CN117088788A - Preparation method of N, N-dimethylaminopropyl methacrylamide - Google Patents
Preparation method of N, N-dimethylaminopropyl methacrylamide Download PDFInfo
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- CN117088788A CN117088788A CN202311043052.2A CN202311043052A CN117088788A CN 117088788 A CN117088788 A CN 117088788A CN 202311043052 A CN202311043052 A CN 202311043052A CN 117088788 A CN117088788 A CN 117088788A
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- dimethylamino
- propyl
- dimethylaminopropyl methacrylamide
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- JNDVNJWCRZQGFQ-UHFFFAOYSA-N 2-methyl-N,N-bis(methylamino)hex-2-enamide Chemical compound CCCC=C(C)C(=O)N(NC)NC JNDVNJWCRZQGFQ-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000003054 catalyst Substances 0.000 claims abstract description 41
- IUNMPGNGSSIWFP-UHFFFAOYSA-N dimethylaminopropylamine Chemical compound CN(C)CCCN IUNMPGNGSSIWFP-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000003112 inhibitor Substances 0.000 claims abstract description 26
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 24
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000007864 aqueous solution Substances 0.000 claims abstract description 16
- MGTPQUHIJZMPRF-UHFFFAOYSA-N n-[3-(dimethylamino)propyl]-3-[3-(dimethylamino)propylamino]-2-methylpropanamide Chemical compound CN(C)CCCNCC(C)C(=O)NCCCN(C)C MGTPQUHIJZMPRF-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000007112 amidation reaction Methods 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 15
- 238000007259 addition reaction Methods 0.000 claims abstract description 14
- 159000000003 magnesium salts Chemical class 0.000 claims abstract description 9
- 238000010335 hydrothermal treatment Methods 0.000 claims abstract description 8
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims abstract description 7
- 150000001412 amines Chemical class 0.000 claims abstract description 7
- 150000007529 inorganic bases Chemical class 0.000 claims abstract description 3
- 238000006386 neutralization reaction Methods 0.000 claims abstract description 3
- 238000001556 precipitation Methods 0.000 claims abstract description 3
- 238000010438 heat treatment Methods 0.000 claims description 33
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 17
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 claims description 10
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 claims description 8
- 229950000688 phenothiazine Drugs 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 238000003776 cleavage reaction Methods 0.000 claims description 5
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 4
- 239000011777 magnesium Substances 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 3
- BZIYQZKSEDEBFA-UHFFFAOYSA-N [O].OC1CCN(CC1)O Chemical compound [O].OC1CCN(CC1)O BZIYQZKSEDEBFA-UHFFFAOYSA-N 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims description 2
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 2
- 238000010526 radical polymerization reaction Methods 0.000 claims description 2
- 230000007017 scission Effects 0.000 claims 2
- 238000004523 catalytic cracking Methods 0.000 claims 1
- 238000001027 hydrothermal synthesis Methods 0.000 claims 1
- 239000002904 solvent Substances 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 13
- 239000000047 product Substances 0.000 abstract description 12
- 238000005336 cracking Methods 0.000 abstract description 10
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 230000000694 effects Effects 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 239000013067 intermediate product Substances 0.000 abstract 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 21
- 239000000543 intermediate Substances 0.000 description 18
- 238000000197 pyrolysis Methods 0.000 description 17
- 239000007795 chemical reaction product Substances 0.000 description 12
- 239000012467 final product Substances 0.000 description 12
- 238000010992 reflux Methods 0.000 description 12
- 238000003756 stirring Methods 0.000 description 11
- 239000007788 liquid Substances 0.000 description 9
- 230000006837 decompression Effects 0.000 description 8
- 239000006166 lysate Substances 0.000 description 8
- -1 4-hydroxypiperidinol oxygen free radical Chemical class 0.000 description 6
- 238000000605 extraction Methods 0.000 description 6
- 239000000243 solution Substances 0.000 description 5
- 238000001035 drying Methods 0.000 description 4
- 230000014759 maintenance of location Effects 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- FLCAEMBIQVZWIF-UHFFFAOYSA-N 6-(dimethylamino)-2-methylhex-2-enamide Chemical compound CN(C)CCCC=C(C)C(N)=O FLCAEMBIQVZWIF-UHFFFAOYSA-N 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000007233 catalytic pyrolysis Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000012544 monitoring process Methods 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 238000004227 thermal cracking Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 230000009435 amidation Effects 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000008394 flocculating agent Substances 0.000 description 1
- 229920001002 functional polymer Polymers 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910001510 metal chloride Inorganic materials 0.000 description 1
- 229910001960 metal nitrate Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 150000003512 tertiary amines Chemical group 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C231/00—Preparation of carboxylic acid amides
- C07C231/14—Preparation of carboxylic acid amides by formation of carboxamide groups together with reactions not involving the carboxamide groups
-
- 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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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention discloses a preparation method of N, N-dimethylaminopropyl methacrylamide, which comprises the following steps: adding organic amine into aqueous solution of soluble magnesium salt and soluble aluminum salt, then adding aqueous solution of inorganic base, carrying out neutralization precipitation, and carrying out hydrothermal treatment to obtain a catalyst; under the action of a catalyst and a polymerization inhibitor, methyl methacrylate and N, N-dimethyl-1, 3-propylene diamine are subjected to addition and amidation reaction to obtain an intermediate product, namely N- (3- (dimethylamino) propyl) -3- ((3- (dimethylamino) propyl) amino) -2-methylpropanamide; and then cracking, rectifying and separating the obtained intermediate product to obtain the N, N-dimethylaminopropyl methacrylamide. The method selects the catalyst with low cost, simple synthesis, high reaction activity and good selectivity to prepare the target product with high yield.
Description
Technical Field
The invention belongs to the technical field of synthesis of organic compounds, and particularly relates to a preparation method of N, N-dimethylaminopropyl methacrylamide.
Background
N, N-dimethylaminopropyl methacrylamide (DMAPMA) is an important chemical material, has polymerizable double bonds and tertiary amine groups, is used for manufacturing functional polymers, and can be widely used for producing fine polymer fields such as flocculating agents for water treatment, antistatic coatings, papermaking additives, oilfield chemicals, fiber additives, electronic chemicals, biological intelligent materials and the like.
Related reports exist in the synthetic technical route of dimethylaminopropyl methacrylamide. For example, U.S. Pat. nos. 4321411, 4206143 and 4549017 each disclose that methyl methacrylate and N, N-dimethyl-1, 3-propanediamine are used as raw materials, and are heated in the presence of an organotin catalyst and a polymerization inhibitor to undergo transesterification and rectified to give dimethylaminopropyl methacrylamide (see fig. 5 for a specific synthetic route). The method uses an organotin catalyst, has high biotoxicity and high price, and has the by-products close to the boiling point of the target product and difficult rectification separation. The requirements on the water index of the raw materials are strict, the byproducts of the azeotrope of the generated methanol and the methyl methacrylate are increased, the separation is difficult, and the selectivity is poor when the catalyst is reused.
U.S. Pat. No. 3, 3878247 discloses the preparation of N, N-dimethylaminopropyl methacrylamide by thermal cracking, first of all by the addition and amidation of methyl methacrylate with an excess of N, N-dimethyl-1, 3-propanediamine to give N- (3- (dimethylamino) propyl) -3- ((3- (dimethylamino) propyl) amino) -2-methylpropanamide, followed by removal of the addition group N, N-dimethyl-1, 3-propanediamine to give N, N-dimethylaminopropyl methacrylamide, the synthetic route being shown in FIG. 4. The method adopts a thermal cracking method without using a catalyst, but the method is easy to cause side reaction and has lower yield.
U.S. patent No. 4287363 and chinese patent No. CN10136270 use the same method, i.e., using metal chloride and nitrate as catalysts to prepare N, N-dimethylaminopropyl methacrylamide, which can reduce the reaction temperature and increase the reaction speed, but since the metal salt used in the method easily forms a coordination molecule with an amine group, the heavy component is increased, the yield is reduced, and using nitrate as a catalyst, explosion easily occurs, and the process safety is low.
Disclosure of Invention
Aiming at the problems existing in the prior art, the invention aims to provide a preparation method of N, N-dimethylaminopropyl methacrylamide, which aims to solve the defects of high toxicity, high cost, poor selectivity, low process safety, low yield and the like of a catalyst used in the existing synthesis method.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
a method for preparing N, N-dimethylamino propyl methacrylamide, comprising the following steps:
s1, carrying out addition and amidation reaction: under the action of a catalyst and a polymerization inhibitor, sequentially carrying out addition reaction and amidation reaction on methyl methacrylate and N, N-dimethyl-1, 3-propanediamine to obtain N- (3- (dimethylamino) propyl) -3- ((3- (dimethylamino) propyl) amino) -2-methylpropanamide;
wherein, the preparation steps of the catalyst are as follows: adding organic amine into aqueous solution of soluble magnesium salt and soluble aluminum salt, then adding aqueous solution of inorganic base, carrying out neutralization precipitation, and carrying out hydrothermal treatment to obtain a catalyst;
s2, cracking: the obtained N- (3- (dimethylamino) propyl) -3- ((3- (dimethylamino) propyl) amino) -2-methylpropanamide is cracked under the condition of reduced pressure to obtain N, N-dimethyl-1, 3-propanediamine and N, N-dimethylamino propyl methacrylamide, and then the N, N-dimethylamino propyl methacrylamide is obtained through rectification separation.
Preferably, in step S1, the molar ratio of the soluble magnesium salt to the soluble aluminum salt is 1 to 3:1, the soluble magnesium salt is Mg (NO 3 ) 2 ·6H 2 O or magnesium chloride, the soluble aluminum salt is Al (NO 3 ) 3 ·9H 2 O or aluminum chloride; the organic amine is N, N-dimethyl-1, 3-propylene diamine, and the dosage of the organic amine is 2 to 20 weight percent of soluble magnesium salt aqueous solution; the aqueous solution of the inorganic alkali is NaOH and Na 2 CO 3 NaOH and Na 2 CO 3 The concentration of (2) is 2.0M and the concentration of (0.5) is 0M respectively;
preferably, in step S1, the temperature of the hydrothermal treatment is 100-160 ℃, and the time of the hydrothermal treatment is 18-24 hours.
Preferably, in step S1, the molar ratio of methyl methacrylate to N, N-dimethyl-1, 3-propanediamine is 1:2.1 to 3.
Preferably, the polymerization inhibitor is one or the combination of more than two of phenothiazine, para-hydroxyanisole and 4-hydroxypiperidinol oxygen radical polymerization inhibitor, and the dosage of the polymerization inhibitor is 0.01-0.5 wt% of the total mass of the catalyst, the polymerization inhibitor, methyl methacrylate and N, N-dimethyl-1, 3-propanediamine.
Preferably, the catalyst is used in an amount of 0.2 to 10.0wt% based on the total mass of the catalyst, the polymerization inhibitor, the methyl methacrylate and the N, N-dimethyl-1, 3-propanediamine.
Preferably, in step S1, the process of sequentially performing the addition reaction and the amidation reaction is as follows: heating to 40-60 deg.c for addition reaction for 1-3.5 hr, heating to 120-135 deg.c for amidation reaction for 1-4 hr.
Preferably, in the step S2, the pressure during the pyrolysis is-0.09 to-0.098 Mpa, and the temperature of the pyrolysis is 160-200 ℃.
Compared with the prior art, the invention has the following beneficial effects:
(1) The catalyst used in the invention has simple preparation process and low cost, and does not relate to toxic and harmful products such as organic tin and the like or explosive products such as nitrate and the like;
(2) The catalyst used in the invention has high reaction activity and good selectivity, and the yield of the prepared N, N-dimethylaminopropyl methacrylamide is high;
(3) The catalyst used in the invention can be reused for a plurality of times, thereby saving the cost and reducing the residue of the heavy component kettle;
(4) The components in the preparation process of the invention are easy to rectify and purify, and the purity of the target finished product N, N-dimethylaminopropyl methacrylamide is high.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are needed in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a synthetic route diagram of N, N-dimethylaminopropyl methacrylamide provided by the invention;
FIG. 2 is an XRD pattern of the catalyst MC prepared in example 1;
FIG. 3 is a GC chromatogram of N, N-dimethylaminopropyl methacrylamide prepared in example 2;
FIG. 4 is a nuclear magnetic resonance spectrum of N, N-dimethylaminopropyl methacrylamide prepared in example 2;
FIG. 5 is a synthetic scheme for the preparation of N, N-dimethylaminopropyl methacrylamide in the prior art.
Detailed Description
In the following description, for purposes of explanation and not limitation, specific details are set forth such as the particular system architecture, techniques, etc., in order to provide a thorough understanding of the embodiments of the present invention. It will be apparent, however, to one skilled in the art that the present invention may be practiced in other embodiments that depart from these specific details.
Example 1
Referring to fig. 1, the synthetic route of N, N-dimethylaminopropyl methacrylamide is shown, and the preparation method comprises the following specific steps:
(1) Preparation of catalyst (MC): into a pressure-resistant stainless steel reaction vessel, 100mL of Mg (NO) having a concentration of 2M was added 3 ) 2 ·6H 2 O aqueous solution and 100mL of A1 (NO) with concentration of 2M 3 ) 3 ·9H 2 O aqueous solution, mixing, heating to 40 ℃, and dropwise adding NaOH and Na 2 CO 3 Wherein, naOH and Na in the mixed aqueous solution 2 CO 3 Continuously monitoring pH change at 2.0M and 0.5M respectively, stopping dripping when the pH is monitored to 9.5, sealing the reaction kettle, heating to 120 ℃, performing hydrothermal treatment, preserving heat for 24 hours, cooling, filtering, repeatedly washing with water to be neutral, drying at 90 ℃ for 5 hours, heating to 220 ℃, and drying for 2 hours to obtain a catalyst (MC); XRD analysis is carried out on the sample, and an XRD spectrum is shown in figure 2;
(2) In a round bottom flask with a heating, stirring, fractionating column and a condensing reflux distributor, adding 200g (2.0 mol) of methyl methacrylate, 550g (5.38 mol) of N, N-dimethyl-1, 3-propanediamine, a polymerization inhibitor (phenothiazine 1g, 1g of p-hydroxyanisole and 0.5g of 4-hydroxypiperidinol oxygen free radical) and 20g of catalyst (MC) in sequence, stirring and heating to 50 ℃ under normal pressure, keeping the temperature for 2 hours, then slowly heating to 120 ℃, taking methanol out of the top of the flask, keeping the temperature for 2 hours, reducing the pressure to-0.05 Mpa, and taking out excessive N, N-dimethyl-1, 3-propanediamine, and simultaneously obtaining an intermediate reaction product containing N- (3- (dimethylamino) propyl) -3- ((3- (dimethylamino) propyl) amino) -2-methylpropanamide;
(3) The obtained intermediate reaction product containing N- (3- (dimethylamino) propyl) -3- ((3- (dimethylamino) propyl) amino) -2-methylpropanamide is placed in a decompression system for catalytic pyrolysis, the system pressure is set to be minus 0.095Mpa, the temperature is firstly increased, when the temperature in a flask reaches 160 ℃, the reflux appears at the top of the tower, the full extraction operation is carried out, the pyrolysis liquid is obtained, the heating strength of the flask is kept, the pyrolysis liquid flow is kept relatively stable, when the temperature in the flask continuously increases, the pyrolysis reaction is stopped when the temperature in the flask reaches 200 ℃, 58g of residues are obtained, the main components are catalysts, polymerization inhibitors, uncleaved intermediates and the like, and the collected pyrolysis liquid is subjected to decompression rectification to obtain 317g of target product N, N-dimethylaminopropyl methacrylamide, the content of which is 99.2%, and the yield of which is 92.5%.
Example 2
The preparation method of the N, N-dimethylaminopropyl methacrylamide comprises the following specific steps:
(1) Preparation of catalyst (MC): into a pressure-resistant stainless steel reaction vessel, 100mL of Mg (NO) having a concentration of 2M was added 3 ) 2 ·6H 2 O aqueous solution and 100mL of A1 (NO) at a concentration of 1M 3 ) 3 ·9H 2 O aqueous solution, mixing, heating to 40 ℃, and dropwise adding NaOH and Na 2 CO 3 Wherein, naOH and Na in the mixed aqueous solution 2 CO 3 Continuously monitoring pH change at 2.0M and 0.5M respectively, stopping dripping when the pH is monitored to 9.5, sealing the reaction kettle, heating to 160 ℃, performing hydrothermal treatment, preserving heat for 20h, cooling, filtering, repeatedly washing with water to be neutral, drying at 90 ℃ for 5h, heating to 220 ℃, and drying for 2h to obtain the catalyst (MC);
(2) In a round bottom flask with a heating, stirring, fractionating column and a condensing reflux distributor, 200g (2.0 mol) of methyl methacrylate, 550g (5.38 mol) of N, N-dimethyl-1, 3-propanediamine, a polymerization inhibitor (phenothiazine 0.4g, 0.25g of p-hydroxyanisole and 0.34g of 4-hydroxypiperidinol oxygen free radical) and 20g of catalyst MC are sequentially added, stirring and heating to 50 ℃ under normal pressure, carrying out addition reaction for 2 hours, then slowly heating to 120 ℃, taking methanol out from the top of the flask, carrying out amidation reaction for 2 hours, reducing pressure to-0.05 Mpa, taking out excessive N, N-dimethyl-1, 3-propanediamine, and simultaneously obtaining an intermediate reaction product containing N- (3- (dimethylamino) propyl) -3- ((3- (dimethylamino) propyl) amino) -2-methylpropanamide;
(3) Placing the obtained intermediate reaction product containing N- (3- (dimethylamino) propyl) -3- ((3- (dimethylamino) propyl) amino) -2-methylpropanamide in a decompression system for cracking, setting the pressure of the system to be-0.095 Mpa, heating first, and when the temperature is raised to 160 ℃, refluxing the top of the tower, and carrying out full extraction operation to obtain a cracking solution; maintaining the heating intensity to keep the flow of the pyrolysis liquid relatively stable, continuously increasing the temperature, stopping the pyrolysis reaction when the temperature reaches 200 ℃, and obtaining 58g of residue at the moment, wherein the main components of the residue are a catalyst, a polymerization inhibitor, an uncleaved intermediate and the like; collecting the lysate, and rectifying the lysate under reduced pressure to obtain 315g of target product N, N-dimethylaminopropyl methacrylamide, wherein the content is 99.2%, and the yield is 91.6%. The obtained N, N-dimethylaminopropyl methacrylamide is characterized, and the obtained GC chromatograms and nuclear magnetic resonance spectra are shown in fig. 3 and 4.
Example 3
To a round-bottomed flask having a heating, stirring, fractionating column and a reflux condenser were successively added 200g (2.0 mol) of methyl methacrylate, 550g (5.38 mol) of N, N-dimethyl-1, 3-propanediamine, 0.6g of a polymerization inhibitor (phenothiazine, 0.37g of p-hydroxyanisole and 0.52g of 4-hydroxypiperidinol oxygen radical) and 58g of the residue obtained by cleavage reaction of example 2, and the mixture was stirred and heated to 55℃under normal pressure, followed by addition reaction for 2 hours, and then by slowly heating to 125℃to obtain methanol at the top of the flask, amidation reaction for 2 hours and decompression to-0.055 MPa, and an excess of N, N-dimethyl-1, 3-propanediamine was obtained, while obtaining an intermediate reaction product containing N- (3- (dimethylamino) propyl) -3- ((3- (dimethylamino) propyl) amino) -2-methylpropanamide.
Placing the obtained intermediate reaction product containing N- (3- (dimethylamino) propyl) -3- ((3- (dimethylamino) propyl) amino) -2-methylpropanamide in a decompression system for cracking, setting the pressure of the system to be-0.090 Mpa, heating first, and when the temperature is raised to 160 ℃, refluxing the top of the tower, and carrying out full extraction operation to obtain a cracking solution; maintaining the heating intensity to keep the flow of the pyrolysis liquid relatively stable, continuously increasing the temperature, stopping the pyrolysis reaction when the temperature reaches 198 ℃, and obtaining 60g of residue at the moment, wherein the main components of the residue are a catalyst, a polymerization inhibitor, an uncleaved intermediate and the like; collecting a lysate, rectifying the lysate under reduced pressure to obtain a final product, detecting the final product as a single spot by TLC, analyzing the final product as a single component by GC, identifying 325g of target product N, N-dimethylaminopropyl methacrylamide with the GC retention time being the same as that of the GC data of the example 2, and the content of the target product N, N-dimethylaminopropyl methacrylamide being 99.5%, and the yield being 95.1%.
Example 4
200g (2.0 mol) of methyl methacrylate, 580g (5.69 mol) of N, N-dimethyl-1, 3-propanediamine, 1.0g of polymerization inhibitor (phenothiazine, 0.62g of p-hydroxyanisole and 0.86g of 4-hydroxypiperidinol oxygen radical) and 60g of residue obtained by cleavage reaction in example 3 were sequentially added to a round bottom flask having a heating, stirring, fractionating column and a condensing reflux distributor, the temperature was raised to 60℃under normal pressure with stirring, the addition reaction was carried out for 2 hours, then the temperature was raised slowly to 135℃with methanol taken out from the top of the flask, amidation reaction was carried out for 2 hours, the pressure was reduced to-0.05 MPa, and an excessive amount of N, N-dimethyl-1, 3-propanediamine was taken out, and an intermediate reaction product containing N- (3- (dimethylamino) propyl) -3- ((3- (dimethylamino) propyl) amino) -2-methylpropanamide was obtained.
Placing the obtained intermediate reaction product containing N- (3- (dimethylamino) propyl) -3- ((3- (dimethylamino) propyl) amino) -2-methylpropanamide in a decompression system for cracking, setting the pressure of the system to be-0.095 Mpa, heating the system first, and when the temperature is raised to 165 ℃, refluxing the top of the tower, and carrying out full extraction operation to obtain a cracking solution; maintaining the heating intensity to keep the flow of the pyrolysis liquid relatively stable, continuously increasing the temperature, stopping the pyrolysis reaction when the temperature reaches 190 ℃, and obtaining 48g of residue at the moment, wherein the main components of the residue are a catalyst, a polymerization inhibitor, an uncleaved intermediate and the like; collecting a lysate, rectifying the lysate under reduced pressure to obtain a final product, detecting the final product as a single spot by TLC, analyzing the final product as a single component by GC, identifying 305g of target product N, N-dimethylaminopropyl methacrylamide with the GC retention time being identical to that of the GC data of the example 2, wherein the content is 99.6%, and the yield is 89.3%.
Example 5
200g (2.0 mol) of methyl methacrylate, 600g (5.88 mol) of N, N-dimethyl-1, 3-propanediamine, 1.0g of polymerization inhibitor (phenothiazine, 0.62g of p-hydroxyanisole and 0.43g of 4-hydroxypiperidinol oxygen radical) and 48g of residue obtained by cleavage reaction in example 4 are sequentially added into a round bottom flask with a heating, stirring, fractionating column and a condensing reflux distributor, stirring and heating are carried out to 45 ℃ under normal pressure, the addition reaction is carried out for 1.5h, then the temperature is slowly increased to 128 ℃, methanol is taken out from the top of the flask, amidation reaction is carried out for 2h, the pressure is reduced to-0.065 Mpa, and excessive N, N-dimethyl-1, 3-propanediamine is taken out, and meanwhile an intermediate reaction product containing N- (3- (dimethylamino) propyl) -3- ((3- (dimethylamino) propyl) amino) -2-methylpropanamide is obtained.
(3) Placing the obtained intermediate reaction product containing N- (3- (dimethylamino) propyl) -3- ((3- (dimethylamino) propyl) amino) -2-methylpropanamide in a decompression system for cracking, setting the pressure of the system to be-0.098 Mpa, heating the system firstly, and when the temperature is raised to 160 ℃, refluxing the top of the tower, and carrying out full extraction operation to obtain a cracking solution; maintaining the heating intensity to keep the flow of the pyrolysis liquid relatively stable, continuously increasing the temperature, stopping the pyrolysis reaction when the temperature reaches 200 ℃, and obtaining residue 62g at the moment, wherein the main components of the residue are a catalyst, a polymerization inhibitor, an uncleaved intermediate and the like; collecting a lysate, rectifying the lysate under reduced pressure to obtain a final product, detecting the final product as a single spot by TLC, analyzing the final product as a single component by GC, identifying 318g of target product N, N-dimethylaminopropyl methacrylamide with the GC retention time being the same as that of the GC data of the example 2, and the content of the target product N, N-dimethylaminopropyl methacrylamide being 99.4%, and the yield being 93.0%.
Comparative example 1
(1) Preparation of the catalyst: substantially the same as in example, except that N, N-dimethyl-1, 3-propanediamine was not added, catalyst MD was obtained;
(2) 200g (2.0 mol) of methyl methacrylate, 550g (5.38 mol) of N, N-dimethyl-1, 3-propylene diamine, a polymerization inhibitor (phenothiazine 1g, 1g of p-hydroxyanisole and 0.5g of 4-hydroxypiperidinol oxygen free radical) and 20g of catalyst MD are sequentially added into a round bottom flask with a heating, stirring, fractionating column and a condensing reflux distributor, stirring and heating are carried out at normal pressure to 50 ℃, an addition reaction is carried out for 2 hours, then the temperature is slowly increased to 120 ℃, methanol is taken out from the top of the flask, amidation reaction is carried out for 2 hours, the pressure is reduced to-0.05 Mpa, and excessive N, N-dimethyl-1, 3-propylene diamine is taken out, and meanwhile an intermediate reaction product is obtained;
(3) The obtained intermediate reaction product is placed in a decompression system for catalytic pyrolysis, the system pressure is set to be minus 0.095Mpa, the temperature is firstly increased, when the temperature in a flask reaches 160 ℃, the reflux appears at the top of the tower, the full extraction operation is carried out, the heating intensity of the flask is continuously kept, the flow rate of the pyrolysis liquid is kept relatively stable, the temperature in the flask is continuously increased, when the temperature in the flask reaches 200 ℃, the pyrolysis reaction is stopped, 158g of residues are obtained at the moment, the main components are catalysts, polymerization inhibitors, uncleaved intermediates and the like, the collected pyrolysis liquid is decompressed and rectified, the final product is obtained, the final product is detected as a single spot by TLC, the GC analysis is carried out, the GC retention time is the same as that of GC data of example 2, and the final product is identified as 185g of N, N-dimethylaminopropyl methacrylamide, the content is 99.1%, and the yield is 53.9%.
The present invention is not limited to the above-described specific embodiments, and various modifications may be made by those skilled in the art without inventive effort from the above-described concepts, and are within the scope of the present invention.
Claims (8)
1. A method for preparing N, N-dimethylaminopropyl methacrylamide, which is characterized by comprising the following steps:
s1, carrying out addition and amidation reaction: under the action of a catalyst and a polymerization inhibitor, sequentially carrying out addition reaction and amidation reaction on methyl methacrylate and N, N-dimethyl-1, 3-propanediamine to obtain N- (3- (dimethylamino) propyl) -3- ((3- (dimethylamino) propyl) amino) -2-methylpropanamide;
wherein, the preparation steps of the catalyst are as follows: adding organic amine into aqueous solution of soluble magnesium salt and soluble aluminum salt, then adding aqueous solution of inorganic base, carrying out neutralization precipitation, and carrying out hydrothermal reaction to obtain a catalyst;
s2, catalytic cracking: the obtained N- (3- (dimethylamino) propyl) -3- ((3- (dimethylamino) propyl) amino) -2-methylpropanamide is cracked under the condition of reduced pressure to obtain N, N-dimethyl-1, 3-propanediamine and N, N-dimethylamino propyl methacrylamide, and then the N, N-dimethylamino propyl methacrylamide is obtained through rectification separation.
2. The method for producing N, N-dimethylaminopropyl methacrylamide according to claim 1, wherein in step S1, the molar ratio of the soluble magnesium salt to the soluble aluminum salt is 1:1 to 3:1, the soluble magnesium salt is Mg (NO 3 ) 2 ·6H 2 O or magnesium chloride, the soluble aluminum salt is Al (NO 3 ) 3 ·9H 2 O or aluminum trichloride; the organic amine is N, N-dimethyl-1, 3-propylene diamine, and the dosage of the organic amine is 2 to 20 weight percent of soluble magnesium salt aqueous solution; the aqueous solution of the inorganic alkali is NaOH and Na 2 CO 3 Is used as a solvent.
3. The method for producing N, N-dimethylaminopropyl methacrylamide according to claim 1, wherein in step S1, the temperature of the hydrothermal treatment is 100 to 160 ℃, and the time of the hydrothermal treatment is 18 to 24 hours.
4. The method for producing N, N-dimethylaminopropyl methacrylamide according to claim 1, wherein in step S1, the molar ratio of methyl methacrylate to N, N-dimethyl-1, 3-propanediamine is 1:2.1 to 3.
5. The method for preparing N, N-dimethylaminopropyl methacrylamide according to claim 2, wherein the polymerization inhibitor is one or a combination of more than two of phenothiazine, para-hydroxyanisole and 4-hydroxypiperidinol oxygen radical polymerization inhibitor, and the amount of the polymerization inhibitor is 0.01-0.5 wt% of the total mass of the catalyst, the polymerization inhibitor, methyl methacrylate and N, N-dimethyl-1, 3-propanediamine.
6. The method for preparing N, N-dimethylaminopropyl methacrylamide according to claim 1, wherein the catalyst is used in an amount of 0.2-10.0wt% of the total mass of the catalyst, the polymerization inhibitor, methyl methacrylate and N, N-dimethyl-1, 3-propanediamine.
7. The method for producing N, N-dimethylaminopropyl methacrylamide according to claim 1, wherein in step S1, the sequential addition reaction and amidation reaction are performed as follows: heating to 40-60 deg.c for addition reaction for 1-3.5 hr, heating to 120-135 deg.c for amidation reaction for 1-4 hr.
8. The method for producing N, N-dimethylaminopropyl methacrylamide according to claim 1, wherein in step S2, the pressure during the cleavage is-0.09 to-0.098 MPa, and the cleavage temperature is 160 to 200 ℃.
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