CN115785513B - Weak acid substrate with high specific surface area and application thereof - Google Patents
Weak acid substrate with high specific surface area and application thereof Download PDFInfo
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- CN115785513B CN115785513B CN202111054697.7A CN202111054697A CN115785513B CN 115785513 B CN115785513 B CN 115785513B CN 202111054697 A CN202111054697 A CN 202111054697A CN 115785513 B CN115785513 B CN 115785513B
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- 239000002253 acid Substances 0.000 title claims abstract description 104
- 239000000758 substrate Substances 0.000 title claims abstract description 50
- 239000000463 material Substances 0.000 claims abstract description 76
- 229920001577 copolymer Polymers 0.000 claims abstract description 38
- 239000000178 monomer Substances 0.000 claims abstract description 33
- 229920000642 polymer Polymers 0.000 claims abstract description 25
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 21
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 14
- 239000003999 initiator Substances 0.000 claims abstract description 14
- 238000004132 cross linking Methods 0.000 claims abstract description 13
- 125000003277 amino group Chemical group 0.000 claims abstract description 6
- 229920000578 graft copolymer Polymers 0.000 claims abstract description 6
- 230000009471 action Effects 0.000 claims abstract description 3
- 230000000379 polymerizing effect Effects 0.000 claims abstract description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 31
- 238000003756 stirring Methods 0.000 claims description 22
- 239000003431 cross linking reagent Substances 0.000 claims description 20
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 18
- 239000004088 foaming agent Substances 0.000 claims description 17
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 125000005442 diisocyanate group Chemical group 0.000 claims description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 14
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 9
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 8
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 8
- 239000004593 Epoxy Substances 0.000 claims description 7
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 7
- 239000003054 catalyst Substances 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 229910000077 silane Inorganic materials 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- 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 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 5
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 5
- 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 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 4
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 4
- BWJUFXUULUEGMA-UHFFFAOYSA-N propan-2-yl propan-2-yloxycarbonyloxy carbonate Chemical compound CC(C)OC(=O)OOC(=O)OC(C)C BWJUFXUULUEGMA-UHFFFAOYSA-N 0.000 claims description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 3
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 3
- LBSXSAXOLABXMF-UHFFFAOYSA-N 4-Vinylaniline Chemical compound NC1=CC=C(C=C)C=C1 LBSXSAXOLABXMF-UHFFFAOYSA-N 0.000 claims description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 3
- PDSKWUZFFRWRCD-UHFFFAOYSA-N hept-6-en-1-amine Chemical compound NCCCCCC=C PDSKWUZFFRWRCD-UHFFFAOYSA-N 0.000 claims description 3
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 3
- 239000011976 maleic acid Substances 0.000 claims description 3
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 3
- PYGHKJQHDXSHES-UHFFFAOYSA-N undec-10-en-1-amine Chemical compound NCCCCCCCCCC=C PYGHKJQHDXSHES-UHFFFAOYSA-N 0.000 claims description 3
- WBYWAXJHAXSJNI-VOTSOKGWSA-M .beta-Phenylacrylic acid Natural products [O-]C(=O)\C=C\C1=CC=CC=C1 WBYWAXJHAXSJNI-VOTSOKGWSA-M 0.000 claims description 2
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 claims description 2
- VLSRKCIBHNJFHA-UHFFFAOYSA-N 2-(trifluoromethyl)prop-2-enoic acid Chemical compound OC(=O)C(=C)C(F)(F)F VLSRKCIBHNJFHA-UHFFFAOYSA-N 0.000 claims description 2
- IFSSSYDVRQSDSG-UHFFFAOYSA-N 3-ethenylaniline Chemical compound NC1=CC=CC(C=C)=C1 IFSSSYDVRQSDSG-UHFFFAOYSA-N 0.000 claims description 2
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 claims description 2
- VFPLSXYJYAKZCT-VOTSOKGWSA-N 4-[(e)-2-phenylethenyl]aniline Chemical compound C1=CC(N)=CC=C1\C=C\C1=CC=CC=C1 VFPLSXYJYAKZCT-VOTSOKGWSA-N 0.000 claims description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 2
- WBYWAXJHAXSJNI-SREVYHEPSA-N Cinnamic acid Chemical compound OC(=O)\C=C/C1=CC=CC=C1 WBYWAXJHAXSJNI-SREVYHEPSA-N 0.000 claims description 2
- 229930016911 cinnamic acid Natural products 0.000 claims description 2
- 235000013985 cinnamic acid Nutrition 0.000 claims description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 2
- 229920001519 homopolymer Polymers 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- WBYWAXJHAXSJNI-UHFFFAOYSA-N methyl p-hydroxycinnamate Natural products OC(=O)C=CC1=CC=CC=C1 WBYWAXJHAXSJNI-UHFFFAOYSA-N 0.000 claims description 2
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims description 2
- HOMWBVGCEKMCBR-UHFFFAOYSA-N oct-7-en-1-amine Chemical compound NCCCCCCC=C HOMWBVGCEKMCBR-UHFFFAOYSA-N 0.000 claims description 2
- UVBBCQLPTZEDHT-UHFFFAOYSA-N pent-4-en-1-amine Chemical compound NCCCC=C UVBBCQLPTZEDHT-UHFFFAOYSA-N 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims description 2
- 229940094938 stannous 2-ethylhexanoate Drugs 0.000 claims description 2
- 150000003512 tertiary amines Chemical class 0.000 claims description 2
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- MTLWTRLYHAQCAM-UHFFFAOYSA-N 2-[(1-cyano-2-methylpropyl)diazenyl]-3-methylbutanenitrile Chemical compound CC(C)C(C#N)N=NC(C#N)C(C)C MTLWTRLYHAQCAM-UHFFFAOYSA-N 0.000 claims 1
- BYDRTKVGBRTTIT-UHFFFAOYSA-N 2-methylprop-2-en-1-ol Chemical compound CC(=C)CO BYDRTKVGBRTTIT-UHFFFAOYSA-N 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 99
- 239000000126 substance Substances 0.000 abstract description 22
- 238000001514 detection method Methods 0.000 abstract description 18
- 239000002585 base Substances 0.000 description 34
- 230000008859 change Effects 0.000 description 28
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 25
- 239000003729 cation exchange resin Substances 0.000 description 25
- 239000008399 tap water Substances 0.000 description 23
- 235000020679 tap water Nutrition 0.000 description 23
- 238000012360 testing method Methods 0.000 description 23
- 230000002378 acidificating effect Effects 0.000 description 19
- 239000011347 resin Substances 0.000 description 18
- 229920005989 resin Polymers 0.000 description 18
- 230000008569 process Effects 0.000 description 7
- 230000009257 reactivity Effects 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 5
- -1 amino hydroxyl Chemical group 0.000 description 4
- 238000010276 construction Methods 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000005187 foaming Methods 0.000 description 4
- 230000000977 initiatory effect Effects 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 229920002125 Sokalan® Polymers 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 235000020188 drinking water Nutrition 0.000 description 2
- 239000003651 drinking water Substances 0.000 description 2
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- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- 239000004584 polyacrylic acid Substances 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- MUZDXNQOSGWMJJ-UHFFFAOYSA-N 2-methylprop-2-enoic acid;prop-2-enoic acid Chemical compound OC(=O)C=C.CC(=C)C(O)=O MUZDXNQOSGWMJJ-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 238000002479 acid--base titration Methods 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
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- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
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- 238000011056 performance test Methods 0.000 description 1
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Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The application discloses a weak acid substrate with high specific surface area and application thereof, wherein the weak acid substrate consists of an organic cross-linked skeleton copolymer material and a graft polymer grafted on the organic cross-linked skeleton copolymer material, and the organic cross-linked skeleton copolymer material is prepared by polymerizing and then cross-linking monomers containing double bonds and hydroxyl groups, monomers containing double bonds and carboxyl groups and monomers containing double bonds and amino groups under the action of an initiator according to a molar ratio of 1:2-4:1-2; the graft polymer is a polycarboxy polymer. The weak acid substrate is not easy to dissolve in water, can quickly react with alkaline substances in water, and quickens the reading time of alkalinity detection.
Description
Technical Field
The application belongs to the technical field of water quality detection, and particularly relates to a weak acid substrate with a high specific surface area and application thereof.
Background
Water is a source spring of life and is a first factor of human life, and along with the deep recommendation of industrialization, drinking water is polluted, so that the real-time monitoring of drinking water for people is of great significance.
The alkalinity of water quality is an important index for judging the water quality, and the method for detecting the alkalinity of water quality mainly comprises the following steps: acid-base titration, potentiometric titration, spectrophotometry, etc., but these methods are complicated and complicated in operation steps, generally require the use of chemical titrants, and require calibration, and cannot meet the requirements of modern industrial production in terms of measurement accuracy and measurement time.
The weak acid resin can react with alkaline matters in water to further ensure the conductivity of the waterChanges occur, and the alkalinity of the water is detected through the change of the conductivity. However, conventional weakly acidic resins do not have a porous structure, have a small specific surface area, and are not easily brought into contact with the weakly acidic groups in the resin due to the alkali ions (carbonate, bicarbonate, etc.) in water, and in addition, the weakly acidic resins react with the alkali substances in the water sample to generate CO 2 In the process of detecting the alkalinity of a water sample, CO 2 The gas can accumulate in the conventional weak acid resin in a large amount, so that the conventional weak acid resin is insufficiently contacted with the alkaline substances in the water, the conventional weak acid resin reacts with the alkaline substances in the water slowly, and the water alkalinity detection efficiency is reduced; in addition, when the existing porous weak acid resin is applied to the alkalinity test of a water sample, the existing porous weak acid resin is easy to dissolve in the water, and the detection error is large.
Disclosure of Invention
Aiming at the defects of the prior art, the application provides a weak acid substrate with high specific surface area, which is prepared by initiating polymerization of monomers containing double bonds and hydroxyl groups, monomers containing double bonds and carboxyl groups and monomers containing double bonds and amino groups through an initiator to obtain a branched chain carboxyl-containing amino hydroxyl polymer, then adding a cross-linking agent to carry out a cross-linking reaction to obtain an organic cross-linking framework, and finally grafting a multi-carboxyl polymer on the organic cross-linking framework, and foaming to obtain the porous resin with carboxyl on the surface. The weak acid substrate is not easy to dissolve in water, can quickly react with alkaline substances in water, and quickens the reading time of alkalinity detection.
The application aims to provide a weak acid substrate with a high specific surface area, which consists of an organic cross-linked skeleton copolymer material and a graft polymer grafted on the organic cross-linked skeleton copolymer material, wherein the organic cross-linked skeleton copolymer material is prepared by polymerizing and then cross-linking monomers containing double bonds and hydroxyl groups, monomers containing double bonds and carboxyl groups and monomers containing double bonds and amino groups under the action of an initiator according to a molar ratio of 1:2-4:1-2; the graft polymer is a polycarboxy polymer.
Preferably, the monomer containing double bonds and hydroxyl groups is one or more of hydroxyethyl acrylate, 2-methyl-2-propylene-1-ol and hydroxypropyl acrylate; the double bond of the monomer containing double bond and hydroxyl has higher reactivity, and the molecular chain of the copolymer obtained by polymerization contains more hydroxyl active reactive groups and keeps higher reactivity with the crosslinking agent.
Preferably, the monomer containing double bond and carboxyl is one or more of methacrylic acid, 2- (trifluoromethyl) acrylic acid, cinnamic acid, acrylic acid, maleic acid and itaconic acid; the double bond of the monomer containing double bond and carboxyl has higher reactivity, and the molecular chain of the copolymer obtained by polymerization contains more carboxyl active reactive groups and keeps higher reactivity with the crosslinking agent.
Preferably, the monomer containing double bond and amino is one or more of 1-amino-10-undecene, 4-pentene-1-amine, 7-octene-1-amine, hept-6-ene-1-amine, 4-vinylaniline, 4-aminostilbene and 3-vinylaniline; the double bond of the monomer containing double bond and amino group adopted by the scheme has higher reactivity, and the molecular chain of the copolymer obtained by polymerization contains more amino active reactive groups and keeps higher reactivity with the crosslinking agent.
Preferably, the initiator is one or more of azodiisobutyronitrile, azodiisovaleronitrile, azodiisoheptanenitrile, dibenzoyl peroxide and diisopropyl peroxydicarbonate; the initiator selected by the scheme has low decomposition temperature and high activity; the selected azodiisobutyronitrile, azodiisovaleronitrile and azodiisoheptanenitrile produce nitrogen in the process of decomposition initiation reaction, and the selected dibenzoyl peroxide and diisopropyl peroxydicarbonate produce carbon dioxide in the process of decomposition initiation reaction, so that the azodiisobutyronitrile, azodiisovaleronitrile and azodiisoheptanenitrile have the effects of initiating polymerization and foaming.
Preferably, the polycarboxy polymer is an acrylic acid homopolymer or copolymer.
More preferably, the polycarboxy polymer is one or more of polyacrylic acid, acrylic acid-methacrylic acid copolymer, acrylic acid- [2- (trifluoromethyl) acrylic acid ] copolymer, acrylic acid-cinnamic acid copolymer, acrylic acid-maleic acid copolymer, acrylic acid-itaconic acid copolymer; the selected multi-carboxyl polymer molecular chain contains more carboxyl groups, and the reaction with alkaline substances of a water sample is quickened when the multi-carboxyl polymer molecular chain is applied to the alkalinity test of the water sample.
Another object of the present application is to provide a method for preparing a weak acid substrate having a high specific surface area, comprising the steps of:
s1, under the protection of nitrogen, mixing a monomer containing double bonds and hydroxyl, a monomer containing double bonds and carboxyl, a monomer containing double bonds and amino, a solvent and an initiator, stirring, and heating to obtain a mixed material for later use;
s2, adding a cross-linking agent and a foaming agent into the mixed material prepared in the step S1, stirring, and reacting to obtain an organic cross-linked backbone copolymer mixed material;
s3, adding diisocyanate and a catalyst into the organic cross-linked skeleton copolymer mixed material prepared in the step S2, stirring for reaction, and adding a polycarboxy polymer and a foaming agent to obtain a weak acid substrate with high specific surface area.
Further, in the step S1, the initiator is used in an amount of 1-5% of the total amount of the monomers.
Further, in the step S1, the heating temperature is 69-105 ℃; the heating temperature of the scheme is selected based on the decomposition temperature of the initiator, at which the initiator can be effectively decomposed, the monomer and the solvent remain stable, the high-temperature evaporation is avoided, and the reaction rate is high.
Further, in the step S1, the solvent is one or more of acetonitrile, butyl acetate, ethyl acetate, toluene and xylene; the solvent is selected based on the heating temperature, and is not easy to volatilize at 69-105 ℃, so that the stability of a reaction system is maintained.
Further, in step S2, the crosslinking agent is an epoxy silane crosslinking agent; the epoxy group in the epoxy silane cross-linking agent selected in the scheme can react with the hydrophilic group carboxyl, amino and hydroxyl of the polymer prepared in the step S1, so that the cross-linking density of the polymer is improved, and the alkoxy in the epoxy silane cross-linking agent can undergo a hydrolytic condensation reaction with water to form a silicon-oxygen bond, so that the water resistance of the weak acid substrate is greatly improved, and the weak acid substrate is not easy to dissolve in a water sample.
In step S2, the weight ratio of the mixed material prepared in step S1 to the cross-linking agent to the foaming agent is 1:0.5-1:0.1-0.5; at this mass ratio, the step S2 organic crosslinked backbone copolymer hybrid material maintains a high degree of crosslinking, and carboxyl, amino, hydroxyl groups in the organic crosslinked backbone copolymer hybrid material are not reacted almost with the crosslinking agent due to excessive crosslinking, so that the group reactive with diisocyanate is absent in the step S3.
Further, in step S2, the foaming agent is one or two of n-hexane and n-heptane; the foaming agent has low boiling point, is volatile, nontoxic, low in price and not easy to leave in a reaction system, and has good foaming effect.
Further, in the step S3, the weight ratio of the organic cross-linked backbone copolymer material, diisocyanate, polycarboxy polymer and foaming agent prepared in the step S2 is 1:1-2:5-10:0.1-0.5; the excessive amount of the polycarboxy polymer is used for ensuring that a great amount of carboxyl groups which can react with alkaline substances in water are reserved in the obtained weak acid substrate after the carboxyl groups of the polycarboxy polymer react with diisocyanate; however, the mass ratio of the polycarboxy polymer to the organic cross-linked backbone copolymer material cannot exceed 1:10, otherwise the prepared weak acid substrate is readily soluble.
Further, in step S3, the diisocyanate is one of TDI, MDI, HDI, NDI; the N=C=O bond in the diisocyanate can react with the carboxyl, amino and hydroxyl which are not crosslinked in the organic crosslinked skeletal copolymer material prepared in the step S2,
further, in the step S3, the catalyst is one or more of dibutyl tin dilaurate, stannous 2-ethylhexanoate and tertiary amine; the catalyst selected by the scheme can effectively catalyze N=C=O bonds in diisocyanate to react with carboxyl, amino and hydroxyl in the polymer, and higher catalytic activity and thermal stability are maintained at corresponding reaction temperature.
Further, in step S3, the catalyst is used in an amount of 2 to 5% by weight of the reactants.
Further, in step S3, the foaming agent is one or two of n-hexane and n-heptane; the foaming agent has low boiling point, is volatile, nontoxic, low in price and not easy to leave in a reaction system, and has good foaming effect.
Compared with the prior art, the application has the following beneficial effects:
(1) The organic framework structure of the weak acid substrate with high specific surface area prepared by the application contains carboxyl amino hydroxyl, the adopted cross-linking agent can react with the carboxyl amino hydroxyl, the obtained weak acid substrate has high cross-linking degree, is not easy to dissolve in water, has high stability, and can be repeatedly applied to water alkalinity detection.
(2) The application grafts the multi-carboxyl polymer on the organic crosslinking skeleton by the diisocyanate, and in the process of preparing the weak acid base material, CO can be generated when the diisocyanate reacts with the organic crosslinking skeleton and the diisocyanate reacts with the multi-carboxyl polymer 2 Plays a role in pore-forming, so that the prepared weak acid base material has high porosity and high specific surface area; meanwhile, in the process of preparing the weakly acidic base material, a foaming agent is additionally added, so that the porosity and the specific surface area of the weakly acidic base material are further increased.
(3) The weak acid base material prepared by the application has high porosity and specific surface area, and is favorable for CO generated by the reaction of the weak acid base material and water sample alkaline substances in the water quality detection process 2 And is beneficial to increasing the contact area of the alkaline substance and the weak acid base material and accelerating the reaction efficiency of the weak acid base material and the alkaline substance of the water sample.
(4) According to the application, the multi-carboxyl polymer is grafted on the organic crosslinking skeleton through the diisocyanate, and in the water sample detection process, carboxyl in the multi-carboxyl polymer reacts with alkaline substances in the water sample, so that the conductivity is changed, the alkalinity of the water sample is tested, the preparation process is simple, economical and reasonable, the reaction condition is mild, high temperature and high pressure are not needed, and the method is suitable for industrial mass production.
Drawings
FIG. 1 is a graph showing a linear relationship between conductivity change and alkalinity of a water sample, constructed from the weak acid substrate prepared in example 1.
FIG. 2 is a graph showing a linear relationship between conductivity change and alkalinity of a water sample, constructed from the weak acid substrate prepared in example 2.
FIG. 3 is a graph showing a linear relationship between conductivity change and alkalinity of a water sample, constructed from the weak acid substrate prepared in example 3.
FIG. 4 is a graph showing a linear relationship between the conductivity change and alkalinity of a water sample, constructed by using macroporous weakly acidic acrylic cation exchange resin D113.
Detailed Description
In order to make the technical solution of the present application better understood by those skilled in the art, the technical solution of the present application will be clearly and completely described below with reference to the embodiments of the present application and the accompanying drawings, and it is obvious that the described embodiments are only some embodiments of the present application, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the present application without making any inventive effort, shall fall within the scope of the present application.
Example 1
S1, under the protection of nitrogen, mixing hydroxyethyl acrylate (5 mmol), methacrylic acid (10 mmol), 1-amino-10-undecene (5 mmol), ethyl acetate 15mL and azodiisobutyronitrile (0.2 mmol), stirring, and heating at 69 ℃ to react for 0.5 hour to obtain a mixed material for later use;
s2, adding epoxy silane cross-linking agent XR-500 (5 g) and n-hexane (1 g) into the mixed material (10 g) prepared in the step S1, stirring, keeping the temperature unchanged, and reacting for 1 hour to obtain an organic cross-linked backbone copolymer mixed material;
s3, adding TDI (5 g) and dibutyltin dilaurate (0.7 g) into the organic cross-linked skeleton copolymer mixed material (5 g) prepared in the step S2, keeping the temperature unchanged, stirring and reacting for 1 hour, and adding polyacrylic acid (25 g) and n-hexane (0.5 g) to obtain the weak acid substrate with high specific surface area.
Example 2
S1, mixing 2-methyl-2-propylene-1-ol (5 mmol), acrylic acid (15 mmol), hept-6-ene-1-amine (7.5 mmol), acetonitrile 20mL and diisopropyl peroxydicarbonate (0.825 mmol) under the protection of nitrogen, stirring, and heating at 85 ℃ to react for 0.5 hour to obtain a mixed material for later use;
s2, adding epoxy silane cross-linking agent XR-500 (8 g) and n-hexane (3 g) into the mixed material (10 g) prepared in the step S1, stirring, keeping the temperature unchanged, and reacting for 1 hour to obtain an organic cross-linked backbone copolymer mixed material;
s3, adding NDI (7.5 g) and dibutyltin dilaurate (2.1 g) into the organic cross-linked skeleton copolymer mixed material (5 g) prepared in the step S2, keeping the temperature unchanged, stirring and reacting for 1 hour, and adding acrylic acid-cinnamic acid copolymer (40 g) and n-hexane (1.5 g) to obtain the weak acid substrate with high specific surface area.
Example 3
S1, under the protection of nitrogen, mixing 2-methyl-2-propylene-1-alcohol (5 mmol), maleic acid (20 mmol), 4-vinylaniline (10 mmol), 25mL of dimethylbenzene and dibenzoyl peroxide (1.75 mmol), stirring, and heating at 105 ℃ to react for 0.5 hour to obtain a mixed material for later use;
s2, adding epoxy silane cross-linking agent XR-500 (10 g) and n-heptane (5 g) into the mixed material (10 g) prepared in the step S1, stirring, keeping the temperature unchanged, and reacting for 1 hour to obtain an organic cross-linked backbone copolymer mixed material; s3, adding MDI (10 g) and dibutyltin dilaurate (3.25 g) into the organic cross-linked skeleton copolymer mixed material (5 g) prepared in the step S2, keeping the temperature unchanged, stirring and reacting for 1 hour, and adding acrylic acid- [2- (trifluoromethyl) acrylic acid ] copolymer (50 g) and n-heptane (2.5 g) to obtain a weak acid substrate with high specific surface area.
Performance test:
the weak acid base material with high specific surface area and the macroporous weak acid acrylic cation exchange resin D113 prepared in the related examples 1-3 are subjected to the following pretreatment before use: weighing a certain mass of the weak acid base material with high specific surface area and the macroporous weak acid acrylic cation exchange resin D113 prepared in examples 1-3, respectively soaking in deionized water to remove the dissolved substances in the weak acid base material with high specific surface area and the macroporous weak acid acrylic cation exchange resin D113 prepared in examples 1-3, continuously soaking and continuously stirring, taking out the weak acid base material with high specific surface area and the macroporous weak acid acrylic cation exchange resin D113 prepared in examples 1-3 after about 12 hours, and washing and drying the acidic resin with a large amount of deionized water for standby.
After immersing the weak acid substrates prepared in examples 1 to 3 in pure water and tap water, respectively, for 24 hours, the conductivity change was observed, and the test results are shown in Table 1.
Table 1. The weak acid substrates prepared in examples 1-3 were tested for conductivity changes in pure water and tap water.
| Examples | Conductivity change of immersed pure water | Conductivity change of immersed tap water |
| Example 1 | ＜10％ | 42.4％ |
| Example 2 | ＜10％ | 39.3％ |
| Example 3 | ＜10％ | 45.1％ |
As can be seen from Table 1, the weak acid base materials prepared in examples 1-3 of the application are immersed in pure water, the conductivity change of the pure water is less than 10%, the weak acid base materials prepared in examples 1-3 of the application hardly contribute to the conductivity of water, the weak acid base materials prepared in examples 1-3 of the application are immersed in tap water, the conductivity change of the tap water is obvious, the weak acid base materials prepared in examples 1-3 of the application can fully react with a water sample, the conductivity of the water sample is obviously changed, and the weak acid base materials are suitable for detecting the alkalinity of the water sample.
Testing the alkalinity of a water sample:
s1, taking a water sample with a gradient alkalinity value (shown in table 2) as a gradient standard substance, and respectively measuring the conductivity of each gradient standard substance;
s2, respectively mixing and stirring each gradient standard with the weak acid base material prepared in the examples 1-3 or the commercial macroporous weak acid acrylic cation exchange resin D113;
s3, testing conductivity values of the gradient standard substances;
s4, for the same standard, the conductivity value measured for the first time is T1, the conductivity value measured for the second time is T2, the data of conductivity change values (namely T1-T2) before and after the gradient standard reacts with the weak acid base material prepared in the embodiment 1-3 or the commercial acid resin respectively are arranged, the mass of the test water is 80g, the weak acid base material prepared in the embodiment 1-3 is drained by 5g, the drained macroporous weak acid acrylic cation exchange resin D113 is 20g, the conductivity change value is an abscissa, the alkalinity value of a water sample is an ordinate, and a linear relation curve is fitted, wherein the linear relation curve is shown in the figures 1, 2, 3 and 4.
Table 2. Data relating to the construction of linear relationships for the weak acid substrates prepared in example 1.
| Standard substance | Initial alkalinity (mg/L) | T1/μs | T1-T2/μs | Theoretical conductivity decrease value/. Mu.s | Relative error |
| Tap water in the A-place | 42 | 116.7 | 42.2 | 41.7 | 1.2％ |
| Tap water in the B-site | 125 | 476.8 | 176.8 | 184.7 | 4.3％ |
| C floor tap water | 97 | 324.1 | 140.1 | 136.5 | 2.6％ |
| D floor tap water | 204 | 701.5 | 321.5 | 320.8 | 0.2％ |
| E tap water | 158 | 598.5 | 238.5 | 241.5 | 1.2％ |
| F floor tap water | 172 | 646.3 | 276.3 | 265.7 | 4.0％ |
| G-land tap water | 276 | 823.8 | 436.2 | 444.8 | 1.9％ |
| Tap water for H land | 71 | 219.4 | 89.4 | 91.7 | 2.5％ |
| I tap water | 231 | 956.2 | 373.8 | 367.3 | 1.8％ |
As can be seen from Table 2 and FIG. 1, when the weak acid substrate prepared in example 1 is applied to the detection of alkalinity of a water sample, the conductivity change value of the water sample has a strong linear relationship with the alkalinity of the water sample, which indicates that the weak acid substrate prepared in example 1 of the application can be applied to the detection of alkalinity of the water sample, and when the weak acid substrate is applied to the detection of alkalinity of the water sample, the relative error of the conductivity change value is below 4.3%.
Table 3. Data relating to the construction of linear relationships for the weak acid substrates prepared in example 2.
As can be seen from Table 3 and FIG. 2, when the weak acid substrate prepared in example 2 is applied to the detection of alkalinity of a water sample, the conductivity change value of the water sample has a strong linear relationship with the alkalinity of the water sample, which indicates that the weak acid substrate prepared in example 2 of the application can be used for the detection of the alkalinity of the water sample, and the relative error of the conductivity change value is below 4.9%.
Table 4. Data relating to the construction of linear relationships for the weak acid substrates prepared in example 3.
| Standard substance | Initial alkalinity (mg/L) | T1/μs | T1-T2/μs | Theoretical conductivity decrease value/. Mu.s | Relative error |
| Tap water in the A-place | 42 | 116.7 | 40.3 | 41.1 | 1.9％ |
| Tap water in the B-site | 125 | 476.8 | 173.8 | 181.1 | 4.0％ |
| C floor tap water | 97 | 324.1 | 133.5 | 133.9 | 0.3％ |
| D floor tap water | 204 | 701.5 | 310.5 | 314.3 | 1.2％ |
| E tap water | 158 | 598.5 | 230.7 | 236.7 | 2.5％ |
| F floor tap water | 172 | 646.3 | 265.1 | 260.3 | 1.8％ |
| G-land tap water | 276 | 823.8 | 432.7 | 435.7 | 0.7％ |
| Tap water for H land | 71 | 219.4 | 90.7 | 90.0 | 0.8％ |
| I tap water | 231 | 956.2 | 365.6 | 359.8 | 1.6％ |
As can be seen from Table 4 and FIG. 3, when the weak acid substrate prepared in example 3 is applied to the detection of alkalinity of a water sample, the conductivity change value of the water sample has a strong linear relationship with the alkalinity of the water sample, which indicates that the weak acid substrate prepared in example 3 of the application can be used for the detection of the alkalinity of the water sample, and the relative error of the conductivity change value is below 4.0%.
Table 5. Data relating to the construction of linear relationships for macroporous weakly acidic acrylic cation exchange resin D113.
As can be seen from Table 5 and FIG. 4, when the macroporous weakly acidic acrylic cation exchange resin D113 is applied to the detection of the alkalinity of a water sample, the conductivity change value of the water sample has a strong linear relationship with the alkalinity of the water sample, which proves that the macroporous weakly acidic acrylic cation exchange resin D113 can be applied to the detection of the alkalinity of the water sample, and the relative error of the conductivity change value is below 15.8%.
In summary, the weak acid substrates prepared in examples 1-3 of the present application have small relative errors in the conductivity change values compared to the commercial acidic resins (e.g., macroporous weakly acidic acrylic cation exchange resin D113) when used in water sample alkalinity tests.
Testing the alkalinity of a water sample:
the alkalinity test of the water sample is carried out by utilizing the weak acid base material and the macroporous weak acid acrylic cation exchange resin D113 prepared in the embodiment 1-3 and the linear relation shown in the attached figures 1-4, and the specific operation is as follows:
s1, measuring the conductivity of test water by using a conductivity meter before testing a water sample, recording the conductivity as C1, respectively mixing the weak acid base material and the macroporous weak acid acrylic cation exchange resin D113 prepared in the examples 1-3 with the test water, stirring for about 1h, wherein the mass of the test water is 80g, the drained resin materials for water quality detection prepared in the examples 4-6 are 5g, the drained macroporous weak acid acrylic cation exchange resin D113 is 20g, measuring the conductivity of the water after stirring for 1h, and recording the conductivity as C2.
S2, calculating conductivity change values (namely C1-C2) before and after the water sample reacts with the weak acid base material and the macroporous weak acid acrylic cation exchange resin D113 prepared in the embodiment 1-3 respectively, bringing the calculated conductivity change values into the linear relation shown in the attached drawings 1-4 respectively, and calculating the alkalinity value of the water sample, wherein the result is shown in the table 6:
TABLE 6 estimation of alkalinity values of water samples using the linear relationship shown in FIGS. 1-4.
As can be seen from Table 6, when the weak acid substrates prepared in examples 1 to 3 of the present application were used in the alkalinity test of water samples, the relative errors of the measured alkalinity of water samples were all less than 5%, while when the commercial acidic resins (e.g., macroporous weakly acidic acrylic cation exchange resin D113) were used in the alkalinity test of water samples, the relative errors of the measured alkalinity of water samples were all greater than 10%.
In summary, when the weak acid base materials prepared in the embodiments 1 to 3 of the present application are used for alkalinity test of water samples, the weak acid base materials have small relative error and high accuracy compared with the commercial acidic resins (such as macroporous weak acid acrylic cation exchange resin D113).
Test time comparison of water sample alkalinity:
the weak acid base material and the macroporous weak acid acrylic cation exchange resin D113 prepared in the examples 1-3 are respectively added into a water sample to react with alkaline substances of the water sample, and the change of conductivity in different time periods is observed, and the specific operation is as follows:
the conductivity of the test water is measured by a conductivity meter before the water sample is tested, the conductivity value T1 is recorded, the weak acid base material prepared in the embodiment 1-3 is mixed with the test water and stirred for 0.25-1 hour, the macroporous weak acid acrylic cation exchange resin D113 is mixed with the test water and stirred for 0.25-1.25 hours, the conductivity value T2 is recorded respectively, the conductivity change value (T1-T2) before and after the water sample reacts with the weak acid base material prepared in the embodiment 1-3 or the macroporous weak acid acrylic cation exchange resin D113 is calculated, the mass of the test water is 80g, the weak acid base material prepared in the embodiment 1-3 is 5g, the drained macroporous weak acid acrylic cation exchange resin D113 is 20g, and the result is shown in Table 7.
Table 7. Conductivity change values of the weak acid base material and the macroporous weakly acidic acrylic cation exchange resin D113.
As can be seen from Table 7, when the weak acid base materials prepared in examples 1 to 3 of the present application were added to a water sample, the conductivity values did not change after 0.5 hours, which means that the weak acid base materials prepared in examples 1 to 3 of the present application reacted completely with the alkaline substances in the water sample after 0.5 hours, whereas the commercial acid resins (macroporous weakly acidic acrylic cation exchange resin D113) did not change after 1 hour, which means that the commercial acid resins (macroporous weakly acidic acrylic cation exchange resin D113) reacted completely with the alkaline substances in the water sample after 1 hour, so that the weak acid base materials prepared in examples 1 to 3 of the present application reacted more rapidly with the alkaline substances in the water sample, which requires shorter time for the alkalinity test, and reduced the reading time for the alkalinity test, compared with the commercial acid base materials prepared in examples 1 to 3 of the present application (macroporous weakly acidic acrylic cation exchange resin D113).
Finally, it should be noted that the above-mentioned embodiments are only for illustrating the technical solution of the present application and not for limiting the same, and although the present application has been described in detail with reference to the above-mentioned embodiments, it should be understood by those skilled in the art that modifications and equivalents may be made to the specific embodiments of the present application after reading the present specification, and these modifications and variations do not depart from the scope of the application as claimed in the pending claims.
Claims (10)
1. The weak acid substrate with the high specific surface area is characterized by comprising an organic cross-linked skeleton copolymer material and a graft polymer grafted on the organic cross-linked skeleton copolymer material, wherein the organic cross-linked skeleton copolymer material is prepared by polymerizing and then cross-linking monomers containing double bonds and hydroxyl groups, monomers containing double bonds and carboxyl groups and monomers containing double bonds and amino groups under the action of an initiator according to a molar ratio of 1:2-4:1-2; the graft polymer is a polycarboxy polymer;
the preparation method of the weak acid substrate with the high specific surface area comprises the following steps:
s1, under the protection of nitrogen, mixing a monomer containing double bonds and hydroxyl, a monomer containing double bonds and carboxyl, a monomer containing double bonds and amino, a solvent and an initiator, stirring, and heating to obtain a mixed material for later use;
s2, adding a cross-linking agent and a foaming agent into the mixed material prepared in the step S1, stirring, and reacting to obtain an organic cross-linked backbone copolymer mixed material;
s3, adding diisocyanate and a catalyst into the organic cross-linked skeleton copolymer mixed material prepared in the step S2, stirring for reaction, and adding a polycarboxy polymer and a foaming agent to obtain a weak acid substrate with high specific surface area.
2. The substrate according to claim 1, wherein the monomer containing a double bond and a hydroxyl group is one or more of hydroxyethyl acrylate, 2-methyl-2-propen-1-ol, and hydroxypropyl acrylate.
3. The substrate of claim 1, wherein the monomer containing double bonds and carboxyl groups is one or more of methacrylic acid, 2- (trifluoromethyl) acrylic acid, cinnamic acid, acrylic acid, maleic acid, itaconic acid.
4. The weak acid substrate having a high specific surface area according to claim 1, wherein the monomer containing a double bond and an amino group is one or more of 1-amino-10-undecene, 4-penten-1-amine, 7-octen-1-amine, hept-6-en-1-amine, 4-vinylaniline, 4-aminostilbene, 3-vinylaniline.
5. The weak acid substrate having a high specific surface area according to claim 1, wherein the initiator is one or more of azobisisobutyronitrile, azobisisovaleronitrile, azobisisoheptonitrile, dibenzoyl peroxide, diisopropyl peroxydicarbonate.
6. The weak acid substrate with high specific surface area according to claim 1, wherein the polycarboxy polymer is an acrylic homopolymer or copolymer.
7. A method for preparing a weak acid substrate having a high specific surface area, comprising the steps of:
s1, under the protection of nitrogen, mixing a monomer containing double bonds and hydroxyl, a monomer containing double bonds and carboxyl, a monomer containing double bonds and amino, a solvent and an initiator, stirring, and heating to obtain a mixed material for later use;
s2, adding a cross-linking agent and a foaming agent into the mixed material prepared in the step S1, stirring, and reacting to obtain an organic cross-linked backbone copolymer mixed material;
s3, adding diisocyanate and a catalyst into the organic cross-linked skeleton copolymer mixed material prepared in the step S2, stirring for reaction, and adding a polycarboxy polymer and a foaming agent to obtain a weak acid substrate with high specific surface area.
8. The method for producing a weak acid substrate having a high specific surface area according to claim 7, wherein in step S1, the initiator is used in an amount of 1 to 5% of the total amount of monomers; the solvent is one or more of acetonitrile, butyl acetate, ethyl acetate, toluene and xylene.
9. The method for preparing a weak acid substrate with a high specific surface area according to claim 7, wherein in the step S2, the weight ratio of the mixed material prepared in the step S1 to the cross-linking agent and the foaming agent is 1:0.5-1:0.1-0.5;
the cross-linking agent is epoxy silane cross-linking agent;
the foaming agent is one or two of n-hexane and n-heptane.
10. The method for preparing a weak acid substrate having a high specific surface area according to claim 7, wherein in the step S3, the weight ratio of the organic cross-linked backbone copolymer material, diisocyanate, polycarboxy polymer, and foaming agent prepared in the step S2 is 1:1-2:5-10:0.1-0.5;
the diisocyanate is one of TDI, MDI, HDI, NDI;
the catalyst is one or more of dibutyl tin dilaurate, stannous 2-ethylhexanoate and tertiary amine;
the foaming agent is one or two of n-hexane and n-heptane.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1082945A (en) * | 1993-05-27 | 1994-03-02 | 南开大学高分子化学研究所 | Weak-acid cation-exchange resin |
| US6203708B1 (en) * | 1992-06-25 | 2001-03-20 | Monash University | Ion exchange resin |
| US6569910B1 (en) * | 1999-10-27 | 2003-05-27 | Basf Aktiengesellschaft | Ion exchange resins and methods of making the same |
| WO2008107470A1 (en) * | 2007-03-08 | 2008-09-12 | Lanxess Deutschland Gmbh | Use of proton-supplying and/or proton-accepting polymer particles |
| CN109705273A (en) * | 2019-01-11 | 2019-05-03 | 青岛普仁仪器有限公司 | A kind of preparation method of Subacidity cation chromatographic column filler |
-
2021
- 2021-09-09 CN CN202111054697.7A patent/CN115785513B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6203708B1 (en) * | 1992-06-25 | 2001-03-20 | Monash University | Ion exchange resin |
| CN1082945A (en) * | 1993-05-27 | 1994-03-02 | 南开大学高分子化学研究所 | Weak-acid cation-exchange resin |
| US6569910B1 (en) * | 1999-10-27 | 2003-05-27 | Basf Aktiengesellschaft | Ion exchange resins and methods of making the same |
| WO2008107470A1 (en) * | 2007-03-08 | 2008-09-12 | Lanxess Deutschland Gmbh | Use of proton-supplying and/or proton-accepting polymer particles |
| CN109705273A (en) * | 2019-01-11 | 2019-05-03 | 青岛普仁仪器有限公司 | A kind of preparation method of Subacidity cation chromatographic column filler |
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