CN113441118B - Surface molecular imprinting functionalized adsorbent, preparation method thereof and purification method of hexamethylenediamine - Google Patents

Surface molecular imprinting functionalized adsorbent, preparation method thereof and purification method of hexamethylenediamine Download PDF

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CN113441118B
CN113441118B CN202110881293.9A CN202110881293A CN113441118B CN 113441118 B CN113441118 B CN 113441118B CN 202110881293 A CN202110881293 A CN 202110881293A CN 113441118 B CN113441118 B CN 113441118B
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adsorbent
azepine
carrier
hexamethylenediamine
organic solvent
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CN113441118A (en
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王刚
张曦
丁克鸿
徐林
王根林
汪洋
许越
郭玉秀
陆仁标
殷剑虎
王敏娟
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Jiangsu Yangnong Chemical Group Co Ltd
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Jiangsu Yangnong Chemical Group Co Ltd
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Priority to PCT/CN2022/104898 priority patent/WO2023011117A1/en
Priority to JP2023577930A priority patent/JP2024525358A/en
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    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/26—Synthetic macromolecular compounds
    • B01J20/268—Polymers created by use of a template, e.g. molecularly imprinted polymers
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
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    • B01J20/08—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04 comprising aluminium oxide or hydroxide; comprising bauxite
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
    • B01J20/14—Diatomaceous earth
    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
    • B01J20/16—Alumino-silicates
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    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
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    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
    • C07C209/82—Purification; Separation; Stabilisation; Use of additives
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/52—Amides or imides
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    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
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    • C08J2335/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical, and containing at least one other carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Derivatives of such polymers
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Abstract

The invention provides a surface molecular imprinting functionalized adsorbent, a preparation method thereof and a purification method of hexamethylenediamine, wherein the adsorbent comprises a carrier and surface molecules loaded on the carrier; a imprinting cavity is formed between the surface molecules, and the imprinting cavity is matched with the azepine compound; the adsorbent has a short preparation flow, is suitable for industrial production, has a specific adsorption effect on the azepine compound, can be well suitable for adsorption separation of trace impurities in hexamethylenediamine, and remarkably improves the product purity of hexamethylenediamine.

Description

Surface molecular imprinting functionalized adsorbent, preparation method thereof and purification method of hexamethylenediamine
Technical Field
The invention relates to the technical field of separation, in particular to a surface molecular imprinting functionalized adsorbent, a preparation method thereof and a purifying method of hexamethylenediamine.
Background
Nylon 66 is used as the first of five engineering plastics, has extremely wide application in the fields of machinery and electric appliances, and is mainly applied to gears, bearings, electronic and electric appliances, automobile parts and the like. Compared with other general plastics, the nylon 66 has the characteristics of high mechanical strength, good toughness and good wear resistance, and has the excellent performances of self-lubricity, flame retardance, no toxicity, environmental protection and the like. Nylon 66 is a thermoplastic polymer, is a polycrystalline semi-crystalline polymer, is formed by polycondensation of adipic acid and hexamethylenediamine, and is a class of polyamides.
Hexamethylenediamine is a key intermediate for producing nylon 66, is an important chemical raw material, has great influence on the quality of nylon 66 products due to the purity of hexamethylenediamine, and has high requirements on the purity of raw materials due to the polycondensation reaction of high polymers. The synthesis method of hexamethylenediamine mainly comprises a caprolactam method, an adiponitrile method and a hexanediol method, the methods inevitably use rectification to refine hexamethylenediamine, the hexamethylenediamine generates side reaction in the rectification process to generate 3,4,5, 6-tetrahydro-2H-azepine, and the impurities are difficult to thoroughly remove in the rectification process.
CN103936595a discloses a refining method of crude hexamethylenediamine, which adopts a tower for rectification separation to obtain hexamethylenediamine with 99.99% content, but the method has low separation efficiency and high energy consumption.
CN101939286a discloses a purification method of hexamethylenediamine, which separates tetrahydrojingpi present in hexamethylenediamine by distillation, but the method does not involve the separation of 3,4,5, 6-tetrahydro-2H-azepine during the rectification on the one hand, and the separation efficiency of the method is low.
CN106810455a discloses a method for producing high-quality hexamethylenediamine, which comprises the steps of distilling and purifying semi-finished hexamethylenediamine for multiple times to obtain high-quality hexamethylenediamine, dehydrating, removing light components and removing heavy components according to different boiling points of impurities in the semi-finished hexamethylenediamine by adopting a vacuum rectification technology, and finally obtaining the hexamethylenediamine with purity more than or equal to 99.9%, wherein the purity is still lower and the energy consumption is higher.
Thus, there is a need for a gentle preparation process that removes 3,4,5, 6-tetrahydro-2H-azepine from hexamethylenediamine crude products to meet the downstream polycondensation requirements for nylon 66.
Disclosure of Invention
In view of the problems in the prior art, the invention provides the surface molecular imprinting functionalized adsorbent, the preparation method thereof and the purification method of hexamethylenediamine, wherein the adsorbent can specifically adsorb azepine compounds, has a specific adsorption effect on impurities in hexamethylenediamine, and solves the problem that trace impurities in the existing hexamethylenediamine are difficult to remove so as to influence downstream nylon products.
To achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a surface molecularly imprinted functionalized adsorbent comprising a support and a surface molecule supported on the support;
and imprinting cavities are formed between the surface molecules and are matched with the azepine compounds.
The adsorbent provided by the invention has the imprinting cavity matched with the azepine compound, so that the azepine compound can be specifically adsorbed, and the adsorbent has an excellent selective separation effect when applied to the separation process of the azepine compound.
Preferably, the surface molecule is capable of forming a weak chemical bond with an azepine compound.
Preferably, the weak chemical bond comprises a hydrogen bond.
The surface molecules can form weak chemical bonds such as hydrogen bonds with the azepine compounds, so that the azepine compounds can be specifically adsorbed, and the difficulty in separating the azepine compounds from other substances is reduced.
Preferably, the imprinting cavity is matched with the molecular space, shape and group of the azepine compound. Thereby realizing the biospecific adsorption similar to the antibody-antigen and realizing the selective adsorption of trace or trace azepine compounds.
Preferably, the support comprises any one or a combination of at least two of alumina, silica, activated carbon, ZSM-5 molecular sieve or montmorillonite, wherein typical but non-limiting combinations are combinations of alumina and activated carbon, combinations of silica and ZSM-5 molecular sieve, combinations of alumina and silica, combinations of activated carbon and ZSM-5 molecular sieve, preferably alumina.
Preferably, the particle diameter of the adsorbent is 50nm to 5. Mu.m, and may be, for example, 50nm, 60nm, 70nm, 80nm, 90nm, 100nm, 500nm, 1. Mu.m, 1.5. Mu.m, 2. Mu.m, 2.5. Mu.m, 3. Mu.m, 3.5. Mu.m, 4. Mu.m, 4.5. Mu.m, 5. Mu.m, or the like
Preferably, the specific surface area of the adsorbent is 100-1000 m 2 /g, for example, may be 100m 2 /g、200m 2 /g、300m 2 /g、400m 2 /g、500m 2 /g、600m 2 /g、700m 2 /g、800m 2 /g、900m 2 /g or 1000m 2 /g, etc.
Preferably, the azepine compound is selected from 3,4,5, 6-tetrahydro-2H-azepine.
Preferably, the carrier is an amino group-supporting carrier.
The invention further preferably selects the carrier loaded with the amino, and the amino on the surface of the carrier can be well combined with the cross-linking agent so as to connect surface molecules, so that the performance of the adsorbent is more stable.
Preferably, the surface molecules comprise polymerized molecules which polymerize with functional monomers, cross-linking agents and azepine compounds and then remove the azepine compounds.
The surface molecules are realized by seed surface molecular imprinting, the azepine compound is polymerized and then removed, imprinting cavities among the surface molecules are vacated, and the adsorption specificity is improved.
Preferably, the functional monomer is selected from amines and/or pyridines, including any one or a combination of at least two of acrylamide, o-phenylenediamine or 2-vinylpyridine, wherein typical but non-limiting combinations are combinations of acrylamide and o-phenylenediamine, combinations of 2-vinylpyridine and o-phenylenediamine, combinations of acrylamide and 2-vinylpyridine, combinations of acrylamide, o-phenylenediamine and 2-vinylpyridine.
Preferably, the crosslinker comprises any one or a combination of at least two of ethylene glycol diglycidyl ether, ethylene glycol dimethacrylate, or N, N-methylenebisacrylamide, wherein typical but non-limiting combinations are combinations of ethylene glycol diglycidyl ether and ethylene glycol dimethacrylate, combinations of ethylene glycol dimethacrylate and N, N-methylenebisacrylamide, and combinations of ethylene glycol diglycidyl ether and N, N-methylenebisacrylamide.
In a second aspect, the present invention provides a method for preparing a surface molecularly imprinted functionalized adsorbent according to the first aspect, the method comprising the steps of:
(1) Prepolymerizing the functional monomer and the azepine compound template to obtain a prepolymerized reaction material;
(2) The pre-polymerization reaction material, the carrier, the cross-linking agent and the initiator are subjected to polymerization reaction to obtain polymer particles;
(3) And removing the azepine compound template from the polymer particles to obtain the surface molecular imprinting functionalized adsorbent.
According to the preparation method of the adsorbent provided by the second aspect of the invention, the azepine compound template and the functional monomer are prepolymerized and then are loaded on the carrier through reaction with the crosslinking agent and the carrier, and finally template molecules in the template are removed, so that an imprinting cavity matched with the azepine compound template is reserved between surface molecules loaded on the surface of the carrier, the adsorbent has specific adsorption performance on the azepine compound during use, and the excellent adsorbent is provided for solving the separation of the azepine compound template. In addition, the method of pre-polymerizing the azepine compound template and the functional monomer by weakening chemical bonds such as hydrogen bonds and polymerizing the functional monomer can better ensure the combination of the azepine compound template and the functional monomer, avoid adverse reaction of the azepine compound template and a cross-linking agent, and ensure the matching property of a imprinting cavity and the azepine compound molecule.
Preferably, the azepine compound template of step (1) is selected from 3,4,5, 6-tetrahydro-2H-azepine.
The invention preferably selects a template aiming at specific impurities in hexamethylenediamine products, wherein nitrogen-containing groups can form weak chemical bonds such as hydrogen bonds with functional monomers, and the 3,4,5, 6-tetrahydro-2H-aza Zhuo Moban can be removed in a milder mode later, so that the adsorbent with the imprinted cavity matched with the adsorbent can be obtained.
Preferably, the functional monomer is selected from the group consisting of amines and/or pyridines, preferably comprising any one or a combination of at least two of acrylamide, o-phenylenediamine or 2-vinylpyridine, wherein typical but non-limiting combinations are combinations of acrylamide and o-phenylenediamine, combinations of 2-vinylpyridine and o-phenylenediamine, and combinations of acrylamide and 2-vinylpyridine.
Preferably, the molar ratio of the functional monomer to the azepine compound template is 1-6:1, for example, 1:1, 1.6:1, 2.2:1, 2.7:1, 3.3:1, 3.8:1, 4.4:1, 4.9:1, 5.5:1 or 6:1, etc., but not limited to the recited values, and other non-recited values in the range are equally applicable.
Preferably, the prepolymerization is carried out in a first organic solvent.
Preferably, the first organic solvent comprises an alcohol, for example, methanol, ethanol, propanol, or the like, preferably ethanol.
Preferably, the ratio of the azepine compound template to the first organic solvent is 0.5-10 g:1L, for example, but not limited to the recited values, and other non-recited values within the range are equally applicable.
The reaction temperature of the preliminary polymerization is preferably 10 to 40 ℃, and may be, for example, 10 ℃, 14 ℃, 17 ℃, 20 ℃, 24 ℃, 27 ℃, 30 ℃, 34 ℃, 37 ℃, 40 ℃, or the like, but is not limited to the values recited, and other values not recited in the range are applicable as well, and room temperature is preferred.
Preferably, the prepolymerization is carried out under stirring conditions.
The stirring mode is not particularly limited, and any stirring mode known to those skilled in the art can be adopted, and the stirring mode can be adjusted according to actual processes, such as magnetic stirring, stirring paddle stirring and the like.
The reaction time of the preliminary polymerization is preferably 1 to 20 hours, and may be, for example, 1 hour, 4 hours, 6 hours, 8 hours, 10 hours, 12 hours, 14 hours, 16 hours, 18 hours, or 20 hours, etc., but is not limited to the recited values, and other values not recited in the range are equally applicable.
Preferably, the ratio of the carrier to the first organic solvent in the step (2) is 5-30 g:1L, for example, 5g:1L, 8g:1L, 11g:1L, 14g:1L, 17g:1L, 19g:1L, 22g:1L, 25g:1L, 28g:1L or 30g:1L, etc., but not limited to the recited values, and other non-recited values in the range are equally applicable.
Preferably, the molar ratio of the crosslinking agent to the azepine compound template is 18-22:1, for example, 18.0:1, 18.5:1, 19.0:1, 19.4:1, 19.8:1, 20.0:1, 20.5:1, 21.0:1, 21.5:1 or 22:1, etc., but not limited to the recited values, and other non-recited values within the range are equally applicable.
Preferably, the ratio of the initiator to the first organic solvent is 0.1 to 1 g/1L, for example, 0.1 g/1L, 0.2 g/1L, 0.3 g/1L, 0.4 g/1L, 0.5 g/1L, 0.6 g/1L, 0.7 g/1L, 0.8 g/1L, 0.9 g/1L, or 1 g/1L, etc., but not limited to the above values, and other non-listed values in this range are equally applicable.
Preferably, the crosslinker comprises any one or a combination of at least two of ethylene glycol diglycidyl ether, ethylene glycol dimethacrylate, or N, N-methylenebisacrylamide, wherein typical but non-limiting combinations are combinations of ethylene glycol diglycidyl ether and ethylene glycol dimethacrylate, combinations of ethylene glycol dimethacrylate and N, N-methylenebisacrylamide, and combinations of ethylene glycol diglycidyl ether and N, N-methylenebisacrylamide.
Preferably, the initiator comprises azobisisobutyronitrile and/or ammonium persulfate.
The polymerization reaction temperature is preferably 40 to 80 ℃, and may be, for example, 40 ℃, 45 ℃, 49 ℃, 54 ℃, 58 ℃, 63 ℃, 67 ℃, 72 ℃, 76 ℃, 80 ℃ or the like, but is not limited to the values recited, and other values not recited in the range are equally applicable.
The polymerization reaction time is preferably 10 to 48 hours, and may be, for example, 10 hours, 15 hours, 19 hours, 23 hours, 27 hours, 32 hours, 36 hours, 40 hours, 44 hours, or 48 hours, etc., but is not limited to the recited values, and other non-recited values within the range are equally applicable.
Preferably, the polymerization reaction comprises: mixing the pre-polymerization reaction material and the carrier, dispersing for the first time, and then adding the cross-linking agent and the initiator to perform polymerization reaction.
Preferably, the first dispersion comprises ultrasonic dispersion.
Preferably, the first dispersing time is 10 to 60 minutes, for example, 10 minutes, 16 minutes, 22 minutes, 27 minutes, 33 minutes, 38 minutes, 44 minutes, 49 minutes, 55 minutes or 60 minutes, etc., but not limited to the recited values, and other non-recited values within the range are equally applicable.
Preferably, after the first dispersion, a crosslinking agent and an initiator are added in a first protective atmosphere.
Preferably, the first protective atmosphere comprises any one or a combination of at least two of nitrogen, helium or argon, wherein typical but non-limiting combinations are combinations of nitrogen and helium, combinations of argon and helium, and combinations of nitrogen and argon.
Preferably, the method for removing the azepine compound template comprises any one of solvent washing extraction, solid phase extraction, supercritical extraction, gas purging or Soxhlet extraction.
Preferably, the step of removing the azepine compound template in the step (3) comprises: and extracting the azepine compound templates in the polymer particles by adopting mixed acid liquor.
Preferably, the extraction comprises soxhlet extraction.
Preferably, the mixed acid solution contains formic acid and acetic acid.
Preferably, the volume ratio of formic acid to acetic acid is 5-10:1, for example, it may be 5.0:1, 5.5:1, 6.0:1, 7.0:1, 7.3:1, 7.5:1, 8.0:1, 8.5:1, 9.5:1 or 10:1, etc., but not limited to the recited values, other non-recited values within this range are equally applicable, preferably 8:1. Has better solvent removal effect.
Preferably, the method further comprises first drying after removing the azepine compound template.
The temperature of the first drying is preferably 40 to 100 ℃, and may be, for example, 40 ℃, 47 ℃, 54 ℃, 60 ℃, 67 ℃, 74 ℃, 80 ℃, 87 ℃, 94 ℃, or 100 ℃, etc., but is not limited to the values recited, and other values not recited in the range are equally applicable.
Preferably, the carrier is modified before being added to step (2).
Preferably, the modification method of the carrier comprises: mixing the primary carrier, the second organic solvent and the organic matter containing amino group for modification reaction, and sequentially carrying out solid-liquid separation, washing and second drying on the obtained modified reaction material to obtain the modified carrier.
The solid-liquid separation method of the present invention is not particularly limited, and may be carried out by any method known to those skilled in the art as being applicable to solid-liquid separation, and may be, for example, filtration, sedimentation separation, centrifugal separation, or the like.
Preferably, the primary support comprises any one or a combination of at least two of aluminum oxide, silicon dioxide, aluminum or silicon, wherein typical but non-limiting combinations are combinations of aluminum oxide and aluminum, combinations of silicon dioxide and aluminum, combinations of aluminum oxide and silicon dioxide, combinations of silicon and aluminum, combinations of aluminum oxide and silicon, preferably aluminum oxide.
Preferably, the second organic solvent comprises toluene.
Preferably, the amino-containing organic matter comprises an aminosilane, preferably 3-aminopropyl triethoxysilane.
The temperature of the modification reaction is preferably 80 to 100 ℃, and may be, for example, 80 ℃, 83 ℃, 85 ℃, 87 ℃, 89 ℃, 92 ℃, 94 ℃, 96 ℃, 98 ℃, or 100 ℃, etc., but is not limited to the values recited, and other values not recited in the range are equally applicable.
Preferably, the mass ratio of the organic matter containing amino groups to the primary carrier is 1 to 10:1, for example, 1:1, 2:1, 3:1, 4:1, 5:1, 6:1, 7:1, 8:1, 9:1 or 10:1, etc., but not limited to the recited values, and other non-recited values within the range are equally applicable.
Preferably, the ratio of the primary carrier to the second organic solvent is 15 to 30g:1L, for example, 15g:1L, 17g:1L, 19g:1L, 20g:1L, 22g:1L, 24g:1L, 25g:1L, 27g:1L, 29g:1L or 30g:1L, etc., but not limited to the recited values, and other non-recited values within the range are equally applicable.
Preferably, the order of mixing the primary carrier, the second organic solvent and the amino group-containing organic matter includes: mixing the primary carrier and the second organic solvent, dispersing the mixture, and adding the organic matter containing amino groups.
Preferably, the amino-containing organic matter is added dropwise. Preferably, the dripping mode is adopted, so that the uniformity of modification can be better improved, and the adsorption effect of the final adsorbent is improved.
Preferably, the second dispersion is an ultrasonic dispersion.
The power of the ultrasonic dispersion in the first dispersion and the second dispersion is not particularly significant, and can be adjusted according to the actual process, for example, 200W, 300W, 400W, 500W, 550W, 600W or 700W, etc.
Preferably, the second dispersing time is 10 to 60 minutes, for example, 10 minutes, 16 minutes, 20 minutes, 27 minutes, 30 minutes, 38 minutes, 40 minutes, 45 minutes, 55 minutes or 60 minutes, etc., but not limited to the recited values, and other non-recited values within the range are equally applicable.
Preferably, after the second dispersion, an organic substance containing an amino group is added under a second protective atmosphere.
Preferably, the second protective atmosphere comprises any one or a combination of at least two of nitrogen, argon or helium, wherein typical but non-limiting combinations are combinations of nitrogen and argon, combinations of helium and argon, and combinations of nitrogen and helium.
Preferably, the washing includes toluene washing and methanol washing performed sequentially.
Preferably, the number of times of the toluene washing is at least three, and for example, may be 3 times, 4 times, 5 times, 6 times, 8 times, or the like.
Preferably, the number of times of the methanol washing is at least three, and for example, may be 3 times, 4 times, 5 times, 6 times, 8 times, or the like.
The second drying temperature is preferably 40 to 100 ℃, and may be, for example, 40 ℃, 47 ℃, 54 ℃, 60 ℃, 67 ℃, 74 ℃, 80 ℃, 87 ℃, 94 ℃, or 100 ℃, etc., but is not limited to the recited values, and other non-recited values within the range are equally applicable.
The manner of the first drying and the second drying is not particularly limited, and any manner known to those skilled in the art as being applicable to drying may be employed, for example, vacuum drying or forced air drying, etc., preferably vacuum drying.
As a preferable technical scheme of the invention, the preparation method comprises the following steps:
(1) Prepolymerizing a functional monomer and an azepine compound template in a first organic solvent for 1-20 h at a temperature of 10-40 ℃ according to a molar ratio of 1-6:1, wherein the ratio of the azepine compound template to the first organic solvent is 0.5-10 g:1L, so as to obtain a prepolymerized reaction material;
(2) Firstly mixing a prepolymerization reaction material and a modified carrier, wherein the ratio of the modified carrier to a first organic solvent is 5-30 g:1L, adding a cross-linking agent and an initiator into a first protective atmosphere after first dispersion, wherein the molar ratio of the cross-linking agent to an azepine compound template is 18-22:1, the ratio of the initiator to the first organic solvent is 0.1-1 g:1L, and carrying out polymerization reaction for 10-48 hours at 40-80 ℃ to obtain polymer particles;
(3) And extracting the azepine compound template in the polymer particles by adopting mixed acid liquid of formic acid and acetic acid with the volume ratio of 5-10:1 to obtain the surface molecular imprinting functionalized adsorbent.
In a third aspect, the present invention provides the use of a surface molecularly imprinted functionalized adsorbent according to the first aspect, for separating an azepine compound, preferably for removing impurities from an azepine compound.
The adsorbent disclosed by the invention can specifically adsorb the azepine compound, has stronger adsorption selectivity and can be obviously different from other substances which are dissimilar substances, so that the adsorbent is particularly suitable for removing trace azepine compound impurities and trace azepine compound impurities, and has the advantages of low energy consumption and high removal efficiency compared with other methods.
The trace of the invention refers to the content of the azepine compound is less than 0.01 percent; the trace amount means that the content of the azepine compound is 0.01-1%.
In a fourth aspect, the present invention provides a purification method of hexamethylenediamine, wherein the purification method adopts the surface molecular imprinting functionalized adsorbent according to the first aspect to perform adsorption separation of impurities.
According to the purification method of hexamethylenediamine provided by the fourth aspect of the invention, because byproducts such as azepine compounds are generated in the purification and production processes of the existing hexamethylenediamine, the azepine compounds are difficult to remove in a rectification mode, and azepine compound impurities still remain after preliminary purification, and the inventor develops a method for adsorbing, separating and purifying hexamethylenediamine through multi-party exploration, the method of the invention has the following two invention points: (1) Although hexamethylenediamine and azepine are both organic substances and both have polar groups, the inventors have still isolated from the prior art: it was found that the impurity and hexamethylenediamine can be separated by adsorption in the methods of rectification, adsorption, filtration, extraction, membrane separation, and the like; (2) The conventional adsorbent is found to have a higher adsorption effect on hexamethylenediamine, so that selective adsorption of the azepine compound is difficult to realize, and the surface molecular imprinting functionalized adsorbent in the first aspect is selected, so that the azepine compound can be specifically adsorbed, the adsorption amount of the hexamethylenediamine is low, and impurities in the hexamethylenediamine can be removed under the condition of high yield.
The purification method of the adsorption separation has the advantages of recycling the adsorbent and low energy consumption, and can obviously reduce the production cost in industry.
Preferably, the purification method comprises: and adsorbing the azepine compound impurities in the crude hexamethylenediamine by using the adsorbent.
Preferably, the mass ratio of the crude hexamethylenediamine to the adsorbent is 300 to 600:1, for example, 300:1, 334:1, 367:1, 400:1, 434:1, 467:1, 500:1, 534:1, 567:1 or 600:1, etc., but not limited to the recited values, other non-recited values within the range are equally applicable. From the mass ratio, the adsorbent of the present invention has a large treatment capacity and high treatment efficiency.
The specific adsorption mode of the present invention is not particularly limited, and any mode known to those skilled in the art to be applicable to adsorption may be employed, and for example, a kettle type, a fixed bed type, a tower type or a moving bed type may be employed. The adsorption mode can also be adjusted according to the actual process.
Preferably, the adsorbent is recycled after being regenerated after being saturated by adsorption.
The method of the regeneration treatment is not particularly limited, and may be carried out by any method known to those skilled in the art as being applicable to the regeneration treatment of an adsorbent, and may be, for example, any of solvent washing, soxhlet extraction, gas purging, solid phase extraction, or supercritical extraction.
Compared with the prior art, the invention has at least the following beneficial effects:
(1) The surface molecular imprinting functionalized adsorbent provided by the invention can be recycled for a plurality of times, and after repeated regeneration for 5 times, hexamethylenediamine can be purified to more than 99.98%, and has the characteristics of low cost, simplicity in operation, high selectivity, environment friendliness and the like;
(2) The preparation method of the surface molecular imprinting functionalized adsorbent adopts the surface molecular imprinting technology to prepare the molecular imprinting polymer with specific recognition sites and specific adsorption on the azepine compound, and the preparation process is simple and easy to implement;
(3) The purification method of hexamethylenediamine provided by the invention can further purify and rectify the hexamethylenediamine, so that the purity of the hexamethylenediamine reaches the polymerization requirement of nylon 66, the purity of the hexamethylenediamine is increased to more than 99.98wt% and the yield of the hexamethylenediamine is more than 98wt%, the loss rate is low, the content of 3,4,5, 6-tetrahydro-2H-azepine is reduced to less than 0.011wt%, the content of the 3,4,5, 6-tetrahydro-2H-azepine is reduced to less than 0.008wt% under the preferential condition, the selective adsorption effect of the adsorbent on the azepine compound impurities is good, and the yield of the hexamethylenediamine is high.
Drawings
Fig. 1 is a schematic flow chart of a preparation method of a surface molecular imprinting functionalized adsorbent provided in example 1 of the present invention.
FIG. 2 is an SEM image of a surface molecularly imprinted functionalized adsorbent prepared in example 1 of the invention.
FIG. 3 is a BET adsorption and desorption graph of the surface molecular imprinting functionalized adsorbent prepared in example 1 of the present invention.
Detailed Description
The technical scheme of the invention is further described below by the specific embodiments with reference to the accompanying drawings.
The present invention will be described in further detail below. The following examples are merely illustrative of the present invention and are not intended to represent or limit the scope of the invention as defined in the claims.
Example 1
The embodiment provides a preparation method of a surface molecular imprinting functionalized adsorbent, and the flow of the preparation method is shown in fig. 1, and specifically comprises the following steps:
firstly, 50g of carrier Al is mixed 2 O 3 And 2L of anhydrous toluene, after ultrasonic dispersion for 30min, dropwise adding 0.1L3-aminopropyl triethoxysilane in a nitrogen atmosphere, and carrying out modification reaction for 18h at 90 ℃ to obtain a modified reaction material in sequenceFiltering, washing with toluene for 3 times, washing with methanol for 3 times, and drying at 60 ℃ in a vacuum drying oven to obtain a modified carrier;
(1) 3g of acrylamide is taken as a functional monomer and 2g of 3,4,5, 6-tetrahydro-2H-azepine is taken as an azepine compound template to be prepolymerized in 2L of ethanol for 10 hours at room temperature (25 ℃) to obtain a prepolymerization reaction material containing prepolymer;
(2) Firstly mixing the prepolymerization reaction material in the step (1) with 20g of modified carrier, performing ultrasonic dispersion for 30min, then adding 71.5g of ethylene glycol dimethacrylate serving as a cross-linking agent and 0.8g of azodiisobutyronitrile serving as an initiator in nitrogen atmosphere, and performing polymerization reaction at 60 ℃ for 24h to obtain polymer particles;
(3) Extracting 2,3,4,5, 6-tetrahydro-2H-aza Zhuo Moban in the polymer particles by adopting mixed acid of formic acid and acetic acid with the volume ratio of 8:1 in a Soxhlet extractor until 3,4,5, 6-tetrahydro-2H-aza is not detected in the extracting solution, and placing the polymer particles with the 3,4,5, 6-tetrahydro-2H-aza templates removed in vacuum drying at 60 ℃ to constant weight, thereby obtaining the adsorbent with the surface molecular imprinting functionalization.
The surface molecular imprinting functionalized adsorbent prepared in the embodiment comprises a carrier Al 2 O 3 Supported on carrier Al 2 O 3 A surface molecule thereon; and imprinting cavities are formed between the surface molecules and are matched with the azepine compounds. The SEM image of the adsorbent is shown in figure 2, and it can be seen from figure 2 that the surface of the irregular microspherical carrier is coated with molecularly imprinted polymer, wherein the irregular microspherical carrier is shown in a circular frame ring in the figure, and the polymer is shown in a white frame, so that the polymer is slightly agglomerated, which indicates successful preparation of the molecularly imprinted composite, and the polymer coated on the carrier has porosity, so that the specific area and the adsorption performance are improved. The BET adsorption/desorption curve is shown in FIG. 3, wherein the boxes represent the desorption curves and the circles represent the adsorption curves, and it can be seen that the adsorbent belongs to the type IV isothermal adsorption line and also belongs to the type H3 hysteresis loop, which is a typical porous feature, and the surface area is measured to be 100.2m 2 The/g has larger specific surface area, can provide more adsorption sites, and proves the micro of SEMAnd (5) observing characteristics.
Example 2
This example provides a method for preparing a surface molecularly imprinted functionalized adsorbent, which is the same as example 1 except that 0.15L3-aminopropyl triethoxysilane is added dropwise during the modification reaction, 5.7g acrylamide is added as a functional monomer in step (1), 79.3g ethylene glycol dimethacrylate is added as a crosslinking agent in step (2).
Example 3
This example provides a method for preparing a surface molecularly imprinted functionalized adsorbent, which is the same as example 1 except that 0.15L3-aminopropyl triethoxysilane is added dropwise during the modification reaction, 8.4g of 2-vinylpyridine is added as a functional monomer in step (1), and 61.7g of N, N-methylenebisacrylamide is added as a crosslinking agent in step (2).
Example 4
This example provides a method for preparing a surface molecularly imprinted functionalized adsorbent, which is the same as example 1 except that 0.15L3-aminopropyl triethoxysilane is added dropwise in the modification reaction, 8.53g of acrylamide is added as a functional monomer in step (1), and 87.2g of ethylene glycol dimethacrylate is added as a crosslinking agent in step (2).
Example 5
This example provides a method for preparing a surface molecularly imprinted functionalized adsorbent, which is the same as example 1 except that 0.15L3-aminopropyl triethoxysilane is added dropwise during the modification reaction, 5.7g of acrylamide is added as a functional monomer in step (1), 79.3g of ethylene glycol dimethacrylate is added as a crosslinking agent in step (2).
Example 6
The embodiment provides a preparation method of a surface molecular imprinting functionalized adsorbent, which does not aim at a carrier Al 2 O 3 The modification was performed in the same manner as in example 1.
Example 7
This example provides a surface molecularly imprinted functionalized adsorbentThe preparation method comprises removing carrier Al 2 O 3 The procedure of example 1 was repeated except that the silica was used instead of the silica.
Example 8
The present embodiment provides a method for preparing a surface molecularly imprinted functionalized adsorbent, which is the same as that of embodiment 1 except that the step (1) of prepolymerization is not performed, and the functional monomer, the azepine compound template, the crosslinking agent and the initiator are directly polymerized together.
The method comprises the following specific steps:
(1) 3g of acrylamide is used as a functional monomer, 2g of 3,4,5, 6-tetrahydro-2H-azepine is used as an azepine compound template and 20g of modified carrier are added into 2L of ethanol, after ultrasonic dispersion is carried out for 30min, 71.5g of ethylene glycol dimethacrylate is used as a cross-linking agent and 0.8g of azobisisobutyronitrile is used as an initiator, and polymerization reaction is carried out at 60 ℃ for 24H to obtain polymer particles;
(2) Extracting 2,3,4,5, 6-tetrahydro-2H-aza Zhuo Moban in the polymer particles by adopting mixed acid of formic acid and acetic acid with the volume ratio of 8:1 in a Soxhlet extractor until 3,4,5, 6-tetrahydro-2H-aza is not detected in the extracting solution, and placing the polymer particles with the 3,4,5, 6-tetrahydro-2H-aza templates removed in vacuum drying at 60 ℃ to constant weight, thereby obtaining the adsorbent with the surface molecular imprinting functionalization.
Example 9
The embodiment provides a preparation method of a surface molecular imprinting functionalized adsorbent, which comprises the following steps:
15g of carrier Al are firstly mixed 2 O 3 And 1L of anhydrous toluene, after ultrasonic dispersion for 45min, dropwise adding 15mL of 3-aminopropyl triethoxysilane in a nitrogen atmosphere, carrying out modification reaction for 10h at 80 ℃, and sequentially filtering, washing the obtained modified reaction material with toluene for 4 times, washing with methanol for 3 times and drying in a vacuum drying oven at 40 ℃ to obtain a modified carrier;
(1) 3.2g of acrylamide is taken as a functional monomer and 1g of 3,4,5, 6-tetrahydro-2H-azepine is taken as an azepine compound template, and the mixture is stirred and prepolymerized in 1L of ethanol at 15 ℃ for 20 hours to obtain a prepolymerization reaction material containing prepolymer;
(2) Firstly mixing the prepolymerization reaction material in the step (1) with 30g of modified carrier, performing ultrasonic dispersion for 60min, then adding 78.6g of ethylene glycol dimethacrylate serving as a cross-linking agent and 1g of azobisisobutyronitrile serving as an initiator in nitrogen atmosphere, and performing polymerization reaction at 40 ℃ for 48h to obtain polymer particles;
(3) Extracting 2,3,4,5, 6-tetrahydro-2H-aza Zhuo Moban in the polymer particles by adopting mixed acid of formic acid and acetic acid with the volume ratio of 10:1 in a Soxhlet extractor until 3,4,5, 6-tetrahydro-2H-aza is not detected in the extracting solution, and placing the polymer particles with the 3,4,5, 6-tetrahydro-2H-aza templates removed in vacuum drying at 100 ℃ to constant weight, thereby obtaining the adsorbent with the surface molecular imprinting functionalization.
Example 10
The embodiment provides a preparation method of a surface molecular imprinting functionalized adsorbent, which comprises the following steps:
mixing 60g of carrier Al 2 O 3 And 2L of anhydrous toluene, after ultrasonic dispersion for 60min, dropwise adding 0.1L3-aminopropyl triethoxysilane in a nitrogen atmosphere, carrying out modification reaction at 100 ℃ for 25h, and sequentially filtering, washing toluene for 3 times, washing methanol for 4 times and drying in a vacuum drying oven at 100 ℃ to obtain a modified carrier;
(1) 5.7g of acrylamide serving as a functional monomer and 2g of 3,4,5, 6-tetrahydro-2H-azepine serving as an azepine compound template are stirred and prepolymerized in 0.5L of ethanol at room temperature (25 ℃) for 10 hours to obtain a prepolymerization reaction material containing prepolymer;
(2) Firstly mixing the prepolymerization reaction material in the step (1) with 2.5g of modified carrier, performing ultrasonic dispersion for 20min, then adding 79.0g of ethylene glycol dimethacrylate serving as a cross-linking agent and 0.05g of azodiisobutyronitrile serving as an initiator in nitrogen atmosphere, and performing polymerization reaction at 60 ℃ for 24h to obtain polymer particles;
(3) Extracting 2,3,4,5, 6-tetrahydro-2H-aza Zhuo Moban in the polymer particles by adopting mixed acid of formic acid and acetic acid with the volume ratio of 5:1 in a Soxhlet extractor until 3,4,5, 6-tetrahydro-2H-aza is not detected in the extracting solution, and placing the polymer particles with the 3,4,5, 6-tetrahydro-2H-aza templates removed in vacuum drying at 40 ℃, and drying to constant weight to obtain the adsorbent with the surface molecular imprinting functionalization.
Comparative example 1
This comparative example provides a method for preparing an adsorbent, which is the same as example 1 except that 3,4,5, 6-tetrahydro-2H-azepine is not added as an azepine compound template.
Application example 1
The application example provides a purification method of hexamethylenediamine, which comprises the following steps: 1kg of the adsorbent prepared in example 1 was added to 1m 3 500kg of hexamethylenediamine after rectification treatment is added into the reaction kettle, the mixture is stirred and dispersed uniformly, the mixture is stirred and adsorbed for 20 hours at room temperature (25 ℃), then the adsorbent is filtered and separated, and the filtrate is subjected to gas chromatography for content analysis.
Application examples 2 to 8
Application examples 2 to 8 respectively provide a purification method of hexamethylenediamine, which is the same as application example 1 except that adsorbents provided in examples 2 to 8 respectively are used.
Application example 9
The application example provides a purification method of hexamethylenediamine, which comprises the following steps: 1kg of the adsorbent prepared in example 9 was packed into 4 adsorption columns connected in series, followed by 0.5h -1 And (3) introducing hexamethylenediamine subjected to rectification at a speed, adsorbing at 35 ℃, and performing liquid phase gas chromatography analysis on the content after adsorption.
Application example 10
The application example provides a purification method of hexamethylenediamine, which comprises the following steps: 2.5kg of the adsorbent prepared in example 10 were added to 2m 3 500kg of hexamethylenediamine is added into the reaction kettle, stirred and dispersed uniformly, vibration adsorption is carried out for 35 hours at room temperature (25 ℃), then the adsorbent is filtered and separated, and the content of the filtrate is analyzed by gas chromatography.
Comparative example 1 was used
This comparative application example provides a purification method of hexamethylenediamine, which is the same as that of application example 1, except that the adsorbent provided in comparative example 1 is used.
Comparative example 2 was used
The present comparative application provides a purification method of hexamethylenediamine using the purification method provided in example 1 of CN103936595 a.
The test results of the above application examples and application comparative examples are shown in table 1.
TABLE 1
Figure BDA0003192439410000181
Figure BDA0003192439410000191
As can be seen from Table 1, firstly, comprehensive application examples 1 to 5 and application examples 9 to 10 show that aiming at hexamethylenediamine with different impurity contents, the purification method provided by the invention can improve the purity of hexamethylenediamine to more than 99.99wt%, the yield of hexamethylenediamine is more than 98wt%, the loss rate is low, and the content of 3,4,5, 6-tetrahydro-2H-azepine after adsorption is less than or equal to 0.011wt%;
Secondly, as can be seen from the comprehensive application example 1 and the application comparative example 1, the invention can improve the purity of hexamethylenediamine to more than 99.98wt% by adopting the adsorption purification of the adsorbent with the surface molecular imprinting functionalization, and has excellent effect on further removing trace impurities;
again, it can be seen from the combination of application example 1 and application examples 6 to 7 that the modified alumina carrier used in application example 1 has a purity of 99.992wt% after adsorption in application example 1 and only 99.989wt% and 99.990wt% after adsorption of hexamethylenediamine in application examples 6 to 7, respectively, compared with the unmodified alumina carrier used in application example 6 and the silica carrier used in application example 7, thus showing that the impurity removal performance can be further improved by preferably using the modified alumina as a carrier in the present invention;
finally, as can be seen from the comprehensive application examples 1 and 8, the adsorbent is prepared in the application example 1 by a prepolymerization method, compared with the direct complete polymerization in the application example 8, the purity of the adsorbed hexamethylenediamine in the application example 1 is 99.992wt%, the content of the adsorbed 3,4,5, 6-tetrahydro-2H-azepine is only 0.005wt%, and the purity of the adsorbed hexamethylenediamine in the application example 8 is only 99.988wt%, and the content of the adsorbed 3,4,5, 6-tetrahydro-2H-azepine is as high as 0.011wt%, so that the purification effect of the hexamethylenediamine is remarkably improved and the content of the adsorbed 3,4,5, 6-tetrahydro-2H-azepine is reduced by further preferably preparing the adsorbent by the prepolymerization method.
Taking the adsorbent provided in example 2 as an example, the method provided in application example 2 was used for adsorption purification of hexamethylenediamine, and the adsorption effect after the catalyst was regenerated a plurality of times was examined, wherein the regeneration treatment method comprises the following steps: and (3) placing the recovered adsorbent in a Soxhlet extractor, continuously extracting template molecules in the adsorbent by using a mixed solution of methanol and acetic acid in a ratio of 8:1 until the template molecules are not detected in the extracting solution, and placing the adsorbent in a vacuum drying oven to be dried to constant weight, thereby obtaining the regenerated adsorbent. The regenerated adsorbent was used for adsorption by the method of application example 2, and the method was repeated 5 times to examine the regenerability of the adsorbent. The specific examination results are shown in table 2.
TABLE 2
Figure BDA0003192439410000201
As can be seen from table 2: after repeated regeneration for 4 times, the adsorbent can purify the hexamethylenediamine to more than 99.99%, shows good regeneration performance, and after repeated regeneration for 5 times, the performance of the adsorbent is slightly reduced, but the hexamethylenediamine can still be purified to more than 99.98%, so that the adsorbent can be repeatedly used for many times, and the use cost is reduced.
In conclusion, the surface molecular imprinting functionalized adsorbent provided by the invention can be recycled for multiple times, has the characteristics of low cost, simplicity in operation, high selectivity, environmental friendliness and the like, can be applied to the purification process of hexamethylenediamine, can realize the technical effects that the purity of hexamethylenediamine is increased to more than 99.99wt% and the yield of hexamethylenediamine is increased to more than 98wt%, and the content of 3,4,5, 6-tetrahydro-2H-azepine is reduced to less than 0.011wt% under the optimal condition, so that the influence on a later nylon product is reduced.
The applicant states that the detailed structural features of the present invention are described by the above embodiments, but the present invention is not limited to the above detailed structural features, i.e. it does not mean that the present invention must be implemented depending on the above detailed structural features. It should be apparent to those skilled in the art that any modifications of the present invention, equivalent substitutions of selected components of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope of the present invention and the scope of the disclosure.

Claims (41)

1. A surface molecular imprinting functionalized adsorbent, which is characterized by comprising a carrier and surface molecules loaded on the carrier;
a imprinting cavity is formed between the surface molecules, and the imprinting cavity is matched with the azepine compound;
the azepine compound is 3,4,5, 6-tetrahydro-2H-azepine;
the carrier is a carrier loaded with amino;
the surface molecules comprise polymerized molecules which polymerize functional monomers, cross-linking agents and azepine compounds and then remove the azepine compounds.
2. The adsorbent of claim 1, wherein the support comprises any one or a combination of at least two of aluminum oxide, silica, activated carbon, ZSM-5 molecular sieve, or montmorillonite.
3. The adsorbent of claim 1, wherein the adsorbent has a particle size of 50nm to 5 μm.
4. The adsorbent of claim 1, wherein the adsorbent has a specific surface area of 100～1000m 2 /g。
5. The adsorbent according to claim 1, wherein the functional monomer is selected from amines and/or pyridines.
6. The sorbent of claim 5, wherein the functional monomer comprises any one or a combination of at least two of acrylamide, o-phenylenediamine, or 2-vinylpyridine.
7. A method of preparing a surface molecularly imprinted functionalized adsorbent according to any one of claims 1-6, characterized in that the preparation method comprises the steps of:
(1) Prepolymerizing the functional monomer and the azepine compound template to obtain a prepolymerized reaction material; the azepine compound template is selected from 3,4,5, 6-tetrahydro-2H-azepine;
(2) The pre-polymerization reaction material, the carrier, the cross-linking agent and the initiator are subjected to polymerization reaction to obtain polymer particles; the carrier is modified into an amino-containing carrier and then added into the step (2);
(3) And removing the azepine compound template from the polymer particles to obtain the surface molecular imprinting functionalized adsorbent.
8. The method according to claim 7, wherein the functional monomer is selected from amines and/or pyridines.
9. The method according to claim 8, wherein the functional monomer comprises any one or a combination of at least two of acrylamide, o-phenylenediamine, and 2-vinylpyridine.
10. The method according to claim 7, wherein the molar ratio of the functional monomer to the azepine compound template is 1-6:1.
11. The method of claim 7, wherein the pre-polymerization is performed in a first organic solvent.
12. The method according to claim 11, wherein the ratio of the azepine compound template to the first organic solvent is 0.5-10 g/1 l.
13. The method of claim 12, wherein the ratio of the carrier to the first organic solvent in step (2) is 5-30 g/1 l.
14. The method of claim 11, wherein the molar ratio of the cross-linking agent to the azepine compound template is 18-22:1.
15. The method of claim 11, wherein the ratio of the initiator to the first organic solvent is 0.1-1 g/1 l.
16. The method of claim 11, wherein the cross-linking agent comprises any one or a combination of at least two of ethylene glycol diglycidyl ether, ethylene glycol dimethacrylate, or N, N-methylenebisacrylamide.
17. The process according to claim 11, wherein the polymerization reaction temperature is 40 to 80 ℃.
18. The method according to claim 11, wherein the polymerization reaction time is 10 to 48 hours.
19. The method of preparation of claim 11, wherein the polymerization reaction comprises: mixing the pre-polymerization reaction material and the carrier, dispersing for the first time, and then adding the cross-linking agent and the initiator to perform polymerization reaction.
20. The method of claim 19, wherein after the first dispersion, a crosslinking agent and an initiator are added in a first protective atmosphere.
21. The method of claim 20, wherein the first protective atmosphere comprises any one or a combination of at least two of nitrogen, helium, or argon.
22. The method of claim 11, wherein the step of removing the azepine template in step (3) comprises: and extracting the azepine compound templates in the polymer particles by adopting mixed acid liquor.
23. The method according to claim 22, wherein the mixed acid solution contains formic acid and acetic acid.
24. The process of claim 23, wherein the volume ratio of formic acid to acetic acid is from 5 to 10:1.
25. The method of claim 7, wherein the method of modifying the support comprises: mixing the primary carrier, the second organic solvent and the organic matter containing amino group for modification reaction, and sequentially carrying out solid-liquid separation, washing and second drying on the obtained modified reaction material to obtain the modified carrier.
26. The method of claim 25, wherein the primary support comprises any one or a combination of at least two of aluminum oxide, silica, activated carbon, ZSM-5 molecular sieve, or montmorillonite.
27. The method of claim 25, wherein the second organic solvent comprises toluene.
28. The method of claim 25, wherein the amino-containing organic compound comprises an aminosilane.
29. The method of claim 28, wherein the amino group-containing organic compound is 3-aminopropyl triethoxysilane.
30. The method according to claim 25, wherein the temperature of the modification reaction is 80 to 100 ℃.
31. The method according to claim 25, wherein the mass ratio of the amino group-containing organic substance to the primary carrier is 1 to 10:1.
32. The method of claim 25, wherein the ratio of the primary carrier to the second organic solvent is 15-30 g/1 l.
33. The method of claim 25, wherein the order of mixing the primary carrier, the second organic solvent, and the amino-containing organic material comprises: mixing the primary carrier and the second organic solvent, dispersing the mixture, and adding the organic matter containing amino groups.
34. The method of claim 33, wherein after the second dispersing, adding an organic compound containing amino groups under a second protective atmosphere.
35. The method of claim 34, wherein the second protective atmosphere comprises any one or a combination of at least two of nitrogen, argon, or helium.
36. The method according to claim 25, wherein the washing comprises toluene washing and methanol washing performed sequentially.
37. Use of a surface molecularly imprinted functionalized adsorbent according to any one of claims 1-6, characterized in that the adsorbent is used for separating azepine compounds.
38. The use according to claim 37, wherein the adsorbent is used for the removal of azepine impurities.
39. A purification method of hexamethylenediamine, characterized in that the purification method adopts the surface molecular imprinting functionalized adsorbent according to any one of claims 1 to 6 to perform adsorption separation of impurities.
40. The purification process of claim 39, wherein the purification process comprises: and adsorbing the azepine compound impurities in the crude hexamethylenediamine by using the adsorbent.
41. The purification process of claim 40, wherein the mass ratio of crude hexamethylenediamine to adsorbent is 300 to 600:1.
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