CN115785513A - Weak acid base material with high specific surface area and application thereof - Google Patents
Weak acid base material with high specific surface area and application thereof Download PDFInfo
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- CN115785513A CN115785513A CN202111054697.7A CN202111054697A CN115785513A CN 115785513 A CN115785513 A CN 115785513A CN 202111054697 A CN202111054697 A CN 202111054697A CN 115785513 A CN115785513 A CN 115785513A
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- 239000000463 material Substances 0.000 title claims abstract description 100
- 239000002253 acid Substances 0.000 title claims abstract description 89
- 229920001577 copolymer Polymers 0.000 claims abstract description 36
- 239000000178 monomer Substances 0.000 claims abstract description 30
- 229920000642 polymer Polymers 0.000 claims abstract description 24
- 238000004132 cross linking Methods 0.000 claims abstract description 20
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 19
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 14
- 239000003999 initiator Substances 0.000 claims abstract description 13
- 125000003277 amino group Chemical group 0.000 claims abstract description 10
- 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
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- 238000006243 chemical reaction Methods 0.000 claims description 25
- 238000003756 stirring Methods 0.000 claims description 21
- 239000003431 cross linking reagent Substances 0.000 claims description 19
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 18
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 16
- 239000004088 foaming agent Substances 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 15
- 239000000758 substrate Substances 0.000 claims description 15
- 125000005442 diisocyanate group Chemical group 0.000 claims description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
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- 238000010438 heat treatment Methods 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
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- 239000004593 Epoxy Substances 0.000 claims description 7
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- 229910000077 silane Inorganic materials 0.000 claims description 7
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- 239000003054 catalyst Substances 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 239000002904 solvent Substances 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
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 4
- 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
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- 239000000203 mixture Substances 0.000 claims description 3
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- PYGHKJQHDXSHES-UHFFFAOYSA-N undec-10-en-1-amine Chemical compound NCCCCCCCCCC=C PYGHKJQHDXSHES-UHFFFAOYSA-N 0.000 claims description 3
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- 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
- 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 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
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- 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
- 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
- 150000003512 tertiary amines Chemical class 0.000 claims description 2
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 claims 2
- 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 101
- 239000000126 substance Substances 0.000 abstract description 18
- 238000001514 detection method Methods 0.000 abstract description 10
- 230000002378 acidificating effect Effects 0.000 description 32
- 230000008859 change Effects 0.000 description 31
- 238000012360 testing method Methods 0.000 description 27
- 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
- 239000011347 resin Substances 0.000 description 19
- 229920005989 resin Polymers 0.000 description 19
- 230000008569 process Effects 0.000 description 7
- 230000009257 reactivity Effects 0.000 description 6
- 238000010276 construction Methods 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- -1 carboxyl amino hydroxyl groups Chemical group 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005187 foaming Methods 0.000 description 3
- 230000000977 initiatory effect Effects 0.000 description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 229920002125 Sokalan® Polymers 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
- 238000005259 measurement Methods 0.000 description 2
- 231100000956 nontoxicity Toxicity 0.000 description 2
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- 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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Images
Abstract
The invention discloses a weak acid base material with high specific surface area and application thereof, wherein the weak acid base material consists of an organic cross-linked framework copolymer material and a graft polymer grafted on the organic cross-linked framework copolymer material, and the organic cross-linked framework copolymer material is prepared by polymerizing and then cross-linking a monomer containing double bonds and hydroxyl groups, a monomer containing double bonds and carboxyl groups and a monomer containing double bonds and amino groups according to a molar ratio of 1:2-4:1-2 under the action of an initiator; the graft polymer is a polycarboxy polymer. The weak acid base material is not easy to dissolve out in water, can quickly react with alkaline substances in water, and quickens the reading time of alkalinity detection.
Description
Technical Field
The invention belongs to the technical field of water quality detection, and particularly relates to a weak acid base material with a high specific surface area and application thereof.
Background
Water is a source of life and is the first element of human life, and drinking water for life is polluted along with deep industrial recommendation, so that the method has very important significance for monitoring drinking water of people in real time.
The water quality alkalinity is an important index for judging water quality, and the water quality alkalinity detection methods mainly comprise the following steps: acid-base titration, potentiometric titration, spectrophotometry and the like, but the methods are complicated and complex in operation steps, generally require the use of chemical titrants and calibration, and cannot meet the requirements of modern industrial production in terms of measurement accuracy and measurement time.
The weak acidic resin can react with alkaline substances in water, so that the conductivity of the water quality is changed, and the alkalinity of the water quality is detected through the change of the conductivity. However, the conventional weak acidic resin has no porous structure and small specific surface area, basic ions (carbonate, bicarbonate and the like) in water are not easy to contact and react with weak acid groups in the resin, and in addition, the weak acidic resin can generate CO when reacting with basic substances in a water sample 2 In the process of detecting the alkalinity of a water sample, CO 2 Gas can be accumulated in the conventional weak acidic resin in a large amount, so that the conventional weak acidic resin is not fully contacted with alkaline substances in water, the reaction of the conventional weak acidic resin and the alkaline substances in the water is slowed, and the water alkalinity detection efficiency is reduced; moreover, when the existing porous weakly acidic resin is applied to alkalinity test of a water sample, the existing porous weakly acidic resin is easy to dissolve out in water, and the detection error is large.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a weak acid base material with high specific surface area, which is characterized in that a monomer containing double bonds and hydroxyl groups, a monomer containing double bonds and carboxyl groups and a monomer containing double bonds and amino groups are initiated by an initiator to polymerize to obtain a branched polymer containing carboxyl amino hydroxyl groups, then a cross-linking agent is added to carry out cross-linking reaction to obtain an organic cross-linking framework, and finally a polycarboxyl polymer is grafted on the organic cross-linking framework and foamed to obtain the porous resin with the surface containing carboxyl groups. The weak acid base material is not easy to dissolve out in water, can quickly react with alkaline substances in water, and quickens the reading time of alkalinity detection.
The invention aims to provide a weak acid base material with high specific surface area, which consists of an organic crosslinking framework copolymer material and a graft polymer grafted on the organic crosslinking framework copolymer material, wherein the organic crosslinking framework copolymer material is prepared by polymerizing and crosslinking a monomer containing double bonds and hydroxyl groups, a monomer containing double bonds and carboxyl groups and a monomer containing double bonds and amino groups according to a molar ratio of 1:2-4:1-2 under the action of an initiator; the graft polymer is a polycarboxy polymer.
Preferably, the monomer containing double bonds and hydroxyl is one or more of hydroxyethyl acrylate, 2-methyl-2-propylene-1-ol and hydroxypropyl acrylate; the double bonds of the monomers containing double bonds and hydroxyl groups have higher reactivity, and the molecular chain of the copolymer obtained by polymerization contains more hydroxyl active reaction groups and keeps higher reactivity with the cross-linking agent.
Preferably, the monomer containing double bonds and carboxyl is one or more of methacrylic acid, 2- (trifluoromethyl) acrylic acid, cinnamic acid, acrylic acid, maleic acid and itaconic acid; the double bonds of the monomers containing double bonds and carboxyl have higher reactivity, and the molecular chain of the copolymer obtained by polymerization contains more carboxyl active reaction groups and keeps higher reactivity with the cross-linking agent.
Preferably, the monomer containing double bonds and amino groups 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 and 3-vinylaniline; the double bonds of the monomers containing double bonds and amino groups have higher reactivity, and the molecular chain of the copolymer obtained by polymerization contains more amino-active reaction groups and keeps higher reactivity with the cross-linking agent.
Preferably, the initiator is one or more of azobisisobutyronitrile, azobisisovaleronitrile, azobisisoheptonitrile, dibenzoyl peroxide and diisopropyl peroxydicarbonate; the initiator selected by the scheme has low decomposition temperature and high activity; the selected azodiisobutyronitrile, azodiisovaleronitrile and azodiisoheptanonitrile generate nitrogen in the process of decomposition initiation reaction, and the selected dibenzoyl peroxide and diisopropyl peroxydicarbonate generate carbon dioxide in the process of decomposition initiation reaction, so that the polymerization initiation function and the foaming function can be realized.
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 molecular chain of the selected polycarboxy polymer contains more carboxyl, and the reaction with alkaline substances in a water sample is accelerated when the polycarboxy polymer is used for testing the alkalinity of the water sample.
Another object of the present invention is to provide a method for preparing a weak acid base material with a high specific surface area, comprising the steps of:
s1, under the protection of nitrogen, mixing a monomer containing double bonds and hydroxyl groups, a monomer containing double bonds and carboxyl groups, a monomer containing double bonds and amino groups, 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 mixture prepared in the step S1, stirring, and reacting to obtain an organic cross-linked skeleton copolymer mixed material;
and 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 the weak acid base material with high specific surface area.
Further, in step S1, the amount of the initiator is 1-5% of the total amount of the monomers.
Further, in the step S1, the heating temperature is 69-105 ℃; the heating temperature is selected based on the decomposition temperature of the initiator, at which the initiator can be effectively decomposed, the monomer and the solvent are kept stable, evaporation at high temperature is avoided, and the reaction rate is high.
Further, in 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 the heating temperature of 69-105 ℃, so that the stability of a reaction system is favorably kept.
Further, in step S2, the crosslinking agent is an epoxy silane crosslinking agent; epoxy groups in the epoxy silane cross-linking agent selected by the scheme can react with carboxyl, amino and hydroxyl of hydrophilic groups of the polymer prepared in the step S1, so that the cross-linking density of the polymer is improved, and alkoxy groups in the epoxy silane cross-linking agent can be subjected to hydrolysis condensation reaction with water to form silicon-oxygen bonds, so that the water resistance of the weak acid base material is greatly improved, and the weak acid base material is not easy to dissolve out in a water sample.
Further, in step S2, the weight ratio of the mixed material prepared in step S1 to the crosslinking agent and the foaming agent is 1; at this mass ratio, the organic crosslinked skeleton copolymer hybrid material of step S2 maintains a high degree of crosslinking, and carboxyl groups, amino groups, and hydroxyl groups in the organic crosslinked skeleton copolymer hybrid material are not caused to react almost with the crosslinking agent by excessive crosslinking, so that groups reactive with diisocyanate are absent in step S3.
Further, in step S2, the foaming agent is one or two of n-hexane and n-heptane; the selected foaming agent has low boiling point, is easy to volatilize, has no toxicity, is low in price, is not easy to remain in a reaction system, and has good foaming effect.
Further, in step S3, the weight ratio of the organic crosslinked skeleton copolymer material prepared in step S2, the diisocyanate, the polycarboxy polymer and the foaming agent is 1:1-2:5-10; the excessive amount of the polycarboxy polymer is to ensure that a large amount of carboxyl groups capable of reacting with alkaline substances in water are reserved in the obtained weak acid base material after the carboxyl groups of the polycarboxy polymer react with diisocyanate; however, the mass ratio of the polycarboxy polymer to the organic crosslinked skeleton copolymer material cannot exceed 1.
Further, in step S3, the diisocyanate is one of TDI, MDI, HDI, and NDI; in the scheme, the bond N = C = O in the diisocyanate can react with the carboxyl, amino and hydroxyl which are not crosslinked in the organic crosslinking skeleton copolymer material prepared in the step S2,
further, in step S3, the catalyst is one or more of dibutyltin dilaurate, stannous 2-ethylhexanoate, and tertiary amine; the catalyst selected by the scheme can effectively catalyze the reaction of N = C = O bond in diisocyanate and carboxyl, amino and hydroxyl in a polymer, and keeps higher catalytic activity and thermal stability at corresponding reaction temperature.
Further, in step S3, the catalyst is used in an amount of 2-5% by weight based on the reactants.
Further, in step S3, the foaming agent is one or two of n-hexane and n-heptane; the selected foaming agent has low boiling point, is easy to volatilize, has no toxicity, is low in price, is not easy to remain in a reaction system, and has good foaming effect.
Compared with the prior art, the invention has the following beneficial effects:
(1) The organic framework structure of the weak acid base material with high specific surface area prepared by the invention contains carboxyl amino hydroxyl, the adopted cross-linking agent can react with the carboxyl amino hydroxyl, and the obtained weak acid base material has high cross-linking degree, is difficult to dissolve out in water and has high stability, and can be repeatedly applied to water alkalinity detection.
(2) According to the invention, the polycarboxyl polymer is grafted on the organic crosslinking framework through the diisocyanate, and in the process of preparing the weakly acidic base material, CO can be generated in the reaction of the diisocyanate and the organic crosslinking framework and in the reaction of the diisocyanate and the polycarboxyl polymer 2 The porous material has the function of pore making, so that the prepared weakly acidic 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 added, so that the porosity and the specific surface area of the weakly acidic base material are further increased.
(3) The weakly acidic base material prepared by the method has high porosity and specific surface area, and is beneficial to CO generated by the reaction of the weakly acidic base material and alkaline substances in a water sample in the water quality detection process 2 The discharge of the water sample is beneficial to increasing the contact area of the alkaline substance and the weakly acidic base material and accelerating the reaction efficiency of the weakly acidic base material and the water sample alkaline substance.
(4) According to the invention, the polycarboxy polymer is grafted on the organic crosslinking skeleton through the diisocyanate, and in the water sample detection process, carboxyl in the polycarboxy polymer reacts with alkaline substances in a water sample, so that the change of conductivity is caused, and the alkalinity test of the water sample is realized.
Drawings
Fig. 1 is a fitting graph of a linear relationship between the conductivity change value and the alkalinity value of a water sample constructed by the weak acid substrate prepared in example 1.
FIG. 2 is a fitting graph of linear relationship between conductivity change value and alkalinity value of water samples constructed by the weak acid base material prepared in example 2.
Fig. 3 is a fitting graph of the linear relationship between the conductivity change value and the alkalinity value of the water sample constructed by the weak acid substrate prepared in example 3.
FIG. 4 is a fitting graph of linear relation of correlation of conductivity change value and alkalinity value of a water sample, constructed by macroporous weakly acidic acrylic cation exchange resin D113.
Detailed Description
In order to make those skilled in the art better understand the technical solutions of the present invention, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention and the accompanying drawings. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
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 azobisisobutyronitrile (0.2 mmol), stirring, and heating at 69 ℃ for reaction for 0.5 hour to obtain a mixed material for later use;
s2, adding an 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 skeleton 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 for reacting for 1 hour, and adding polyacrylic acid (25 g) and n-hexane (0.5 g) to obtain the weak acid base material with the high specific surface area.
Example 2
S1, under the protection of nitrogen, 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), stirring, and heating at 85 ℃ for reaction for 0.5 hour to obtain a mixed material for later use;
s2, adding an 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 skeleton 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 for reacting for 1 hour, and adding acrylic acid-cinnamic acid copolymer (40 g) and n-hexane (1.5 g) to obtain a weak acid substrate with a high specific surface area.
Example 3
S1, under the protection of nitrogen, mixing 2-methyl-2-propylene-1-ol (5 mmol), maleic acid (20 mmol), 4-vinylaniline (10 mmol), xylene (25 mL) and dibenzoyl peroxide (1.75 mmol), stirring, and heating at 105 ℃ for reaction for 0.5 hour to obtain a mixed material for later use;
s2, adding an 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 skeleton 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 for 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 base material with a high specific surface area.
And (3) performance testing:
the weak acid base material having a high specific surface area and the macroporous weak acid acrylic cation exchange resin D113 prepared in examples 1 to 3 were each 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 the embodiments 1 to 3, respectively soaking in deionized water to remove 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 the embodiments 1 to 3, continuously soaking and continuously stirring, fishing out the weak acid base material with high specific surface area and the macroporous weak acid acrylic cation exchange resin D113 prepared in the embodiments 1 to 3 after about 12 hours, washing the acidic resin with a large amount of deionized water, and drying for later use.
After the weak acid substrates prepared in examples 1 to 3 were soaked in pure water and tap water, respectively, for 24 hours, the change in conductivity was observed, and the test results are shown in table 1.
Table 1. Results of the tests of the conductivity change of the weak acid base materials prepared in examples 1 to 3 for pure water and tap water.
| Examples | Change of conductivity of soaked pure water | Change of conductivity of soaked tap water |
| Example 1 | ＜10％ | 42.4％ |
| Example 2 | ＜10％ | 39.3％ |
| Example 3 | ＜10％ | 45.1％ |
Table 1 shows that the change of the conductivity of pure water is less than 10% in the weak acid base materials prepared in examples 1 to 3 of the present invention, which indicates that the weak acid base materials prepared in examples 1 to 3 of the present invention hardly contribute to the conductivity of water, and the change of the conductivity of tap water is significant when the weak acid base materials prepared in examples 1 to 3 of the present invention soak tap water, which indicates that the weak acid base materials prepared in examples 1 to 3 of the present invention can fully react with a water sample to significantly change the conductivity of the water sample, and is suitable for detecting the alkalinity of the water sample.
Testing the alkalinity of the water sample:
s1, adopting a water sample (shown in a table 2) with a gradient alkalinity value as a gradient standard, and respectively measuring the conductivity of each gradient standard;
s2, mixing and stirring each gradient standard product with the weak acid base material prepared in the embodiment 1-3 or the commercial macroporous weak acid acrylic cation exchange resin D113 respectively;
s3, testing the conductivity value of each gradient standard product;
s4, regarding the same standard, with the conductivity value measured for the first time as T1 and the conductivity value measured for the second time as T2, finishing the conductivity change value (namely T1-T2) data before and after the gradient standard respectively reacts with the weak acid base materials prepared in the examples 1-3 or the commercial acidic resins, wherein the mass of the water used for the test is 80g, the mass of the drained weak acid base materials prepared in the examples 1-3 is 5g, the drained macroporous weakly acidic acrylic acid cation exchange resin D113 is 20g, the conductivity change value is used as an abscissa, and the alkalinity value of a water sample is used as an ordinate, and fitting a linear relation curve, as shown in the graph 1, the graph 2, the graph 3 and the graph 4.
Table 2. Data relating to the construction of a linear relationship for the weak acid base material produced in example 1.
| Standard article | Initial alkalinity (mg/L) | T1/μs | T1-T2/μs | Theoretical conductivity reduction value/μ s | Relative error |
| Tap water of A ground | 42 | 116.7 | 42.2 | 41.7 | 1.2％ |
| Tap water of B place | 125 | 476.8 | 176.8 | 184.7 | 4.3％ |
| Tap water from C ground | 97 | 324.1 | 140.1 | 136.5 | 2.6％ |
| D ground tap water | 204 | 701.5 | 321.5 | 320.8 | 0.2％ |
| E ground tap water | 158 | 598.5 | 238.5 | 241.5 | 1.2％ |
| F ground tap water | 172 | 646.3 | 276.3 | 265.7 | 4.0％ |
| Tap water from G ground | 276 | 823.8 | 436.2 | 444.8 | 1.9％ |
| H ground tap water | 71 | 219.4 | 89.4 | 91.7 | 2.5％ |
| I ground tap water | 231 | 956.2 | 373.8 | 367.3 | 1.8％ |
It can be found from table 2 and fig. 1 that the change value of the conductivity of the water sample has a strong linear relationship with the alkalinity of the water sample when the weak acid substrate prepared in example 1 is used for detecting the alkalinity of the water sample, which indicates that the weak acid substrate prepared in example 1 of the present invention can be used for detecting the alkalinity of the water sample, and the relative error of the change value of the conductivity is below 4.3% when the weak acid substrate prepared in example 1 is used for detecting the alkalinity of the water sample.
Table 3. Data relating to the construction of a linear relationship for the weak acid base material produced in example 2.
From table 3 and fig. 2, it can be found that when the weak acid substrate prepared in example 2 is used for detecting the alkalinity of a water sample, the change value of the conductivity 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 present invention can be used for detecting the alkalinity of the water sample, and the relative error of the change value of the conductivity is below 4.9%.
Table 4. Data relating to the construction of a linear relationship for the weak acid base material produced in example 3.
| Standard article | Initial alkalinity (mg/L) | T1/μs | T1-T2/μs | Theoretical conductivity reduction value/μ s | Relative error |
| Tap water of A ground | 42 | 116.7 | 40.3 | 41.1 | 1.9％ |
| Tap water of B place | 125 | 476.8 | 173.8 | 181.1 | 4.0％ |
| Tap water from C ground | 97 | 324.1 | 133.5 | 133.9 | 0.3％ |
| D ground tap water | 204 | 701.5 | 310.5 | 314.3 | 1.2％ |
| E ground tap water | 158 | 598.5 | 230.7 | 236.7 | 2.5％ |
| F ground tap water | 172 | 646.3 | 265.1 | 260.3 | 1.8％ |
| Tap water from G ground | 276 | 823.8 | 432.7 | 435.7 | 0.7％ |
| H ground tap water | 71 | 219.4 | 90.7 | 90.0 | 0.8％ |
| I ground tap water | 231 | 956.2 | 365.6 | 359.8 | 1.6％ |
From table 4 and fig. 3, it can be found that, when the weak acid substrate prepared in example 3 is used for detecting the alkalinity of a water sample, the change value of the conductivity 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 present invention can be used for detecting the alkalinity of the water sample, and the relative error of the change value of the conductivity is below 4.0%.
TABLE 5 data relating to the construction of linear relationships for macroporous weakly acidic acrylic cation exchange resin D113.
From table 5 and fig. 4, it can be found that when the macroporous weakly acidic acrylic cation exchange resin D113 is used for detecting the alkalinity of a water sample, the change value of the conductivity of the water sample has a strong linear relationship with the alkalinity of the water sample, which indicates that the macroporous weakly acidic acrylic cation exchange resin D113 can be used for testing the alkalinity of the water sample, and the relative error of the change value of the conductivity is below 15.8%.
In summary, when the weak acid base materials prepared in examples 1-3 of the present invention are used for alkalinity testing of water samples, the relative error of the change value of the conductivity is small compared to that of the commercially available acidic resin (e.g., macroporous weak acid acrylic cation exchange resin D113).
Testing the alkalinity of the water sample:
the alkalinity of a water sample is tested by utilizing the weak acid base material prepared in the embodiments 1-3 of the invention, the macroporous weak acid acrylic cation exchange resin D113 and the linear relationship shown in the attached drawings 1-4, and the concrete operation is as follows:
s1, before testing a water sample, measuring the conductivity of test water by using a conductivity meter, recording the conductivity as C1, mixing the weak acid base material and the macroporous weak acid acrylic cation exchange resin D113 prepared in examples 1-3 with the test water respectively, stirring the mixture for about 1 hour, wherein the mass of the test water is 80g, the drained resin materials for water quality detection prepared in examples 4-6 are 5g, the drained macroporous weak acid acrylic cation exchange resin D113 is 20g, and measuring the conductivity of the water after stirring for 1 hour, and recording the conductivity as C2.
S2, calculating the conductivity change values (namely C1-C2) before and after the water sample reacts with the weak acid base material prepared in the embodiments 1-3 and the macroporous weak acid acrylic cation exchange resin D113 respectively, bringing the conductivity change values obtained by calculation into the linear relationship shown in the accompanying drawings 1-4 respectively, and calculating the alkalinity value of the water sample, wherein the results are shown in Table 6:
and 6, calculating the alkalinity value of the water sample by using the linear relation shown in the attached figures 1-4.
As can be seen from Table 6, when the weak acid base materials prepared in examples 1-3 of the present invention are used for alkalinity testing of water samples, the relative error of measured alkalinity of the water samples is less than 5%, and when the commercially available acidic resin (e.g., macroporous weak acid acrylic cation exchange resin D113) is used for alkalinity testing of water samples, the relative error of measured alkalinity of the water samples is greater than 10%.
In summary, when the weak acid base material prepared in embodiments 1-3 of the present invention is used for alkalinity testing of water sample, the error is small and the accuracy is high compared with the commercial acidic resin (e.g., macroporous weak acid acrylic cation exchange resin D113).
And (3) comparing the test time of the alkalinity of the water sample:
the weak acid base material and the macroporous weak acid acrylic cation exchange resin D113 prepared in examples 1 to 3 were added to a water sample, and reacted with an alkaline substance in the water sample, and the change of the conductivity in different periods of time was observed, specifically as follows:
before testing a water sample, measuring the conductivity of test water by using a conductivity meter, recording a conductivity value T1, mixing the weak acid base material prepared in the embodiment 1-3 with the test water and stirring for 0.25-1 hour, mixing the macroporous weak acid acrylic cation exchange resin D113 with the test water and stirring for 0.25-1.25 hours, respectively recording a conductivity value T2, calculating the conductivity change value (T1-T2) before and after the reaction of the water sample with the weak acid base material prepared in the embodiment 1-3 or the macroporous weak acid acrylic cation exchange resin D113, wherein the mass of the test water is 80g, the mass of the drained 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 results are shown in Table 7.
TABLE 7 conductivity change values for the weak acid base material and the macroporous weak acid 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 invention are added to a water sample, the value of the conductivity does not change after 0.5 hour, which indicates that the weak acid base materials prepared in examples 1 to 3 and the basic substance in the water sample have completely reacted after 0.5 hour, and the value of the conductivity does not change after 1 hour for the commercial acidic resin (macroporous weak acidic acrylic cation exchange resin D113), which indicates that the commercial acidic resin (macroporous weak acidic acrylic cation exchange resin D113) and the basic substance in the water sample have completely reacted after 1 hour, so that the weak acid base materials prepared in examples 1 to 3 of the present invention have faster reaction with the basic substance in the water sample, and the time required for alkalinity test of the water sample is shorter, and the reading time for alkalinity test is reduced compared with the commercial acidic resin (macroporous weak acidic acrylic cation exchange resin D113).
It should be noted that, although the present invention has been described in detail with reference to the above embodiments, those skilled in the art should understand that they can modify and substitute the specific embodiments of the present invention without departing from the scope of the appended claims.
Claims (10)
1. A weak acid base material with high specific surface area is characterized in that the weak acid base material is composed of an organic crosslinking framework copolymer material and a graft polymer grafted on the organic crosslinking framework copolymer material, wherein the organic crosslinking framework copolymer material is prepared by polymerizing and crosslinking a monomer containing double bonds and hydroxyl groups, a monomer containing double bonds and carboxyl groups and a monomer containing double bonds and amino groups according to a molar ratio of 1:2-4:1-2 under the action of an initiator; the graft polymer is a polycarboxy polymer.
2. Weak acid substrate with high specific surface area according to claim 1, characterised in that said double bond and hydroxyl group containing monomer is one or several of hydroxyethyl acrylate, 2-methyl-2-propen-1-ol, hydroxypropyl acrylate.
3. Weak acid substrate with high specific surface area according to claim 1, characterized in that the monomer containing double bond and carboxyl group is one or more of methacrylic acid, 2- (trifluoromethyl) acrylic acid, cinnamic acid, acrylic acid, maleic acid, itaconic acid.
4. Weak acid substrate with high specific surface area according to claim 1, characterised in that the double bond and amino group containing monomer 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. A weak acid substrate with high specific surface area according to claim 1, characterized in that said initiator is one or more of azobisisobutyronitrile, azobisisovaleronitrile, azobisisoheptonitrile, dibenzoyl peroxide, diisopropyl peroxydicarbonate.
6. Weak acid base material with high specific surface area according to claim 1, characterised in that the polycarboxy polymer is an acrylic acid homo-or copolymer.
7. A method for preparing a weak acid base material with high specific surface area is characterized by comprising the following steps:
s1, under the protection of nitrogen, mixing a monomer containing double bonds and hydroxyl groups, a monomer containing double bonds and carboxyl groups, a monomer containing double bonds and amino groups, 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 mixture prepared in the step S1, stirring, and reacting to obtain an organic cross-linked skeleton copolymer mixed material;
and 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 the weak acid base material with high specific surface area.
8. The method for preparing a weak acid base material with high specific surface area according to claim 7, wherein in step S1, the amount of the initiator is 1-5% of the total amount of the monomers; the solvent is one or more of acetonitrile, butyl acetate, ethyl acetate, toluene and xylene.
9. A method for preparing a weak acid base material with high specific surface area according to claim 7, wherein in step S2, the weight ratio of the mixed material prepared in step S1 to the cross-linking agent and the foaming agent is 1;
the cross-linking agent is an epoxy silane cross-linking agent;
the foaming agent is one or two of n-hexane and n-heptane.
10. A method for preparing a weak acid base material with high specific surface area according to claim 7, wherein in step S3, the weight ratio of the organic crosslinked skeleton copolymer material prepared in step S2, the diisocyanate, the polycarboxy polymer and the foaming agent is 1:1-2:5-10;
the diisocyanate is one of TDI, MDI, HDI and NDI;
the catalyst is one or more of dibutyltin dilaurate, 2-ethylhexanol stannous 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 |
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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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