CN117586165A - 2, 3-dihydroxyaziridinyl acrylamide DNMA and preparation method thereof - Google Patents
2, 3-dihydroxyaziridinyl acrylamide DNMA and preparation method thereof Download PDFInfo
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- CN117586165A CN117586165A CN202310903907.8A CN202310903907A CN117586165A CN 117586165 A CN117586165 A CN 117586165A CN 202310903907 A CN202310903907 A CN 202310903907A CN 117586165 A CN117586165 A CN 117586165A
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- acrylamide
- dihydroxyaziridinyl
- quaternary ammonium
- dnma
- hydroxide
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- -1 2, 3-dihydroxyaziridinyl acrylamide Chemical compound 0.000 title claims abstract description 60
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- 239000003054 catalyst Substances 0.000 claims abstract description 50
- 238000006243 chemical reaction Methods 0.000 claims abstract description 31
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 claims abstract description 31
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims abstract description 26
- 125000001453 quaternary ammonium group Chemical group 0.000 claims abstract description 26
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229940015043 glyoxal Drugs 0.000 claims abstract description 15
- 238000010438 heat treatment Methods 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims abstract description 13
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims abstract description 13
- 238000010992 reflux Methods 0.000 claims abstract description 12
- 239000002994 raw material Substances 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims description 21
- 239000000047 product Substances 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 13
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 238000005470 impregnation Methods 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 239000006228 supernatant Substances 0.000 claims description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 9
- 150000001412 amines Chemical group 0.000 claims description 9
- 238000000199 molecular distillation Methods 0.000 claims description 9
- 238000006116 polymerization reaction Methods 0.000 claims description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- 150000007522 mineralic acids Chemical class 0.000 claims description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 6
- 239000003112 inhibitor Substances 0.000 claims description 6
- 239000000376 reactant Substances 0.000 claims description 6
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 claims description 6
- 239000000706 filtrate Substances 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 5
- 239000002244 precipitate Substances 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- OKIZCWYLBDKLSU-UHFFFAOYSA-M N,N,N-Trimethylmethanaminium chloride Chemical compound [Cl-].C[N+](C)(C)C OKIZCWYLBDKLSU-UHFFFAOYSA-M 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 230000001105 regulatory effect Effects 0.000 claims description 4
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 4
- MFGOFGRYDNHJTA-UHFFFAOYSA-N 2-amino-1-(2-fluorophenyl)ethanol Chemical compound NCC(O)C1=CC=CC=C1F MFGOFGRYDNHJTA-UHFFFAOYSA-N 0.000 claims description 3
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 claims description 3
- HUCVOHYBFXVBRW-UHFFFAOYSA-M caesium hydroxide Inorganic materials [OH-].[Cs+] HUCVOHYBFXVBRW-UHFFFAOYSA-M 0.000 claims description 3
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 3
- 239000000920 calcium hydroxide Substances 0.000 claims description 3
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 3
- 239000007810 chemical reaction solvent Substances 0.000 claims description 3
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 3
- 239000000347 magnesium hydroxide Substances 0.000 claims description 3
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 3
- 230000007935 neutral effect Effects 0.000 claims description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- DPKBAXPHAYBPRL-UHFFFAOYSA-M tetrabutylazanium;iodide Chemical compound [I-].CCCC[N+](CCCC)(CCCC)CCCC DPKBAXPHAYBPRL-UHFFFAOYSA-M 0.000 claims description 3
- HWCKGOZZJDHMNC-UHFFFAOYSA-M tetraethylammonium bromide Chemical compound [Br-].CC[N+](CC)(CC)CC HWCKGOZZJDHMNC-UHFFFAOYSA-M 0.000 claims description 3
- YMBCJWGVCUEGHA-UHFFFAOYSA-M tetraethylammonium chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC YMBCJWGVCUEGHA-UHFFFAOYSA-M 0.000 claims description 3
- UQFSVBXCNGCBBW-UHFFFAOYSA-M tetraethylammonium iodide Chemical compound [I-].CC[N+](CC)(CC)CC UQFSVBXCNGCBBW-UHFFFAOYSA-M 0.000 claims description 3
- DDFYFBUWEBINLX-UHFFFAOYSA-M tetramethylammonium bromide Chemical compound [Br-].C[N+](C)(C)C DDFYFBUWEBINLX-UHFFFAOYSA-M 0.000 claims description 3
- RXMRGBVLCSYIBO-UHFFFAOYSA-M tetramethylazanium;iodide Chemical compound [I-].C[N+](C)(C)C RXMRGBVLCSYIBO-UHFFFAOYSA-M 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 12
- 239000007788 liquid Substances 0.000 description 10
- 239000000126 substance Substances 0.000 description 8
- 238000000746 purification Methods 0.000 description 6
- 238000005481 NMR spectroscopy Methods 0.000 description 4
- 238000004132 cross linking Methods 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 239000000908 ammonium hydroxide Substances 0.000 description 2
- 125000004069 aziridinyl group Chemical group 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 239000000976 ink Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000010926 purge Methods 0.000 description 2
- 230000036632 reaction speed Effects 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 102100035687 Bile salt-activated lipase Human genes 0.000 description 1
- 101710130200 Bile salt-activated lipase Proteins 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- WRQZHNBWNQMAPL-UHFFFAOYSA-N OC1NC1O Chemical group OC1NC1O WRQZHNBWNQMAPL-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000009988 textile finishing Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D203/00—Heterocyclic compounds containing three-membered rings with one nitrogen atom as the only ring hetero atom
- C07D203/04—Heterocyclic compounds containing three-membered rings with one nitrogen atom as the only ring hetero atom not condensed with other rings
- C07D203/06—Heterocyclic compounds containing three-membered rings with one nitrogen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
- C07D203/16—Heterocyclic compounds containing three-membered rings with one nitrogen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with acylated ring nitrogen atoms
- C07D203/18—Heterocyclic compounds containing three-membered rings with one nitrogen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with acylated ring nitrogen atoms by carboxylic acids, or by sulfur or nitrogen analogues thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0235—Nitrogen containing compounds
- B01J31/0239—Quaternary ammonium compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Abstract
The invention provides 2, 3-dihydroxyaziridinyl acrylamide DNMA and a preparation method thereof, wherein the preparation method comprises the following steps: s1: preparation of the supported quaternary ammonium base catalyst: heating and refluxing quaternary ammonium salt and hydroxide in alcohol solution to react and obtain supported quaternary ammonium base catalyst; s2: preparation of 2, 3-dihydroxyaziridinyl acrylamide: and (3) under the action of the supported quaternary ammonium base catalyst prepared in the step (S1), acrylamide and glyoxal are used as raw materials for reaction, so that the 2, 3-dihydroxyaziridinyl acrylamide is prepared. The preparation method can prepare the 2, 3-dihydroxyaziridinyl acrylamide DNMA with high purity, and has higher commercial value and popularization value.
Description
Technical Field
The invention relates to the field of chemical product preparation and purification methods, in particular to 2, 3-dihydroxyaziridinyl acrylamide DNMA and a preparation method thereof.
Background
2, 3-dihydroxyaziridinyl acrylamide (DNMA) is a novel crosslinking monomer with double bonds and reactive functional groups, and has good polymerization performance and simultaneously has a dihydroxyl ternary cyclic aziridine functional group due to the carbon-carbon double bonds of acrylamide and the aziridine group, so that the 2, 3-dihydroxyaziridinyl acrylamide has other special properties, has good application value in various industrial production, and can be widely applied to the aspects of adhesives, curing agents, coatings, paper processing, fiber processing, emulsion polymerization, high molecular emulsifiers, textile finishing agents, inks, printing inks, photosensitive materials and the like. Compared with methylolacrylamide (NMA for short), the terminal 2, 3-dihydroxyaziridine group in DNMA is compared with the terminal monohydroxymethyl-CH in NMA 2 OH is stable, so that the firmness and the crosslinking strength of the polymer produced by using DNMA as a crosslinking monomer are stronger than those of NMA, and moreover, the methylol acrylamide (NMA) is recently listed in the highly interesting Substance (SVHC) list regulated by the european union regulation of chemical registration, evaluation, permission and limitation (REACH) and in the blue mark BSSL forbidden substance list, so that it is clear that the development of a novel green crosslinking monomer is needed to replace the traditional NMA, the research on the application development and preparation and purification methods of DNMA in China is limited, and further research and development are still needed in a few application fields, so that the greater potential and value of the 2, 3-dihydroxyaziridinyl acrylamide DNMA are exerted.
At present, the literature and the patent of the method for synthesizing and purifying the high-purity 2, 3-dihydroxyaziridinyl acrylamide DNMA at home and abroad are temporarily unavailable, so that a synthetic and purifying method for producing the high-purity DNMA, which is convenient and green and can solve the technical problems, is needed to appear.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a preparation method of 2, 3-dihydroxyaziridinyl acrylamide DNMA to fill the gap in the field, and provide a preparation method of 3-dihydroxyaziridinyl acrylamide DNMA.
In order to solve the problems, the invention provides a preparation method of 2, 3-dihydroxyaziridinyl acrylamide DNMA, which comprises the following steps:
s1: preparation of the supported quaternary ammonium base catalyst: heating and refluxing quaternary ammonium salt and hydroxide in alcohol solution to react and obtain supported quaternary ammonium base catalyst;
s2: preparation of 2, 3-dihydroxyaziridinyl acrylamide: and (3) under the action of the supported quaternary ammonium base catalyst prepared in the step (S1), acrylamide and glyoxal are used as raw materials for reaction, so that the 2, 3-dihydroxyaziridinyl acrylamide is prepared.
Preferably, in the step S1, the heating reflux reaction includes: dissolving quaternary ammonium salt in an alcohol solution, adding a certain amount of hydroxide, heating and refluxing for reaction, further centrifugally separating out salt precipitate, and collecting supernatant for later use; and immersing the activated mesoporous aluminum oxide carrier into the supernatant, standing and drying to obtain the supported quaternary ammonium base catalyst.
Preferably, the impregnation is an isovolumetric impregnation method, and the impregnation time is 12-48 hours; the drying mode is that room temperature nitrogen is used for drying; the drying time is 24-48 h.
Too short impregnation time can prevent ions from fully diffusing into the pore channels of the solid phase carrier, too long impregnation time can reduce the catalyst preparation efficiency, and too high drying temperature can lead to quaternary ammonium hydroxide decomposition.
In the step S1, the supported quaternary ammonium base catalyst is mesoporous alumina supported quaternary ammonium base; the alcohol is one of methanol, ethanol, propanol, isopropanol, n-butanol, ethylene glycol and propylene glycol; the quaternary ammonium salt is one of tetramethyl ammonium chloride, tetramethyl ammonium bromide, tetramethyl ammonium iodide, tetraethyl ammonium chloride, tetraethyl ammonium bromide, tetraethyl ammonium iodide, tetrabutyl ammonium chloride, tetrabutyl ammonium bromide and tetrabutyl ammonium iodide; the hydroxide is one or two of sodium hydroxide, potassium hydroxide, cesium hydroxide, calcium hydroxide, magnesium hydroxide and hydroxylamine; and the molar ratio of the quaternary ammonium salt to the hydroxide is 1: (1.3-3).
As a preferred solution, the operation step of step S2 includes: placing the quaternary ammonium base catalyst prepared in the step S1 in a reactor, and adding water as a reaction solvent; respectively adding reactants of acrylamide, glyoxal and polymerization inhibitor; heating the system to react for a period of time; after the reaction is finished, filtering the catalyst while the catalyst is hot, washing the catalyst with clear water, and combining the catalyst with the filtrate to obtain the 2, 3-dihydroxyaziridinyl acrylamide.
As a preferable scheme, the molar ratio of the acrylamide to the glyoxal is 1: (0.96-0.98); the molar ratio of the acrylamide to the polymerization inhibitor is 1: (0.005-0.008); the molar ratio of the acrylamide to the water is 1: (0.7-1.3); the addition amount of the supported quaternary amine base catalyst is 10-35 wt% of that of the acrylamide.
Too low a catalyst content results in a slower reaction rate, and too high a catalyst content results in an increase in byproducts.
In the step S2, the reaction temperature is 50-70 ℃ and the reaction time is 2-7 h. When the reaction temperature is too low, the reaction speed is slower, and polymerization products are easy to appear in a system with too high temperature, so that the products are difficult to separate.
Preferably, after the step S2, the method further includes a step S3 of purifying a product, including:
s3: and (3) purifying a product: and (2) adding inorganic acid into the 2, 3-dihydroxyaziridinyl acrylamide prepared in the step (S2), stirring, regulating a system to be neutral, transferring reactants into a short-path molecular distiller, and obtaining the high-purity 2, 3-dihydroxyaziridinyl acrylamide through molecular distillation.
In a preferred embodiment, in the step S3, the inorganic acid is one of dilute sulfuric acid or dilute hydrochloric acid, and 1mol/L; the molecular distillation conditions are as follows: distilling at 90-95deg.C for 2-10 hr.
The invention aims to solve the other technical problem of providing 2, 3-dihydroxyaziridinyl acrylamide to solve the problem of low purity of the conventional 2, 3-dihydroxyaziridinyl acrylamide.
In order to solve the above problems, the present invention provides a 2, 3-dihydroxyaziridinylacrylamide prepared by the above preparation method.
The invention adopts a molecular distillation method in the purification process of 2, 3-dihydroxyaziridinyl acrylamide, molecular distillation is a special liquid-liquid separation technology, and is different from the traditional distillation which relies on the principle of boiling point differential separation, but realizes separation by the difference of the average free path of molecular movement of different substances. When the liquid mixture flows along the heating plate and is heated, light and heavy molecules can escape from the liquid surface to enter the gas phase, and because the free ranges of the light and heavy molecules are different, the movement distances of molecules of different substances are different after the molecules escape from the liquid surface, if a condensing plate can be properly arranged, the light molecules reach the condensing plate to be condensed and discharged, and the heavy molecules can not reach the condensing plate to be discharged along the mixed liquid. Thus, the purpose of separating substances is achieved. The 2, 3-dihydroxyaziridinylacrylamide solution obtained by synthesis is purified by a short-range molecular distiller, and a high-purity 2, 3-dihydroxyaziridinylacrylamide product is obtained, and the preparation method has the characteristics of high chemical purity, less water content, less glyoxal residue and the like.
According to the synthesis method for preparing the 2, 3-dihydroxyaziridinyl acrylamide by taking acrylamide and glyoxal as raw materials, the supported quaternary ammonium hydroxide is adopted as a catalyst, the reaction condition is mild, the selectivity is high, and the reaction system can realize the efficient conversion of the raw materials without adding other organic solvents as reaction media. The supported quaternary amine base catalyst used in the invention has high catalytic activity, simple preparation process and low cost. The reaction temperature of the system is lower, the reaction time is shorter, the energy consumption is greatly reduced, and the generation of byproducts is avoided. And in the post-treatment process, a large amount of inorganic acid is not needed to be added as a neutralizing agent, so that the operation steps of post-treatment are greatly saved, molecular distillation is adopted in the purification process, three wastes are not generated basically in the synthesis and purification processes, and the prepared product is high-purity 2, 3-dihydroxyaziridinyl acrylamide colorless liquid. The used supported quaternary amine base catalyst can be recycled after being treated, so that the production cost is reduced.
In conclusion, the method has the advantages of mild reaction process conditions, easy control, high safety, simple post-treatment and easy industrial production, and can obtain a high-purity product.
Drawings
FIG. 1 is an infrared spectrum (FT-IR) of 2, 3-dihydroxyaziridinylacrylamide in examples;
FIG. 2 is the resonance hydrogen spectrum (1H-NMR) of the nuclear magnetic resonance of 2, 3-dihydroxyaziridinyl acrylamide in the example.
Detailed Description
The following description of the present invention will be made clearly and fully, and it is apparent that the embodiments described are some, but not all, of the embodiments of the present invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The invention provides a preparation method of 2, 3-dihydroxyaziridinyl acrylamide DNMA, which comprises the following steps:
s1: preparation of the supported quaternary ammonium base catalyst: heating and refluxing quaternary ammonium salt and hydroxide in alcohol solution to react and obtain supported quaternary ammonium base catalyst;
s2: preparation of 2, 3-dihydroxyaziridinyl acrylamide: and (3) under the action of the supported quaternary ammonium base catalyst prepared in the step (S1), acrylamide and glyoxal are used as raw materials for reaction, so that the 2, 3-dihydroxyaziridinyl acrylamide is prepared.
Preferably, in the step S1, the heating reflux reaction includes: dissolving quaternary ammonium salt in an alcohol solution, adding a certain amount of hydroxide, heating and refluxing for reaction, further centrifugally separating out salt precipitate, and collecting supernatant for later use; and immersing the activated mesoporous aluminum oxide carrier into the supernatant, standing and drying to obtain the supported quaternary ammonium base catalyst.
Preferably, the impregnation is an isovolumetric impregnation method, and the impregnation time is 12-48 hours; the drying mode is that room temperature nitrogen is used for drying; the drying time is 24-48 h.
Preferably, in the step S1, the supported quaternary ammonium base catalyst is mesoporous alumina supported quaternary ammonium base; the alcohol is one of methanol, ethanol, propanol, isopropanol, n-butanol, ethylene glycol and propylene glycol; the quaternary ammonium salt is one of tetramethyl ammonium chloride, tetramethyl ammonium bromide, tetramethyl ammonium iodide, tetraethyl ammonium chloride, tetraethyl ammonium bromide, tetraethyl ammonium iodide, tetrabutyl ammonium chloride, tetrabutyl ammonium bromide and tetrabutyl ammonium iodide; the hydroxide is one or two of sodium hydroxide, potassium hydroxide, cesium hydroxide, calcium hydroxide, magnesium hydroxide and hydroxylamine; and the molar ratio of the quaternary ammonium salt to the hydroxide is 1: (1.3-3).
Preferably, the operation step of step S2 includes: placing the quaternary ammonium base catalyst prepared in the step S1 in a reactor, and adding water as a reaction solvent; respectively adding reactants of acrylamide, glyoxal and polymerization inhibitor; heating the system to react for a period of time; after the reaction is finished, filtering the catalyst while the catalyst is hot, washing the catalyst with clear water, and combining the catalyst with the filtrate to obtain the 2, 3-dihydroxyaziridinyl acrylamide.
Preferably, the molar ratio of the acrylamide to the glyoxal is 1: (0.96-0.98); the molar ratio of the acrylamide to the polymerization inhibitor is 1: (0.005-0.008); the molar ratio of the acrylamide to the water is 1: (0.7-1.3); the addition amount of the supported quaternary amine base catalyst is 10-35 wt% of that of the acrylamide.
Preferably, in the step S2, the reaction temperature is 50-70 ℃ and the reaction time is 2-7 h. When the reaction temperature is too low, the reaction speed is slower, and polymerization products are easy to appear in a system with too high temperature, so that the products are difficult to separate.
Preferably, after step S2, the method further includes step S3 of product purification, including:
s3: and (3) purifying a product: and (2) adding inorganic acid into the 2, 3-dihydroxyaziridinyl acrylamide prepared in the step (S2), stirring, regulating a system to be neutral, transferring reactants into a short-path molecular distiller, and obtaining the high-purity 2, 3-dihydroxyaziridinyl acrylamide through molecular distillation.
Preferably, in the step S3, the inorganic acid is one of dilute sulfuric acid or dilute hydrochloric acid, and 1mol/L; the molecular distillation conditions are as follows: distilling at 90-95deg.C for 2-10 hr.
The invention also provides 2, 3-dihydroxyaziridinyl acrylamide, and the 2, 3-dihydroxyaziridinyl acrylamide is prepared by the preparation method.
In order to further describe the scope of the present invention, the following examples are provided to describe the technical aspects of the present invention in conjunction with specific data:
example 1
2, 3-dihydroxyaziridinylacrylamide prepared by the preparation method described above:
s1: 350ml of absolute ethanol, 11g (0.1 mol) of tetramethyl ammonium chloride, 5.2g (0.13 mol) of sodium hydroxide, and heated under reflux for 4 hours were placed in a 500ml round-bottomed flask, cooled to room temperature, and the precipitate was separated by centrifugation, and 200ml of the supernatant was obtained. About 200g of calcined activated alumina (alpha-Al 2O 3) was added to the supernatant to ensure that all of the alumina was immersed in the solution and allowed to stand at room temperature for 24 hours. Filtering out mesoporous alumina, purging with nitrogen at room temperature for 24 hours until the mesoporous alumina is dried to obtain a supported quaternary amine base catalyst, and preserving the supported quaternary amine base catalyst in a vacuum dryer for standby, wherein the obtained catalyst is referred to as Cat Me 4 NOH/AO。
S2: 120g Cat Me was added to a 500ml round bottom flask 4 NOH/AO, 110ml of deionized water was added, 7.5g (0.06 mol) of p-methoxyphenol was added to the system at room temperature, the temperature of the system was gradually raised to 65℃with 600g (8.45 mol) of acrylamide, and the mixture was mechanically stirred until acrylamide was completely dissolved, and 464.32g (8 mol) of glyoxal was added to the system in portions. After the addition is completed, the reaction is carried out for 3 hours at 68-70 ℃, and then the yarn for the catalyst in the system is used when the catalyst is still hotThe cloth was filtered off and the mesoporous alumina was carefully washed with a small amount of deionized water (50 ml).
S3: a small amount of 1M dilute sulfuric acid (about 10 ml) is added into the obtained filtrate, and the pH value of the system is adjusted to 7.5-8.0. The reaction solution was transferred to a short path molecular still and molecular distilled at 90℃for 4 hours. The product was collected from a discharge tube located at the bottom of the evaporator to give 991.64g of a liquid, resulting in a pale yellow transparent 2, 3-dihydroxyaziridinylacrylamide liquid.
The reaction yield was 96.01% as measured in example 1 above, and it was found that the purity was 99.04%, the moisture content was 0.05% and glyoxal was 58ppm.
Example 2
2, 3-dihydroxyaziridinylacrylamide prepared by the preparation method described above:
s1: 350ml of absolute ethanol, 15g (0.1 mol) of tetrabutylammonium bromide, 11.2g (0.2 mol) of potassium hydroxide, and heated under reflux for 4 hours were placed in a 500ml round-bottomed flask, cooled to room temperature, and the precipitate was separated by centrifugation, and 200ml of the supernatant was collected. About 200g of calcined activated aluminum oxide (. Alpha. -Al) was added to the supernatant 2 O 3 ) Ensure that the aluminum oxide is fully immersed in the solution and stands for 24 hours at room temperature. Filtering out mesoporous alumina, purging with nitrogen at room temperature for 24 hours until the mesoporous alumina is dried to obtain a supported quaternary amine base catalyst, and preserving the supported quaternary amine base catalyst in a vacuum dryer for standby, wherein the obtained catalyst is called Cat Bu4NOH/AO.
S2 in a 500ml round bottom flask, 150g Cat Bu was added 4 NOH/AO, 170g of deionized water was added, 4.4g (0.04 mol) of hydroquinone, 579g (8 mol) of acrylamide were added to the system, the temperature of the system was gradually raised to 50 ℃, and the system was mechanically stirred until the acrylamide was completely dissolved, and 450.39g (7.76 mol) of glyoxal was added to the system in portions. After the addition was completed, the reaction was carried out at 50℃for 6 hours, and then the mesoporous alumina in the system was filtered off with gauze while it was still hot, and the mesoporous alumina was carefully washed with a small amount of deionized water (30 ml).
S3, adding a small amount of 1M dilute hydrochloric acid (about 8 ml) into the obtained filtrate, and adjusting the pH value of the system to 7.5-8.0. The reaction solution was transferred to a short path molecular still and molecular distilled at 95℃for 3 hours. The product was collected from a discharge tube located at the bottom of the evaporator to give 951.87g of a liquid, resulting in a pale yellow transparent 2, 3-dihydroxyaziridinylacrylamide liquid.
The reaction yield was 94.98%, and it was found that the purity was 98.6%, the moisture content was 0.2% and glyoxal remained at 36ppm.
As shown in fig. 1, the high purity grade 2, 3-dihydroxyaziridinylacrylamide obtained by the preparation of the present invention is shown in fig. 1 (example 1), and each characteristic peak is analyzed as follows: 3207cm-1 is O-H telescopic vibration 1661cm -1 Stretching vibration of C=O, 1595cm -1 C=C stretching vibration, 1134cm -1 Is C-N telescopic vibration of 1057cm -1 Is asymmetric telescopic vibration of C-O.
As shown in FIG. 2, FIG. 2 shows the `HNMR` of the product obtained by the preparation of the present invention in high purity grade 2, 3-dihydroxyaziridinyl acrylamide nuclear magnetic resonance (1H-NMR) (example 1), using deuteration reagent CDCl3 as solvent, TMS as internal standard, bruker Nuclear Magnetic Resonance (NMR) for analysis of the peaks ascribed to delta 5.77 (dd, 1H, CH) 2 ＝)，5.65(d，2H，-N-CH-)，4.51(t，2H，-O-CH-)，2.07(m，2H，-CH-)。
Further development of the above examples 1 and 2 further prove that the 2, 3-dihydroxyaziridinyl acrylamide prepared by the method has high purity, high reaction yield, and high commercial value and production popularization value.
Although the present disclosure is described above, the scope of protection of the present disclosure is not limited thereto. Various changes and modifications may be made by one skilled in the art without departing from the spirit and scope of the disclosure, and these changes and modifications will fall within the scope of the invention.
Claims (10)
1. A preparation method of 2, 3-dihydroxyaziridinyl acrylamide DNMA is characterized in that: the method comprises the following steps:
s1: preparation of the supported quaternary ammonium base catalyst: heating and refluxing quaternary ammonium salt and hydroxide in alcohol solution to react and obtain supported quaternary ammonium base catalyst;
s2: preparation of 2, 3-dihydroxyaziridinyl acrylamide: and (3) under the action of the supported quaternary ammonium base catalyst prepared in the step (S1), acrylamide and glyoxal are used as raw materials for reaction, so that the 2, 3-dihydroxyaziridinyl acrylamide is prepared.
2. The method for preparing 2, 3-dihydroxyaziridinyl acrylamide DNMA according to claim 1, wherein: in the step S1, the heating reflux reaction includes: dissolving quaternary ammonium salt in an alcohol solution, adding a certain amount of hydroxide, heating and refluxing for reaction, further centrifugally separating out salt precipitate, and collecting supernatant for later use; and immersing the activated mesoporous aluminum oxide carrier into the supernatant, standing and drying to obtain the supported quaternary ammonium base catalyst.
3. The method for preparing 2, 3-dihydroxyaziridinyl acrylamide DNMA according to claim 2, wherein: the impregnation is an isovolumetric impregnation method, and the impregnation time is 12-48 hours; the drying mode is that room temperature nitrogen is used for drying; the drying time is 24-48 h.
4. The method for preparing 2, 3-dihydroxyaziridinyl acrylamide DNMA according to claim 1, wherein: in the step S1, the supported quaternary ammonium base catalyst is mesoporous aluminum oxide supported quaternary ammonium base; the alcohol is one of methanol, ethanol, propanol, isopropanol, n-butanol, ethylene glycol and propylene glycol; the quaternary ammonium salt is one of tetramethyl ammonium chloride, tetramethyl ammonium bromide, tetramethyl ammonium iodide, tetraethyl ammonium chloride, tetraethyl ammonium bromide, tetraethyl ammonium iodide, tetrabutyl ammonium chloride, tetrabutyl ammonium bromide and tetrabutyl ammonium iodide; the hydroxide is one or two of sodium hydroxide, potassium hydroxide, cesium hydroxide, calcium hydroxide, magnesium hydroxide and hydroxylamine; and the molar ratio of the quaternary ammonium salt to the hydroxide is 1: (1.3-3).
5. The method for preparing 2, 3-dihydroxyaziridinyl acrylamide DNMA according to claim 1, wherein: the operation steps of the step S2 include: placing the quaternary ammonium base catalyst prepared in the step S1 in a reactor, and adding water as a reaction solvent; respectively adding reactants of acrylamide, glyoxal and polymerization inhibitor; heating the system to react for a period of time; after the reaction is finished, filtering the catalyst while the catalyst is hot, washing the catalyst with clear water, and combining the catalyst with the filtrate to obtain the 2, 3-dihydroxyaziridinyl acrylamide.
6. The process for preparing 2, 3-dihydroxyaziridinyl acrylamide DNMA according to claim 5, wherein: the molar ratio of the acrylamide to the glyoxal is 1: (0.96-0.98); the molar ratio of the acrylamide to the polymerization inhibitor is 1: (0.005-0.008); the molar ratio of the acrylamide to the water is 1: (0.7-1.3); the addition amount of the supported quaternary amine base catalyst is 10-35 wt% of that of the acrylamide.
7. The method for preparing 2, 3-dihydroxyaziridinyl acrylamide DNMA according to claim 1, wherein: in the step S2, the reaction temperature is 50-70 ℃ and the reaction time is 2-7 h.
8. The method for preparing 2, 3-dihydroxyaziridinyl acrylamide DNMA according to claim 1, wherein:
after the step S2, the method also comprises the step S3 of purifying the product, comprising the following steps:
s3: and (3) purifying a product: and (2) adding inorganic acid into the 2, 3-dihydroxyaziridinyl acrylamide prepared in the step (S2), stirring, regulating a system to be neutral, transferring reactants into a short-path molecular distiller, and obtaining the high-purity 2, 3-dihydroxyaziridinyl acrylamide through molecular distillation.
9. The method for preparing 2, 3-dihydroxyaziridinyl acrylamide DNMA according to claim 8, wherein: in the step S3, the inorganic acid is one of dilute sulfuric acid or dilute hydrochloric acid, and the mol/L is 1; the molecular distillation conditions are as follows: distilling at 90-95deg.C for 2-10 hr.
10. 2, 3-dihydroxyaziridinylacrylamide, characterized in that the 2, 3-dihydroxyaziridinylacrylamide is prepared by the preparation method according to any of claims 1-9.
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