CN117000217B - Preparation method of high-capacity carboxylic acid type cation chromatographic packing and chromatographic packing - Google Patents
Preparation method of high-capacity carboxylic acid type cation chromatographic packing and chromatographic packing Download PDFInfo
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- CN117000217B CN117000217B CN202311053766.1A CN202311053766A CN117000217B CN 117000217 B CN117000217 B CN 117000217B CN 202311053766 A CN202311053766 A CN 202311053766A CN 117000217 B CN117000217 B CN 117000217B
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- polystyrene
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- carboxylic acid
- divinylbenzene
- chromatographic packing
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- 238000012856 packing Methods 0.000 title claims abstract description 38
- 150000001768 cations Chemical class 0.000 title claims abstract description 24
- 150000001732 carboxylic acid derivatives Chemical class 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000004005 microsphere Substances 0.000 claims abstract description 52
- 238000006243 chemical reaction Methods 0.000 claims abstract description 42
- 229920003053 polystyrene-divinylbenzene Polymers 0.000 claims abstract description 41
- 238000011282 treatment Methods 0.000 claims abstract description 18
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000006722 reduction reaction Methods 0.000 claims abstract description 11
- 238000005341 cation exchange Methods 0.000 claims abstract description 7
- 125000002843 carboxylic acid group Chemical group 0.000 claims abstract description 6
- 238000005660 chlorination reaction Methods 0.000 claims abstract description 6
- 238000006277 sulfonation reaction Methods 0.000 claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- 238000005406 washing Methods 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 20
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 15
- 239000004793 Polystyrene Substances 0.000 claims description 12
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 12
- -1 lithium aluminum hydride Chemical compound 0.000 claims description 12
- 229920002223 polystyrene Polymers 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- 238000001914 filtration Methods 0.000 claims description 11
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 239000012670 alkaline solution Substances 0.000 claims description 9
- 239000002245 particle Substances 0.000 claims description 9
- 239000000243 solution Substances 0.000 claims description 9
- 239000003638 chemical reducing agent Substances 0.000 claims description 8
- 238000004132 cross linking Methods 0.000 claims description 8
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 claims description 8
- 239000012320 chlorinating reagent Substances 0.000 claims description 7
- 239000003999 initiator Substances 0.000 claims description 7
- 230000007935 neutral effect Effects 0.000 claims description 7
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims description 6
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 claims description 6
- 239000000178 monomer Substances 0.000 claims description 6
- 238000006116 polymerization reaction Methods 0.000 claims description 6
- 239000003381 stabilizer Substances 0.000 claims description 6
- 230000008961 swelling Effects 0.000 claims description 6
- 230000002194 synthesizing effect Effects 0.000 claims description 6
- 238000011068 loading method Methods 0.000 claims description 5
- 230000020477 pH reduction Effects 0.000 claims description 5
- 239000011148 porous material Substances 0.000 claims description 5
- 238000010992 reflux Methods 0.000 claims description 5
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 4
- 229910019213 POCl3 Inorganic materials 0.000 claims description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 4
- DBJUEJCZPKMDPA-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O DBJUEJCZPKMDPA-UHFFFAOYSA-N 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 239000012280 lithium aluminium hydride Substances 0.000 claims description 4
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 4
- 239000011976 maleic acid Substances 0.000 claims description 4
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 4
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 4
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 3
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 3
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 3
- 229910006024 SO2Cl2 Inorganic materials 0.000 claims description 3
- 230000003113 alkalizing effect Effects 0.000 claims description 3
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 3
- 239000003153 chemical reaction reagent Substances 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 239000003431 cross linking reagent Substances 0.000 claims description 3
- 238000012674 dispersion polymerization Methods 0.000 claims description 3
- 239000003995 emulsifying agent Substances 0.000 claims description 3
- 239000005457 ice water Substances 0.000 claims description 3
- 230000000977 initiatory effect Effects 0.000 claims description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 3
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 3
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 3
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 3
- 150000003254 radicals Chemical class 0.000 claims description 3
- 239000012429 reaction media Substances 0.000 claims description 3
- DAJSVUQLFFJUSX-UHFFFAOYSA-M sodium;dodecane-1-sulfonate Chemical compound [Na+].CCCCCCCCCCCCS([O-])(=O)=O DAJSVUQLFFJUSX-UHFFFAOYSA-M 0.000 claims description 3
- PXQLVRUNWNTZOS-UHFFFAOYSA-N sulfanyl Chemical class [SH] PXQLVRUNWNTZOS-UHFFFAOYSA-N 0.000 claims description 3
- YBBRCQOCSYXUOC-UHFFFAOYSA-N sulfuryl dichloride Chemical compound ClS(Cl)(=O)=O YBBRCQOCSYXUOC-UHFFFAOYSA-N 0.000 claims description 3
- 125000002091 cationic group Chemical group 0.000 claims 4
- 239000000463 material Substances 0.000 claims 1
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 abstract description 12
- 239000000126 substance Substances 0.000 abstract description 10
- 238000000926 separation method Methods 0.000 abstract description 8
- 229920000642 polymer Polymers 0.000 abstract description 7
- 238000012986 modification Methods 0.000 abstract description 6
- 230000004048 modification Effects 0.000 abstract description 6
- 238000013375 chromatographic separation Methods 0.000 abstract description 5
- 239000002253 acid Substances 0.000 abstract description 4
- 238000002386 leaching Methods 0.000 abstract description 4
- 239000003513 alkali Substances 0.000 abstract description 3
- 239000011159 matrix material Substances 0.000 abstract description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 12
- 230000035484 reaction time Effects 0.000 description 9
- 150000001412 amines Chemical class 0.000 description 6
- 229910021529 ammonia Inorganic materials 0.000 description 5
- 238000005277 cation exchange chromatography Methods 0.000 description 5
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 4
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 238000011049 filling Methods 0.000 description 3
- 150000003956 methylamines Chemical class 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- 239000012065 filter cake Substances 0.000 description 2
- 238000000265 homogenisation Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- PQSQBXGSIRXRFL-UHFFFAOYSA-N 2-methylpropanamide;dihydrochloride Chemical compound Cl.Cl.CC(C)C(N)=O PQSQBXGSIRXRFL-UHFFFAOYSA-N 0.000 description 1
- 206010007269 Carcinogenicity Diseases 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 1
- 239000012491 analyte Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 231100000260 carcinogenicity Toxicity 0.000 description 1
- 230000007670 carcinogenicity Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 210000005069 ears Anatomy 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 210000001508 eye Anatomy 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 210000003734 kidney Anatomy 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 210000004185 liver Anatomy 0.000 description 1
- 229940098779 methanesulfonic acid Drugs 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000003541 multi-stage reaction Methods 0.000 description 1
- XKLJHFLUAHKGGU-UHFFFAOYSA-N nitrous amide Chemical compound ON=N XKLJHFLUAHKGGU-UHFFFAOYSA-N 0.000 description 1
- 210000001331 nose Anatomy 0.000 description 1
- 150000002898 organic sulfur compounds Chemical class 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 210000003800 pharynx Anatomy 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 210000002345 respiratory system Anatomy 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 210000003491 skin Anatomy 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
Classifications
-
- 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
- B01J20/281—Sorbents specially adapted for preparative, analytical or investigative chromatography
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- 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
- B01D15/08—Selective adsorption, e.g. chromatography
- B01D15/26—Selective adsorption, e.g. chromatography characterised by the separation mechanism
- B01D15/36—Selective adsorption, e.g. chromatography characterised by the separation mechanism involving ionic interaction
- B01D15/361—Ion-exchange
- B01D15/362—Cation-exchange
-
- 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
-
- 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
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28016—Particle form
- B01J20/28021—Hollow particles, e.g. hollow spheres, microspheres or cenospheres
-
- 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
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/3085—Chemical treatments not covered by groups B01J20/3007 - B01J20/3078
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- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention discloses a preparation method of a high-capacity carboxylic acid type cation chromatographic packing, which takes polystyrene-divinylbenzene as a matrix of polymer microspheres, and obtains the cation exchange chromatographic packing with a grafted carboxylic acid group on the surface after multi-step modification of concentrated sulfuric acid sulfonation, alkali treatment, chlorination reaction, reduction reaction and 'mercapto-ene' modification chemical reaction, and the prepared weak acid type cation chromatographic column has good chromatographic separation performance and can finish the equal separation of 6 cations and 3 methylamine substances by using a single leaching solution.
Description
Technical Field
The invention relates to the field of ion chromatographic packing preparation and analysis application, in particular to a preparation method of high-capacity carboxylic acid type cation chromatographic packing and the chromatographic packing.
Background
Ammonia is a colorless gas with strong irritating malodor at normal temperature and pressure. Amine is a derivative of ammonia molecule in which one or more hydrogen atoms are replaced by hydrocarbon groups, and methylamine, dimethylamine and trimethylamine have ammonia taste or fishy taste. Ammonia and organic amines are malodorous contaminants next to organic sulfur compounds. Ammonia and organic amines are important chemical raw materials and are widely used in various industries. Ammonia and most organic amines are irritating and toxic, and damage to eyes, ears, nose, throat, skin, respiratory tract, liver, kidneys and the like, and can react with nitrite to generate nitrosamine substances with strong carcinogenicity, so that the detection of the amine substances is very necessary. However, the current chromatographic column is only limited to be used for the conventional 6 cations (Li +、Na+、NH4 +、K+、Mg2+、Ca2+), and separation of amine substances cannot be satisfied.
Disclosure of Invention
In order to solve the existing defects, the invention aims to provide a preparation method of a high-capacity carboxylic acid type cation chromatographic packing and the chromatographic packing, wherein the preparation method of the chromatographic packing is carried out by multi-step reaction, the prepared weak acid type cation chromatographic column has good chromatographic separation performance, and the isocratic separation of 6 cations and 3 methylamine substances can be completed by using a single leaching solution.
The technical scheme adopted for solving the technical problems is as follows: a method for preparing a high capacity carboxylic acid type cation chromatographic packing, comprising the following steps:
s1, synthesizing monodisperse polystyrene microsphere seeds by a dispersion polymerization method;
Styrene is taken as a monomer, polyvinylpyrrolidone is taken as a stabilizer, azodiisobutyronitrile is taken as an initiator, and a free radical initiation polymerization reaction is carried out in an ethanol solution serving as a reaction medium to generate monodisperse polystyrene seeds;
s2, synthesizing polystyrene-divinylbenzene microspheres with high crosslinking degree by adopting a single-step seed swelling method;
Adding dibutyl phthalate into a proper amount of polystyrene seeds to activate the seeds, adding monomer styrene, a cross-linking agent divinylbenzene, an emulsifier sodium dodecyl sulfonate, a stabilizer polyvinyl alcohol, an initiator benzoyl peroxide and a pore-forming agent toluene after the polystyrene seeds are activated, fully swelling a reaction system after stirring, and heating to initiate polymerization reaction to generate monodisperse polystyrene-divinylbenzene microspheres with uniform particle size;
S3, sulfonation treatment of concentrated sulfuric acid;
adding a proper amount of concentrated sulfuric acid into polystyrene-divinylbenzene microspheres, performing ultrasonic stirring, pouring cold water after the reaction is finished, filtering and washing for multiple times for later use;
s4, alkalizing;
adding sulfonated polystyrene-divinylbenzene microspheres into an alkaline solution, washing with deionized water to be neutral after a period of time to obtain sulfonic acid-alkalized polystyrene-divinylbenzene microspheres, and then drying for later use;
s5, chlorination reaction;
Condensing and refluxing the polystyrene-divinylbenzene microspheres alkalified by sulfonic acid by using a chlorinating reagent, slowly pouring the microspheres into cold water after finishing, standing for a period of time, filtering, washing and drying for later use to obtain sulfonyl-chlorinated polystyrene-divinylbenzene microspheres;
s6, reduction reaction;
Reducing the sulfonyl-chlorinated polystyrene-divinylbenzene microspheres in an ice-water bath by adopting a reducing agent, acidifying and washing with water to be neutral after the completion of the reduction to obtain the mercapto polystyrene-divinylbenzene microspheres, and drying for later use, wherein the reducing agent is one of SnCl 2、Na2SO3, zinc-acetic acid and lithium aluminum hydride, the concentration is 0.001M-1M, the treatment time is 1 h-24 h, and the reaction temperature is-10-30 ℃;
s7, carrying out a 'mercapto-ene' reaction;
And (3) reacting a carboxylic acid compound containing double bonds with thiolated polystyrene-divinylbenzene microspheres, washing and drying after the reaction is finished to obtain cation exchange chromatographic packing with high-capacity carboxylic acid groups grafted on the surface, and loading the packing into a column by a homogenate method, wherein the carboxylic acid compound containing double bonds is one of acrylic acid, maleic acid and methacrylic acid, the concentration is 0.001M-1M, the treatment time is 1 h-24 h, and the reaction temperature is 10-100 ℃.
Optionally, the particle size of the polystyrene-divinylbenzene microsphere is 3-10 μm, the crosslinking degree is 5% -80%, and the pore diameter is 20-2000A.
Optionally, the proportion of the polystyrene-divinylbenzene microspheres to the concentrated sulfuric acid is arbitrary, and the ultrasonic stirring time is arbitrary.
Optionally, the alkaline solution is one of NaOH and KOH, the concentration is 0.001M-1M, and the treatment time is 1 h-24 h.
Optionally, the chlorinating reagent is one or the combination of two of PCl 5、POCl3、SO2Cl2, the concentration is 0.001M-1M, the treatment time is 1 h-24 h, and the reaction temperature is 30-200 ℃.
Optionally, the reducing agent is one of SnCl 2、Na2SO3, zinc-acetic acid and lithium aluminum hydride, the concentration is 0.001M-1M, the treatment time is 1 h-24 h, and the reaction temperature is-10 ℃ to 30 ℃.
Optionally, when acidification is carried out after the reduction reaction is finished, the reagent used is one of HCl and H 2SO4、CH3 COOH, the concentration is 0.001M-1M, the treatment time is 1H-24H, and the reaction temperature is 30-100 ℃.
Optionally, the carboxylic acid compound containing double bonds is one of acrylic acid, maleic acid and methacrylic acid, the concentration is 0.001M-1M, the treatment time is 1 h-24 h, and the reaction temperature is 10-100 ℃.
The invention also provides a chromatographic packing which is prepared by adopting the method.
From the above, the beneficial effects of the invention are as follows: the invention provides a preparation and application method of a high-capacity carboxylic acid type cation chromatographic packing, which uses polystyrene-divinylbenzene as a matrix of polymer microspheres, and obtains the cation exchange chromatographic packing with a surface grafted with carboxylic acid groups after multi-step modification of concentrated sulfuric acid sulfonation, alkali treatment, chlorination reaction, reduction reaction and 'mercapto-ene' modification chemical reaction, and the prepared weak acid type cation chromatographic column has good chromatographic separation performance, and can complete the equal separation of 6 cations and 3 methylamine substances by using a single leaching solution, thereby expanding the application method of cation chromatography and shortening analysis time.
Drawings
FIG. 1 is a schematic diagram of the synthesis principle of the high capacity carboxylic acid type cation chromatographic packing prepared by the invention.
FIG. 2 is a chromatogram of an ion chromatographic column packed with a high capacity carboxylic acid type cation chromatographic packing prepared by the invention for isocratic separation of conventional 6 cations from 3 methylamines.
Detailed Description
The application is described in further detail below with reference to the drawings and examples. It is to be understood that the specific embodiments described herein are merely illustrative of the application and are not limiting of the application. It should be noted that, for convenience of description, only the portions related to the application are shown in the drawings.
The method for preparing the high capacity carboxylic acid type cation exchange chromatography packing according to the embodiment of the present invention is described below.
As shown in figure 1, the invention discloses a preparation method of a high-capacity carboxylic acid type cation chromatographic packing, which takes polystyrene-divinylbenzene as a matrix of polymer microspheres, and obtains the cation exchange chromatographic packing with surface grafted carboxylic acid groups after multi-step modification of concentrated sulfuric acid sulfonation, alkali treatment, chlorination reaction, reduction reaction and 'mercapto-alkene' modification chemical reaction, and column packing is carried out by a homogenate method.
The preparation method comprises the following specific steps:
s1, synthesizing monodisperse polystyrene microsphere seeds by adopting a dispersion polymerization method.
Styrene is used as a monomer, polyvinylpyrrolidone is used as a stabilizer, azodiisobutyronitrile is used as an initiator, and a free radical initiation polymerization reaction is carried out in an ethanol solution which is used as a reaction medium to generate monodisperse polystyrene seeds;
s2, synthesizing the polystyrene-divinylbenzene microsphere with high crosslinking degree by adopting a single-step seed swelling method.
And adding a proper amount of polystyrene seeds into dibutyl phthalate to activate the seeds, adding monomer styrene, a cross-linking agent divinylbenzene, an emulsifier sodium dodecyl sulfonate, a stabilizer polyvinyl alcohol, an initiator benzoyl peroxide and a pore-forming agent toluene after the polystyrene seeds are activated, fully swelling a reaction system after stirring, and heating to initiate a polymerization reaction to generate monodisperse polystyrene-divinylbenzene microspheres with uniform particle sizes.
The particle size of the polystyrene-divinylbenzene microsphere is 3-10 mu m, the crosslinking degree is 5-80%, and the pore diameter is 20-2000A. In one embodiment of the present invention, the resulting polystyrene-divinylbenzene microspheres had a particle size of 5 μm, a degree of crosslinking of 80% and a pore size of 100 a.
S3, sulfonation treatment of concentrated sulfuric acid:
Adding a proper amount of concentrated sulfuric acid into polystyrene-divinylbenzene microspheres, then carrying out ultrasonic stirring, pouring cold water after the reaction is finished, filtering and washing for multiple times for standby, and obtaining sulfonated polystyrene-divinylbenzene microspheres.
In the invention, the ultrasonic stirring time is any time, but the condition that the surface of each polystyrene-divinylbenzene microsphere particle is stained with concentrated sulfuric acid during stirring is satisfied.
S4, alkalizing:
adding sulfonated polystyrene-divinylbenzene microspheres into alkaline solution, reacting for a period of time, washing with deionized water to neutrality to obtain sulfonic acid-alkalized polystyrene-divinylbenzene microspheres, and then drying for later use.
The alkaline solution is one of NaOH and KOH, and the concentration of the alkaline solution is 0.001M-1M, wherein the reaction time of the alkaline solution and the polystyrene-divinylbenzene microsphere is 1-24 h. In one embodiment of the invention, the alkaline solution is NaOH at a concentration of 0.1M for a reaction time of 12 hours.
S5, chlorination reaction:
Condensing and refluxing the polystyrene-divinylbenzene microspheres alkalified by sulfonic acid by using a chlorinating reagent, slowly pouring the microspheres into cold water after finishing, standing for a period of time, filtering, washing and drying for later use to obtain the sulfonyl-chlorinated polystyrene-divinylbenzene microspheres.
Wherein the chlorinating reagent is one or the combination of two of PCl 5、POCl3、SO2Cl2, the concentration is 0.001M-1M, the condensation reflux reaction time is 1 h-24 h, and the reaction temperature is 30-200 ℃. In one embodiment of the invention, the chlorinating agent is a composition of PCl 5、POCl3 at a concentration of 0.5M for a reaction time of 5 hours at a reaction temperature of 110 ℃.
S6, reduction reaction:
Reducing reaction is carried out on sulfonyl-chloridized polystyrene-divinylbenzene microspheres in ice-water bath by adopting a reducing agent, after the completion, the microspheres are acidified and then washed to be neutral by water, and the thiolated polystyrene-divinylbenzene microspheres are obtained and then dried for later use.
Wherein the reducing agent is one of SnCl 2、Na2SO3, zinc-acetic acid and lithium aluminum hydride, the concentration is 0.001M-1M, the reduction reaction time is 1 h-24 h, and the reaction temperature is-10 ℃ to 30 ℃. In one embodiment of the invention, the reducing agent is SnCl 2, the concentration is 0.1M, the reaction time is 5h, and the reaction temperature is 0 ℃.
The reagent used in acidification is one of HCl and H 2SO4、CH3 COOH, the concentration is 0.001M-1M, the acidification time is 1H-24H, and the reaction temperature is 30-100 ℃. In one embodiment of the invention, the acidulant is HCl at a concentration of 0.1M for a reaction time of 1h at a reaction temperature of 60 ℃.
S7, "mercapto-ene" reaction:
And (3) reacting the carboxylic acid compound containing double bonds with the mercapto polystyrene-divinylbenzene microspheres, washing and drying after the reaction is finished to obtain the cation exchange chromatographic packing with the surface grafted with the high-capacity carboxylic acid groups, and loading the column by using a homogenization method, wherein the column loading pressure is selected to be 20-60MPa, and the column loading time is 0.5-3h, thus obtaining the chromatographic column.
Wherein the carboxylic acid compound containing double bonds is one of acrylic acid, maleic acid and methacrylic acid, the concentration is 0.001M-1M, the reaction time is 1 h-24 h, and the reaction temperature is 10-100 ℃. In one embodiment of the invention, the carboxylic acid compound containing double bonds is acrylic acid, the concentration is 0.2M, the reaction time is 8 hours, and the reaction temperature is 70 ℃.
The cation exchange chromatographic packing is prepared by the preparation method, the prepared weak acid cation chromatographic column has good chromatographic separation performance, and the isocratic separation of 6 cations and 3 methylamine substances can be completed by using a single leaching solution, so that the application method of cation chromatography is expanded, and the analysis time is shortened.
Specific examples of the present invention are described below with reference to fig. 1 and 2, and 6 cations and 3 methylamines were detected using the prepared cation exchange chromatography packing.
Examples
Weighing 4g of polymer microspheres with the particle size of 5 mu m, the crosslinking degree of 80% and the pore diameter of 100A, pouring 40mL of concentrated sulfuric acid, carrying out ultrasonic stirring reaction for 10min, pouring cold water, carrying out suction filtration by using a sand core funnel, and washing with deionized water for multiple times until the washing liquid is neutral, thus obtaining sulfonated polymer microspheres.
Weighing 4g of sulfonated polymer microspheres, pouring 100mL of 0.1M NaOH solution, stirring for 12 hours at room temperature, filtering by a sand core funnel after the reaction is finished, washing for multiple times by deionized water until the washing solution is neutral, obtaining sulfonic acid-alkalized polymer microspheres, and drying for later use.
Pouring the reaction product into a 500mL three-neck flask, adding 10g PCl 5,200mLPOCl3, condensing and refluxing at 110 ℃ for 5h, slowly pouring into cold water after the reaction is finished, standing for a period of time, filtering by a sand core funnel, washing for multiple times by deionized water, and drying for later use.
Placing the reaction product into a three-neck flask, adding 100mL of 0.1M SnCl 2 reducing solution, stirring for reaction for 5 hours in an ice bath, filtering with a sand core funnel after the reaction is finished, washing with deionized water for many times, taking out a filter cake in a beaker, adding 0.1M HCl into the filter cake for acidification reaction for 1 hour at 60 ℃, filtering with the sand core funnel, washing with deionized water for many times, and drying for later use.
The reaction product is placed in a three-neck flask, 100mL of 0.2M acrylic acid aqueous solution and 0.1g of 2, 2-azobis (2-methylpropionamide) dihydrochloride are added as an initiator, and the reaction is mechanically stirred for 8h under the condition of water bath heating at 70 ℃. And immediately filtering the product by a sand core funnel after the reaction is finished, washing the product by deionized water for three times, and drying the product for standby to obtain the chromatographic packing.
Examples
Cation exchange chromatography packing performance test.
Weighing the prepared chromatographic packing, adding 50mL of deionized water, uniformly dispersing by ultrasonic, pouring into a homogenization tank of a column filling machine, adjusting the column filling pressure to 30MPa, filling the column for 1h, taking down the chromatographic column, and performing performance test after packaging.
Test conditions:
analyte: 6 common cations (Li+, na+, NH4+, K+, mg2+, ca2+), 3 methylamines (methylamine, dimethylamine, trimethylamine)
Flow rate: 1.0mL/min
Eluent: 30mM methanesulfonic acid
Chromatographic column: 4.6 x 250mm
As shown in FIG. 2, which shows the chromatographic separation patterns of the 9 substances, the prepared cation chromatographic column can realize baseline separation of all the substances within 20min and has good separation effect.
It should be noted that, without conflict, the embodiments of the present application and features of the embodiments may be combined with each other. The application will be described in detail below with reference to the drawings in connection with embodiments.
The above description is only illustrative of the preferred embodiments of the present application and of the principles of the technology employed. It will be appreciated by persons skilled in the art that the scope of the application referred to in the present application is not limited to the specific combinations of the technical features described above, but also covers other technical features formed by any combination of the technical features described above or their equivalents without departing from the inventive concept. Such as the above-mentioned features and the technical features disclosed in the present application (but not limited to) having similar functions are replaced with each other.
Other technical features besides those described in the specification are known to those skilled in the art, and are not described herein in detail to highlight the innovative features of the present invention.
Claims (6)
1. The preparation method of the high-capacity carboxylic acid type cation chromatographic packing is characterized by comprising the following steps of:
s1, synthesizing monodisperse polystyrene microsphere seeds by a dispersion polymerization method;
Styrene is taken as a monomer, polyvinylpyrrolidone is taken as a stabilizer, azodiisobutyronitrile is taken as an initiator, and a free radical initiation polymerization reaction is carried out in an ethanol solution serving as a reaction medium to generate monodisperse polystyrene seeds;
s2, synthesizing polystyrene-divinylbenzene microspheres with high crosslinking degree by adopting a single-step seed swelling method;
Adding dibutyl phthalate into a proper amount of polystyrene seeds to activate the seeds, adding monomer styrene, a cross-linking agent divinylbenzene, an emulsifier sodium dodecyl sulfonate, a stabilizer polyvinyl alcohol, an initiator benzoyl peroxide and a pore-forming agent toluene after the polystyrene seeds are activated, fully swelling a reaction system after stirring, and heating to initiate polymerization reaction to generate monodisperse polystyrene-divinylbenzene microspheres with uniform particle size;
S3, sulfonation treatment of concentrated sulfuric acid;
adding a proper amount of concentrated sulfuric acid into polystyrene-divinylbenzene microspheres, performing ultrasonic stirring, pouring cold water after the reaction is finished, filtering and washing for multiple times for later use;
s4, alkalizing;
adding sulfonated polystyrene-divinylbenzene microspheres into an alkaline solution, washing with deionized water to be neutral after a period of time to obtain sulfonic acid-alkalized polystyrene-divinylbenzene microspheres, and then drying for later use;
s5, chlorination reaction;
Condensing and refluxing the polystyrene-divinylbenzene microspheres alkalified by sulfonic acid by using a chlorinating reagent, slowly pouring the microspheres into cold water after finishing, standing for a period of time, filtering, washing and drying for later use to obtain sulfonyl-chlorinated polystyrene-divinylbenzene microspheres;
s6, reduction reaction;
Reducing the sulfonyl-chlorinated polystyrene-divinylbenzene microspheres in an ice-water bath by adopting a reducing agent, acidifying and washing with water to be neutral after the completion of the reduction to obtain the mercapto polystyrene-divinylbenzene microspheres, and drying for later use, wherein the reducing agent is one of SnCl 2、Na2SO3, zinc-acetic acid and lithium aluminum hydride, the concentration is 0.001M-1M, the treatment time is 1 h-24 h, and the reaction temperature is-10-30 ℃;
s7, carrying out a 'mercapto-ene' reaction;
And (3) reacting a carboxylic acid compound containing double bonds with thiolated polystyrene-divinylbenzene microspheres, washing and drying after the reaction is finished to obtain cation exchange chromatographic packing with high-capacity carboxylic acid groups grafted on the surface, and loading the packing into a column by a homogenate method, wherein the carboxylic acid compound containing double bonds is one of acrylic acid, maleic acid and methacrylic acid, the concentration is 0.001M-1M, the treatment time is 1 h-24 h, and the reaction temperature is 10-100 ℃.
2. The method for preparing a high-capacity carboxylic acid type cationic chromatographic packing according to claim 1, wherein the polystyrene-divinylbenzene microsphere has a particle size of 3-10 μm, a degree of crosslinking of 5% -80% and a pore size of 20-2000 a.
3. The method for preparing a high-capacity carboxylic acid type cationic chromatographic packing according to claim 1, wherein the alkaline solution is one of NaOH and KOH, the concentration is 0.001 m-1 m, and the treatment time is 1 h-24 h.
4. The preparation method and application of the high-capacity carboxylic acid type cationic chromatographic packing material according to claim 1, wherein the chlorinating agent is one or the combination of two of PCl 5、POCl3、SO2Cl2, the concentration is 0.001M-1M, the treatment time is 1 h-24 h, and the reaction temperature is 30-200 ℃.
5. The method for preparing a high-capacity carboxylic acid type cationic chromatographic packing according to claim 1, wherein the reagent used in the acidification after the completion of the reduction reaction is one of HCl and H 2SO4、CH3 COOH, the concentration is 0.001m to 1m, the treatment time is 1H to 24H, and the reaction temperature is 30 ℃ to 100 ℃.
6. A chromatographic packing prepared by the method of any one of claims 1 to 5.
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