CN113801259A - Preparation method and application of benzimidazole macroporous adsorption resin - Google Patents
Preparation method and application of benzimidazole macroporous adsorption resin Download PDFInfo
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- CN113801259A CN113801259A CN202111249523.6A CN202111249523A CN113801259A CN 113801259 A CN113801259 A CN 113801259A CN 202111249523 A CN202111249523 A CN 202111249523A CN 113801259 A CN113801259 A CN 113801259A
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- 238000001179 sorption measurement Methods 0.000 title claims abstract description 59
- 239000011347 resin Substances 0.000 title claims abstract description 58
- 229920005989 resin Polymers 0.000 title claims abstract description 58
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 63
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims description 50
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 50
- CHRJZRDFSQHIFI-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;styrene Chemical compound C=CC1=CC=CC=C1.C=CC1=CC=CC=C1C=C CHRJZRDFSQHIFI-UHFFFAOYSA-N 0.000 claims description 45
- 239000004005 microsphere Substances 0.000 claims description 45
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 26
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 24
- 238000010438 heat treatment Methods 0.000 claims description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 22
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical group CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 20
- 238000001035 drying Methods 0.000 claims description 19
- OCKJFOHZLXIAAT-UHFFFAOYSA-N 2-methylsulfanyl-1h-benzimidazole Chemical compound C1=CC=C2NC(SC)=NC2=C1 OCKJFOHZLXIAAT-UHFFFAOYSA-N 0.000 claims description 18
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 18
- 229930003935 flavonoid Natural products 0.000 claims description 18
- 235000017173 flavonoids Nutrition 0.000 claims description 18
- 238000005406 washing Methods 0.000 claims description 18
- 239000002270 dispersing agent Substances 0.000 claims description 15
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 13
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 claims description 12
- 229960000907 methylthioninium chloride Drugs 0.000 claims description 12
- 239000011780 sodium chloride Substances 0.000 claims description 12
- 230000008961 swelling Effects 0.000 claims description 12
- 235000019441 ethanol Nutrition 0.000 claims description 11
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 10
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical group C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 10
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 238000000926 separation method Methods 0.000 claims description 10
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 10
- HRQGCQVOJVTVLU-UHFFFAOYSA-N bis(chloromethyl) ether Chemical compound ClCOCCl HRQGCQVOJVTVLU-UHFFFAOYSA-N 0.000 claims description 8
- 238000000746 purification Methods 0.000 claims description 7
- 239000003054 catalyst Substances 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 239000003999 initiator Substances 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 150000002215 flavonoids Chemical class 0.000 claims description 5
- 238000006467 substitution reaction Methods 0.000 claims description 5
- 239000011592 zinc chloride Substances 0.000 claims description 5
- 235000005074 zinc chloride Nutrition 0.000 claims description 5
- 108010010803 Gelatin Proteins 0.000 claims description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 238000007265 chloromethylation reaction Methods 0.000 claims description 4
- 229920000159 gelatin Polymers 0.000 claims description 4
- 239000008273 gelatin Substances 0.000 claims description 4
- 235000019322 gelatine Nutrition 0.000 claims description 4
- 235000011852 gelatine desserts Nutrition 0.000 claims description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 4
- 239000004354 Hydroxyethyl cellulose Substances 0.000 claims description 3
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 claims description 3
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 3
- 239000004088 foaming agent Substances 0.000 claims description 3
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 claims description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 3
- 235000019422 polyvinyl alcohol Nutrition 0.000 claims description 2
- 239000003463 adsorbent Substances 0.000 claims 1
- -1 flavonoid compounds Chemical class 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- 238000000605 extraction Methods 0.000 description 8
- 241000411851 herbal medicine Species 0.000 description 4
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 description 3
- 230000000694 effects Effects 0.000 description 2
- 238000011403 purification operation Methods 0.000 description 2
- 238000012216 screening Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 240000001548 Camellia japonica Species 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 241001122767 Theaceae Species 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000018597 common camellia Nutrition 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000012454 non-polar solvent Substances 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- ROSDSFDQCJNGOL-UHFFFAOYSA-N protonated dimethyl amine Natural products CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 238000001256 steam distillation Methods 0.000 description 1
- 238000005092 sublimation method Methods 0.000 description 1
- 238000010558 suspension polymerization method Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- 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
- C08F8/00—Chemical modification by after-treatment
- C08F8/34—Introducing sulfur atoms or sulfur-containing groups
-
- 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
- B01J20/261—Synthetic macromolecular compounds obtained by reactions only involving carbon to carbon unsaturated bonds
-
- 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
- B01J20/265—Synthetic macromolecular compounds modified or post-treated polymers
-
- C—CHEMISTRY; METALLURGY
- 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
- C08F212/00—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 an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/06—Hydrocarbons
- C08F212/08—Styrene
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Analytical Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- General Chemical & Material Sciences (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention discloses a preparation method and application of benzimidazole macroporous adsorption resin, and relates to the technical field of macroporous adsorption resin.
Description
The technical field is as follows:
the invention relates to the technical field of macroporous adsorption resin, in particular to a preparation method and application of benzimidazole macroporous adsorption resin.
Background art:
the macroporous adsorption resin is a polymer adsorption resin which does not contain exchange groups and has a macroporous structure, and can be divided into non-polar, weak-polar and polar resins according to the surface properties of the resin, wherein the non-polar resin is suitable for adsorbing non-polar substances from a polar solvent, and the polar resin is suitable for adsorbing polar substances from a non-polar solvent. The resin has adsorption property due to the action of hydrogen bond or van der waals force, and simultaneously has screening performance due to the net structure and the larger specific surface area, so the macroporous adsorption resin is a material with adsorption and screening capacities.
In recent years, macroporous adsorption resin is widely applied to extraction of effective components of Chinese herbal medicines, so that the separation operation of the effective components can be simplified, and the separated effective components have high purity and low loss. At present, the macroporous adsorption resin which is most applied is polymerized by taking styrene as a polymerization monomer and divinylbenzene as a cross-linking agent and adding a certain proportion of pore-foaming agent.
The extraction method of the effective components of the Chinese herbal medicines mainly comprises a solvent extraction method, a steam distillation method, a squeezing method and a sublimation method, and a person skilled in the art knows that the obtained extract is in a mixture form by adopting any extraction method, the content of the target effective components is very low, and separation and purification operations are required to separate the target effective components with high purity from the extract.
The macroporous adsorption resin adsorption method is a simple separation and purification method, but needs to improve the adsorption selectivity of the macroporous adsorption resin, and uses the macroporous adsorption resin with good selectivity on target active ingredients. However, the macroporous adsorption resin sold in the market at present cannot meet the single use requirement at all, so the invention synthesizes the macroporous adsorption resin with a special structure to be suitable for separating and purifying the effective components of the specific Chinese herbal medicines.
The invention content is as follows:
the invention aims to solve the technical problem of providing a preparation method of a benzimidazole macroporous adsorption resin, wherein the benzimidazole macroporous adsorption resin is prepared by functionally modifying styrene-divinylbenzene microspheres, and is applied to separation and purification of flavonoid compounds, so that the technical effect of remarkably improving the content of the flavonoid compounds in the product is achieved.
The technical problem to be solved by the invention is realized by adopting the following technical scheme:
the invention aims to provide a preparation method of a benzimidazole macroporous adsorption resin, which comprises the following preparation steps:
(1) adding a dispersing agent, sodium chloride and methylene blue into water, heating and stirring to completely dissolve the dispersing agent, and cooling to obtain a water phase; adding an oil phase consisting of styrene, divinyl benzene, a pore-forming agent and an initiator into the water phase, heating for reaction, stopping the reaction, alternately washing the obtained white balls with hot water and ethanol until the liquid is clear, and drying to obtain styrene-divinyl benzene microspheres;
(2) swelling the styrene-divinylbenzene microspheres obtained in the step (1) in chloromethyl ether, adding a catalyst, heating to carry out a chloromethylation reaction, washing with water, and drying to obtain chloromethylated styrene-divinylbenzene microspheres;
(3) swelling the chloromethylated styrene-divinylbenzene microspheres prepared in the step (2) in N, N-dimethylformamide, then adding 2-methylmercaptobenzimidazole and anhydrous potassium carbonate, heating for substitution reaction, washing with water, and drying to obtain the benzimidazole macroporous adsorption resin.
The dispersant is at least one of polyvinyl alcohol, gelatin and hydroxyethyl cellulose.
The pore-forming agent is isobutanol, and the initiator is benzoyl peroxide.
The dosage of the dispersant is 0.5-1.5% of the mass of the water phase, the dosage of the sodium chloride is 0.05-0.1% of the mass of the water phase, and the dosage of the methylene blue is 0.01-0.05% of the mass of the water phase.
The amount of the divinyl benzene is 20-30% of the mass of the styrene, the amount of the pore-foaming agent is 50-100% of the total mass of the styrene and the divinyl benzene, the amount of the initiator is 0.5-1% of the total mass of the styrene and the divinyl benzene, and the volume ratio of the water phase to the oil phase is (1-3): 1.
The styrene-divinylbenzene microspheres prepared in the step (1) belong to conventional macroporous adsorption resin in the field, and although the adsorption property is strong, the adsorption selectivity of the styrene-divinylbenzene microspheres to flavonoids compounds is poor, so that the high-efficiency separation and purification of the flavonoids compounds cannot be realized.
The catalyst is at least one of anhydrous ferric chloride and anhydrous zinc chloride.
The dosage of the catalyst is 20-50% of the mass of the styrene-divinylbenzene microspheres.
Chloromethyl ether is adopted to perform chloromethylation on the styrene-divinylbenzene microspheres in the step (2), chloromethyl is introduced to the styrene-divinylbenzene microspheres, and chloromethyl is taken as an active group, so that subsequent substitution reaction is facilitated.
The dosage of the 2-methylmercaptobenzimidazole is 15-30% of the mass of the chloromethylated styrene-divinylbenzene microsphere.
The molar ratio of the 2-methylmercaptobenzimidazole to the anhydrous potassium carbonate is 1 (1-1.2). Anhydrous potassium carbonate is adopted to neutralize hydrogen chloride generated in the reaction, so that the reaction rate is improved.
In the step (3), 2-methylmercaptobenzimidazole and chloromethyl are subjected to substitution reaction to prepare the benzimidazole macroporous adsorption resin, and the macroporous adsorption resin can show good adsorption selectivity on flavonoids, so that the flavonoids are efficiently separated and purified.
The invention also aims to provide the application of the benzimidazole macroporous adsorption resin in separation and purification of flavonoids compounds. The benzimidazole macroporous adsorption resin prepared by the invention is used for separating and purifying the Chinese herbal medicine extract containing the flavonoid compounds, and the high-content flavonoid compounds are obtained after adsorption-desorption.
The invention has the beneficial effects that:
(1) the preparation method comprises the steps of preparing styrene-divinylbenzene microspheres by a suspension polymerization method, carrying out chloromethylation on the styrene-divinylbenzene microspheres by using chloromethyl ether to prepare chloromethylated styrene-divinylbenzene microspheres, and carrying out substitution reaction on 2-methylmercaptobenzimidazole and the chloromethylated styrene-divinylbenzene microspheres to prepare the benzimidazole macroporous adsorption resin;
(2) the benzimidazole macroporous adsorption resin prepared by the invention has good adsorption selectivity on flavonoid compounds, is easy to desorb, can obtain high-content flavonoid compounds after desorption, and is suitable for separation and purification of the flavonoid compounds, so that the separation and purification operation of the flavonoid compounds is simplified, the loss of the flavonoid compounds in the separation and purification process is reduced, and the purity of the flavonoid compounds in the product is improved.
The specific implementation mode is as follows:
in order to make the technical means, the creation characteristics, the achievement purposes and the effects of the invention easy to understand, the invention is further described with the specific embodiments.
Example 1
(1) Adding gelatin, sodium chloride and methylene blue into water, wherein the dosage of the gelatin is 1% of the mass of the water phase, the dosage of the sodium chloride is 0.1% of the mass of the water phase, and the dosage of the methylene blue is 0.02% of the mass of the water phase, heating and stirring to completely dissolve the dispersing agent, and cooling to obtain a water phase; adding an oil phase consisting of styrene, divinyl benzene, isobutanol and benzoyl peroxide into the water phase, wherein the dosage of the divinyl benzene is 25% of the mass of the styrene, the dosage of the isobutanol is 100% of the total mass of the styrene and the divinyl benzene, the dosage of the benzoyl peroxide is 0.5% of the total mass of the styrene and the divinyl benzene, the volume ratio of the water phase to the oil phase is 2:1, heating to 80 ℃, reacting for 5 hours, stopping the reaction, alternately washing the obtained white balls with hot water and ethanol until the liquid is clear, and drying to obtain the styrene-divinyl benzene microspheres;
(2) swelling the styrene-divinylbenzene microspheres obtained in the step (1) in chloromethyl ether, adding anhydrous zinc chloride accounting for 25% of the mass of the styrene-divinylbenzene microspheres, heating to 40 ℃, reacting for 12 hours, washing with water, and drying to obtain chloromethylated styrene-divinylbenzene microspheres;
(3) swelling the chloromethylated styrene-divinylbenzene microspheres prepared in the step (2) in N, N-dimethylformamide, adding 2-methylmercaptobenzimidazole and anhydrous potassium carbonate which account for 20% of the mass of the chloromethylated styrene-divinylbenzene microspheres, wherein the molar ratio of the 2-methylmercaptobenzimidazole to the anhydrous potassium carbonate is 1:1, heating to 60 ℃, reacting for 5 hours, washing with water, and drying to obtain the benzimidazole macroporous adsorption resin.
Example 2
(1) Adding hydroxyethyl cellulose, sodium chloride and methylene blue into water, wherein the dosage of a dispersing agent is 1.5 percent of the mass of the water phase, the dosage of the sodium chloride is 0.05 percent of the mass of the water phase, and the dosage of the methylene blue is 0.01 percent of the mass of the water phase, heating and stirring to completely dissolve the dispersing agent, and cooling to obtain the water phase; adding an oil phase consisting of styrene, divinyl benzene, isobutanol and benzoyl peroxide into the water phase, wherein the dosage of the divinyl benzene is 25% of the mass of the styrene, the dosage of the isobutanol is 100% of the total mass of the styrene and the divinyl benzene, the dosage of the benzoyl peroxide is 1% of the total mass of the styrene and the divinyl benzene, the volume ratio of the water phase to the oil phase is 1:1, heating to 80 ℃, reacting for 5 hours, stopping the reaction, alternately washing the obtained white spheres with hot water and ethanol until the liquid is clear, and drying to obtain the styrene-divinyl benzene microspheres;
(2) swelling the styrene-divinylbenzene microspheres obtained in the step (1) in chloromethyl ether, adding anhydrous ferric chloride with the mass of 30% of that of the styrene-divinylbenzene microspheres, heating to 40 ℃, reacting for 12 hours, washing with water, and drying to obtain chloromethylated styrene-divinylbenzene microspheres;
(3) swelling the chloromethylated styrene-divinylbenzene microspheres prepared in the step (2) in N, N-dimethylformamide, adding 2-methylmercaptobenzimidazole and anhydrous potassium carbonate which account for 15% of the mass of the chloromethylated styrene-divinylbenzene microspheres, wherein the molar ratio of the 2-methylmercaptobenzimidazole to the anhydrous potassium carbonate is 1:1.1, heating to 60 ℃, reacting for 5 hours, washing with water, and drying to obtain the benzimidazole macroporous adsorption resin.
Example 3
(1) Adding polyvinyl alcohol, sodium chloride and methylene blue into water, wherein the dosage of a dispersing agent is 0.5 percent of the mass of the water phase, the dosage of the sodium chloride is 0.1 percent of the mass of the water phase, and the dosage of the methylene blue is 0.05 percent of the mass of the water phase, heating and stirring to completely dissolve the dispersing agent, and cooling to obtain the water phase; adding an oil phase consisting of styrene, divinyl benzene, isobutanol and benzoyl peroxide into the water phase, wherein the dosage of the divinyl benzene is 20% of the mass of the styrene, the dosage of the isobutanol is 50% of the total mass of the styrene and the divinyl benzene, the dosage of the benzoyl peroxide is 0.8% of the total mass of the styrene and the divinyl benzene, the volume ratio of the water phase to the oil phase is 3:1, heating to 80 ℃, reacting for 5 hours, stopping the reaction, alternately washing the obtained white balls with hot water and ethanol until the liquid is clear, and drying to obtain the styrene-divinyl benzene microspheres;
(2) swelling the styrene-divinylbenzene microspheres obtained in the step (1) in chloromethyl ether, adding anhydrous zinc chloride accounting for 35% of the mass of the styrene-divinylbenzene microspheres, heating to 40 ℃, reacting for 12 hours, washing with water, and drying to obtain chloromethylated styrene-divinylbenzene microspheres;
(3) swelling the chloromethylated styrene-divinylbenzene microspheres prepared in the step (2) in N, N-dimethylformamide, adding 2-methylmercaptobenzimidazole and anhydrous potassium carbonate which account for 30% of the mass of the chloromethylated styrene-divinylbenzene microspheres, wherein the molar ratio of the 2-methylmercaptobenzimidazole to the anhydrous potassium carbonate is 1:1.2, heating to 60 ℃, reacting for 5 hours, washing with water, and drying to obtain the benzimidazole macroporous adsorption resin.
Example 4
(1) Adding polyvinyl alcohol, sodium chloride and methylene blue into water, wherein the dosage of a dispersing agent is 1% of the mass of the water phase, the dosage of the sodium chloride is 0.1% of the mass of the water phase, and the dosage of the methylene blue is 0.03% of the mass of the water phase, heating and stirring to completely dissolve the dispersing agent, and cooling to obtain the water phase; adding an oil phase consisting of styrene, divinyl benzene, isobutanol and benzoyl peroxide into the water phase, wherein the dosage of the divinyl benzene is 30% of the mass of the styrene, the dosage of the isobutanol is 100% of the total mass of the styrene and the divinyl benzene, the dosage of the benzoyl peroxide is 1% of the total mass of the styrene and the divinyl benzene, the volume ratio of the water phase to the oil phase is 1.5:1, heating to 80 ℃, reacting for 5 hours, stopping the reaction, alternately washing the obtained white balls with hot water and ethanol until the liquid is clear, and drying to obtain the styrene-divinyl benzene microspheres;
(2) swelling the styrene-divinylbenzene microspheres obtained in the step (1) in chloromethyl ether, adding anhydrous zinc chloride accounting for 30% of the mass of the styrene-divinylbenzene microspheres, heating to 40 ℃, reacting for 12 hours, washing with water, and drying to obtain chloromethylated styrene-divinylbenzene microspheres;
(3) swelling the chloromethylated styrene-divinylbenzene microspheres prepared in the step (2) in N, N-dimethylformamide, adding 2-methylmercaptobenzimidazole and anhydrous potassium carbonate which account for 25% of the mass of the chloromethylated styrene-divinylbenzene microspheres, wherein the molar ratio of the 2-methylmercaptobenzimidazole to the anhydrous potassium carbonate is 1:1.1, heating to 60 ℃, reacting for 5 hours, washing with water, and drying to obtain the benzimidazole macroporous adsorption resin.
Comparative example 1
Comparative example 1 was conducted by replacing 2-methylmercaptobenzimidazole with benzimidazole in step (3) of example 4, and the rest was not changed.
Comparative example 2
Comparative example 2 in example 4, 2-methylmercaptobenzimidazole was replaced with dimethylamine in step (3), and the rest of the procedure was not changed.
Comparative example 3
Comparative example 3 the procedure of example 4, step (2) and step (3), was deleted and the rest of the procedure was unchanged.
Loading 100g of camellia seed hulls into an extraction tank, adding 1000g of 70% ethanol, performing reflux extraction at 50 ℃ for three times, performing first extraction for 2 hours, performing second extraction for 1 hour, performing third extraction for 1 hour, filtering, collecting extract, combining, concentrating and recovering ethanol to obtain a water phase; filling the benzimidazole macroporous adsorption resin into a column, wherein the mass ratio of the oil tea seed shells to the benzimidazole macroporous adsorption resin is 1:1, enabling the water phase to pass through the resin column at the flow rate of 0.5BV/h, then sequentially eluting with water, 30% ethanol and 50% ethanol at the flow rate of 2BV/h, collecting 50% ethanol eluent, concentrating and drying to obtain the product.
The content of flavonoids in the product was determined by HPLC method and the results are shown in the following table.
| Content of flavonoids/% | |
| Example 1 | 59.15 |
| Example 2 | 54.26 |
| Example 3 | 65.38 |
| Example 4 | 63.52 |
| Comparative example 1 | 50.23 |
| Comparative example 2 | 24.60 |
| Comparative example 3 | 18.57 |
The foregoing shows and describes the general principles and broad features of the present invention and advantages thereof. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the specification and illustrated only to illustrate the principle of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the present invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (10)
1. The preparation method of the benzimidazole macroporous adsorption resin is characterized by comprising the following preparation steps:
(1) adding a dispersing agent, sodium chloride and methylene blue into water, heating and stirring to completely dissolve the dispersing agent, and cooling to obtain a water phase; adding an oil phase consisting of styrene, divinyl benzene, a pore-forming agent and an initiator into the water phase, heating for reaction, stopping the reaction, alternately washing the obtained white balls with hot water and ethanol until the liquid is clear, and drying to obtain styrene-divinyl benzene microspheres;
(2) swelling the styrene-divinylbenzene microspheres obtained in the step (1) in chloromethyl ether, adding a catalyst, heating to carry out a chloromethylation reaction, washing with water, and drying to obtain chloromethylated styrene-divinylbenzene microspheres;
(3) swelling the chloromethylated styrene-divinylbenzene microspheres prepared in the step (2) in N, N-dimethylformamide, then adding 2-methylmercaptobenzimidazole and anhydrous potassium carbonate, heating for substitution reaction, washing with water, and drying to obtain the benzimidazole macroporous adsorption resin.
2. The preparation method of the benzimidazole macroporous adsorption resin according to claim 1, wherein the benzimidazole macroporous adsorption resin comprises the following steps: the dispersant is at least one of polyvinyl alcohol, gelatin and hydroxyethyl cellulose.
3. The preparation method of the benzimidazole macroporous adsorption resin according to claim 1, wherein the benzimidazole macroporous adsorption resin comprises the following steps: the pore-forming agent is isobutanol, and the initiator is benzoyl peroxide.
4. The preparation method of the benzimidazole macroporous adsorption resin according to claim 1, wherein the benzimidazole macroporous adsorption resin comprises the following steps: the dosage of the dispersant is 0.5-1.5% of the mass of the water phase, the dosage of the sodium chloride is 0.05-0.1% of the mass of the water phase, and the dosage of the methylene blue is 0.01-0.05% of the mass of the water phase.
5. The preparation method of the benzimidazole macroporous adsorption resin according to claim 1, wherein the benzimidazole macroporous adsorption resin comprises the following steps: the amount of the divinyl benzene is 20-30% of the mass of the styrene, the amount of the pore-foaming agent is 50-100% of the total mass of the styrene and the divinyl benzene, the amount of the initiator is 0.5-1% of the total mass of the styrene and the divinyl benzene, and the volume ratio of the water phase to the oil phase is (1-3): 1.
6. The preparation method of the benzimidazole macroporous adsorption resin according to claim 1, wherein the benzimidazole macroporous adsorption resin comprises the following steps: the catalyst is at least one of anhydrous ferric chloride and anhydrous zinc chloride.
7. The preparation method of the benzimidazole macroporous adsorption resin according to claim 1, wherein the benzimidazole macroporous adsorption resin comprises the following steps: the dosage of the catalyst is 20-50% of the mass of the styrene-divinylbenzene microspheres.
8. The preparation method of the benzimidazole macroporous adsorption resin according to claim 1, wherein the benzimidazole macroporous adsorption resin comprises the following steps: the dosage of the 2-methylmercaptobenzimidazole is 15-30% of the mass of the chloromethylated styrene-divinylbenzene microsphere.
9. The preparation method of the benzimidazole macroporous adsorption resin according to claim 1, wherein the benzimidazole macroporous adsorption resin comprises the following steps: the molar ratio of the 2-methylmercaptobenzimidazole to the anhydrous potassium carbonate is 1 (1-1.2).
10. Use of the benzimidazole macroporous adsorbent resin prepared according to any one of claims 1-9 for the separation and purification of flavonoids.
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| CN105837721A (en) * | 2016-06-12 | 2016-08-10 | 东华理工大学 | Macroporous succimide adsorbing resin and preparation method thereof |
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| CN106032432A (en) * | 2015-03-16 | 2016-10-19 | 同济大学 | 2-mercaptobenzimidazole/carbon nano-tube/polyaniline composite material and preparation thereof |
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