG C, taking after aminolysis reaction and proceed in there-necked flask by above-mentioned mixed liquor, decompression distillation obtains amidated products 325g。
Take above-mentioned amidated products and 1200g toluene, 9.6g tetrabutyl ammonium bromide, 3.2g benzoquinone and join in reactor, be warming up to 150 DEG C, catalytic pyrolysis 5h under 0.0747MPa pressure, distillation of finally reducing pressure, obtain long-chain N-alkyl-substituted acrylamide product。
The long-chain N-alkyl-substituted acrylamide product obtained is carried out infrared analysis by the method adopting embodiment 1, it is shown that this product is the long-chain N-alkyl-substituted acrylamide with formula (VII) structure, in formula (VII), and n=11。
Purity and the total recovery of the method for the employing embodiment 1 long-chain N-alkyl-substituted acrylamide product to obtaining are calculated, and result is: purity is 98.2%, and total yield of products is 91%。
Embodiment 5
Preparing the dry four-hole boiling flask being furnished with stirring paddle, reflux condensing tube, thermometer, by 110g acrylic acid methyl ester., 126g diethylamine joins in reaction bulb, mix homogeneously, is warming up to 75 DEG C of reaction 4h, and decompression distillation obtains addition compound product diethylin propionic ester 150g。
Above-mentioned diethylin acrylate, 456g lauryl amine, 12g Feldalat NM are joined in autoclave, reaction pressure be 5MPa, aminolysis reaction 8h at 130 DEG C, taking after aminolysis reaction and proceed in there-necked flask by above-mentioned mixed liquor, decompression distillation obtains amidated products 310g。
Take above-mentioned amidated products and 1200g toluene, catalyst for cracking 9.4g, polymerization inhibitor 3g and join in reactor, be warming up to 150 DEG C, catalytic pyrolysis 3h under 0.0747MPa pressure, distillation of finally reducing pressure, obtain long-chain N-alkyl-substituted acrylamide product。
The long-chain N-alkyl-substituted acrylamide product obtained is carried out infrared analysis by the method adopting embodiment 1, it is shown that this product is the long-chain N-alkyl-substituted acrylamide with formula (VII) structure, in formula (VII), and n=11。
Purity and the total recovery of the method for the employing embodiment 1 long-chain N-alkyl-substituted acrylamide product to obtaining are calculated, and result is: purity is 97.5%, and total yield of products is 87.8%。
The above is only the preferred embodiment of the present invention; it should be pointed out that, for those skilled in the art, under the premise without departing from the principles of the invention; can also making some improvements and modifications, these improvements and modifications also should be regarded as protection scope of the present invention。
Claims (10)
1. a N-alkyl acrylamide intermediate, has formula (I) structure:
In formula (I), R1And R2Independently selected from alkyl, 0≤n≤30。
2. N-alkyl acrylamide intermediate according to claim 1, it is characterised in that described R1And R2Independently selected from C1～C10Alkyl。
3. N-alkyl acrylamide intermediate according to claim 1, it is characterised in that 4≤n≤20。
4. N-alkyl acrylamide intermediate according to claim 1, it is characterised in that described N-alkyl acrylamide intermediate has formula (II) structure:
In formula (II), n=8,11,15 or 17。
5. a preparation method for N-alkyl acrylamide intermediate, comprises the following steps:
Formula (III) structural compounds carries out aminolysis reaction with formula (IV) structural compounds under ammonolysis catalyst exists, and obtains formula (I) structural compounds；
Wherein, R1And R2Independently selected from alkyl, 0≤m≤10,0≤n≤30。
6. preparation method according to claim 5, it is characterised in that described formula (III) structural compounds is prepared in accordance with the following methods:
Formula (V) structural compounds and formula (VI) structural compounds carry out additive reaction, obtain formula (III) structural compounds；
Wherein, 0≤m≤10, R1And R2Independently selected from alkyl。
7. a preparation method for N-alkyl acrylamide, comprises the following steps:
Formula (I) structural compounds carries out cracking reaction under catalyst for cracking exists, and obtains the N-alkyl acrylamide with formula (VII) structure；
Wherein, R1And R2Independently selected from alkyl, 0≤n≤30。
8. preparation method according to claim 7, it is characterised in that described catalyst for cracking is tetrabutyl ammonium bromide, MgO, Ca (OH)2With Ba (OH)2In one or more。
9. preparation method according to claim 7, it is characterised in that described cracking reaction carries out under polymerization inhibitor exists。
10. preparation method according to claim 7, it is characterised in that the reaction pressure of described cracking reaction is 0.01～0.1MPa；The reaction temperature of described cracking reaction is 150～170 DEG C；The response time of described cracking reaction is 3～5h。
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