CN116217928B - A high molecular organic polymer material containing pyridazinone groups and its preparation method and application - Google Patents
A high molecular organic polymer material containing pyridazinone groups and its preparation method and application Download PDFInfo
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- AAILEWXSEQLMNI-UHFFFAOYSA-N 1h-pyridazin-6-one Chemical group OC1=CC=CN=N1 AAILEWXSEQLMNI-UHFFFAOYSA-N 0.000 title claims abstract description 58
- 239000002861 polymer material Substances 0.000 title claims abstract description 56
- 229920000620 organic polymer Polymers 0.000 title claims abstract description 55
- 238000002360 preparation method Methods 0.000 title abstract description 17
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims abstract description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 25
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims abstract description 23
- -1 alkynyl ester Chemical class 0.000 claims abstract description 21
- 239000003344 environmental pollutant Substances 0.000 claims abstract description 7
- 231100000719 pollutant Toxicity 0.000 claims abstract description 7
- 239000002994 raw material Substances 0.000 claims abstract description 6
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 5
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims abstract 8
- 239000003054 catalyst Substances 0.000 claims description 17
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 16
- 239000002904 solvent Substances 0.000 claims description 16
- 229910021595 Copper(I) iodide Inorganic materials 0.000 claims description 14
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 claims description 14
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical group CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 12
- BDAGIHXWWSANSR-NJFSPNSNSA-N hydroxyformaldehyde Chemical compound O[14CH]=O BDAGIHXWWSANSR-NJFSPNSNSA-N 0.000 claims description 12
- 229910000018 strontium carbonate Inorganic materials 0.000 claims description 12
- CSEBNABAWMZWIF-UHFFFAOYSA-N 2,3,3,3-tetrafluoro-2-(heptafluoropropoxy)propanoic acid Chemical compound OC(=O)C(F)(C(F)(F)F)OC(F)(F)C(F)(F)C(F)(F)F CSEBNABAWMZWIF-UHFFFAOYSA-N 0.000 claims description 9
- CXZGQIAOTKWCDB-UHFFFAOYSA-N perfluoropentanoic acid Chemical compound OC(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F CXZGQIAOTKWCDB-UHFFFAOYSA-N 0.000 claims description 9
- 238000007789 sealing Methods 0.000 claims description 8
- PXUULQAPEKKVAH-UHFFFAOYSA-N perfluorohexanoic acid Chemical compound OC(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F PXUULQAPEKKVAH-UHFFFAOYSA-N 0.000 claims description 7
- UZUFPBIDKMEQEQ-UHFFFAOYSA-N perfluorononanoic acid Chemical compound OC(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F UZUFPBIDKMEQEQ-UHFFFAOYSA-N 0.000 claims description 7
- YFSUTJLHUFNCNZ-UHFFFAOYSA-N perfluorooctane-1-sulfonic acid Chemical compound OS(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F YFSUTJLHUFNCNZ-UHFFFAOYSA-N 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 5
- ZWBAMYVPMDSJGQ-UHFFFAOYSA-N perfluoroheptanoic acid Chemical compound OC(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F ZWBAMYVPMDSJGQ-UHFFFAOYSA-N 0.000 claims description 5
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 2
- 239000000376 reactant Substances 0.000 claims description 2
- 125000000304 alkynyl group Chemical group 0.000 claims 3
- 150000002429 hydrazines Chemical class 0.000 claims 2
- 239000000463 material Substances 0.000 abstract description 23
- 239000003463 adsorbent Substances 0.000 abstract description 11
- 238000006452 multicomponent reaction Methods 0.000 abstract description 5
- 229920000642 polymer Polymers 0.000 description 13
- 238000001179 sorption measurement Methods 0.000 description 12
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 10
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 10
- 150000001299 aldehydes Chemical class 0.000 description 9
- 239000000356 contaminant Substances 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- KUCOHFSKRZZVRO-UHFFFAOYSA-N terephthalaldehyde Chemical compound O=CC1=CC=C(C=O)C=C1 KUCOHFSKRZZVRO-UHFFFAOYSA-N 0.000 description 8
- 239000010842 industrial wastewater Substances 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 5
- 238000012512 characterization method Methods 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 230000008030 elimination Effects 0.000 description 4
- 238000003379 elimination reaction Methods 0.000 description 4
- 125000000524 functional group Chemical group 0.000 description 4
- 230000036541 health Effects 0.000 description 4
- 238000002329 infrared spectrum Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000006228 supernatant Substances 0.000 description 4
- 239000002351 wastewater Substances 0.000 description 4
- 238000012986 modification Methods 0.000 description 3
- SNGREZUHAYWORS-UHFFFAOYSA-N perfluorooctanoic acid Chemical compound OC(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F SNGREZUHAYWORS-UHFFFAOYSA-N 0.000 description 3
- YFSUTJLHUFNCNZ-UHFFFAOYSA-M 1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-heptadecafluorooctane-1-sulfonate Chemical compound [O-]S(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F YFSUTJLHUFNCNZ-UHFFFAOYSA-M 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- RPUSRLKKXPQSGP-UHFFFAOYSA-N methyl 3-phenylpropanoate Chemical compound COC(=O)CCC1=CC=CC=C1 RPUSRLKKXPQSGP-UHFFFAOYSA-N 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000011368 organic material Substances 0.000 description 2
- 230000008520 organization Effects 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 238000010490 three component reaction Methods 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 238000006065 biodegradation reaction Methods 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- ABDBNWQRPYOPDF-UHFFFAOYSA-N carbonofluoridic acid Chemical compound OC(F)=O ABDBNWQRPYOPDF-UHFFFAOYSA-N 0.000 description 1
- 231100000357 carcinogen Toxicity 0.000 description 1
- 239000003183 carcinogenic agent Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 1
- 235000020788 dietary exposure Nutrition 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- UTUVIKZNQWNGIM-UHFFFAOYSA-N ethyl 2-phenylpropanoate Chemical compound CCOC(=O)C(C)C1=CC=CC=C1 UTUVIKZNQWNGIM-UHFFFAOYSA-N 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 229910001701 hydrotalcite Inorganic materials 0.000 description 1
- 229960001545 hydrotalcite Drugs 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229910052588 hydroxylapatite Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- 230000015843 photosynthesis, light reaction Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/0622—Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms
- C08G73/0633—Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms with only two nitrogen atoms in the ring
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/12—Halogens or halogen-containing compounds
- C02F2101/14—Fluorine or fluorine-containing compounds
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Water Treatment By Sorption (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Polyethers (AREA)
Abstract
本发明属于材料化学领域，提供了一种含哒嗪酮基团的高分子有机聚合物材料及其制备方法和应用。以醛、肼、炔基酯为原料通过多组分反应一步高效合成了含哒嗪酮基团的高分子有机聚合物材料，其突出特点是所构建的含哒嗪酮基团的高分子有机聚合物材料结构稳定、功能位点分步均匀；该材料作为吸附剂对消除水中氟化物污染物具有广阔的应用前景。本发明公开的含哒嗪酮基团的高分子有机聚合物材料由如下所示结构单元组成，X＝C或N。
The present invention belongs to the field of material chemistry, and provides a high molecular organic polymer material containing pyridazinone groups, and a preparation method and application thereof. The high molecular organic polymer material containing pyridazinone groups is efficiently synthesized in one step through a multi-component reaction using aldehyde, hydrazine, and alkynyl ester as raw materials, and its outstanding feature is that the constructed high molecular organic polymer material containing pyridazinone groups has a stable structure and uniform functional sites; the material has broad application prospects as an adsorbent for eliminating fluoride pollutants in water. The high molecular organic polymer material containing pyridazinone groups disclosed in the present invention is composed of the structural units shown below, X=C or N.
Description
Technical Field
The invention belongs to the field of material chemistry, and particularly relates to a fluoride adsorbent containing pyridazinone groups, and a preparation method and application thereof.
Background
The disclosure of this background section is only intended to increase the understanding of the general background of the invention and is not necessarily to be construed as an admission or any form of suggestion that this information forms the prior art already known to those of ordinary skill in the art.
The fluoride is a fluorine-containing organic matter with important application value, and is widely applied to the industrial and civil fields. However, fluorides contain C-F covalent bonds with extremely high bond energies, resulting in difficulty in photolysis, hydrolysis and biodegradation, have proven to be novel chemical pollutants worldwide. 10.27 in 2017, the world health organization International cancer research organization lists perfluoro octanoic acid as a class 2B carcinogen. Fluoride can build up along the food chain, presenting health risks to humans at the very top of the food chain. In order to protect human health, some governments and organizations have standardized guidelines for PFCA in water. For example, the environmental protection agency water resource office has issued a lifelong health consultation level of 70ng/L for the combined concentrations of perfluorooctanoic acid and perfluorooctane sulfonate in drinking water. Furthermore, in order to assess the risks associated with perfluorocarboxylic acid dietary exposure, the european food safety agency suggests that further data concerning its content in food is required. Perfluorooctanoic acid and perfluorooctane sulfonate are persistent organic pollutants as determined by the 2009 schdule convention.
The adsorption technology has the advantages of environmental protection, simple and convenient operation, recyclable adsorption materials and the like, and is the ecological environment pollution treatment method with the most development prospect at present. In recent years, materials such as activated alumina, layered double hydrotalcite, zeolite, bentonite, hydroxyapatite, graphene and the like have been applied to adsorption removal of fluoride in water. However, some problems remain unsolved, such as a narrow effective pH range and poor selectivity. Since the adsorption mechanism for removing fluoride is mainly concentrated on the hydroxyl exchange with the contaminant, the adsorption performance of the adsorbent is significantly affected by the pH value and the coexisting ions.
Disclosure of Invention
In order to solve the problems, the invention provides a high molecular organic polymer material containing pyridazinone groups, and a reaction preparation method and application thereof. The preparation method has the outstanding characteristics that (1) the designed and constructed high-molecular organic polymer material has stable chemical structure, multiple functional sites and uniform distribution, (2) the high-molecular organic polymer material containing the pyridazinone group is efficiently synthesized in one step by utilizing multi-component reaction, (3) the high-molecular organic polymer material containing the pyridazinone group can be used as an adsorbent to effectively eliminate fluoride in water, and (4) the method provided by the invention has wide application prospect for synthesizing the novel high-molecular organic polymer material containing the functional groups.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
In a first aspect of the present invention, there is provided a pyridazinone group-containing polymeric organic material comprising a basic unit structure represented by the formula I:
Wherein x=c or N.
The invention develops a novel fluoride adsorption mechanism to provide a wide pH range and good selectivity, and has very important significance for the efficient removal of toxic fluoride in the ecological environment.
In a second aspect of the present invention, there is provided a method for producing the above-mentioned pyridazinone group-containing polymer organic material, comprising:
dissolving aldehyde, hydrazine and alkynyl ester in a solvent, heating under vacuum sealing in the presence of a catalyst to react, and purifying to obtain the catalyst;
wherein, the structural formulas of aldehyde, hydrazine and alkynyl ester are shown as follows:
in the structure of alkynyl ester, x=c, N, r=ch 3、CH2CH3.
In a third aspect, the invention provides the use of a pyridazinone group-containing polymeric material described above for the abatement of fluoride contaminants in water, including perfluorooctanecarboxylic acid, perfluorooctanesulfonic acid, perfluorobutanecarboxylic acid, perfluoropentanecarboxylic acid, perfluorohexanecarboxylic acid, perfluoro (2-methyl-3-oxahexanoic acid).
The beneficial effects of the invention are that
(1) The invention designs a high molecular organic polymer material containing pyridazinone groups based on a multicomponent reaction construction strategy, which is characterized by high chemical stability of material structure and pH application range, and particularly prepares special functional group adsorption material by multicomponent reaction in one step with high efficiency, thus not only having simple synthesis, but also needing no post-modification. The high molecular organic polymer material containing the pyridazinone group can be used as an adsorbent to effectively remove fluoride pollutants in water, and has important significance for ecological environment protection.
(2) The preparation method is simple, has strong practicability and is easy to popularize.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the invention.
FIG. 1 is a chart showing the IR spectrum of a pyridazinone group-containing polymer organic polymer material prepared in example 1 of the present invention;
FIG. 2 is a graph showing the IR spectrum of a pyridazinone group-containing polymer organic polymer material prepared in example 2 of the present invention;
FIG. 3 is a scanning electron microscope characterization diagram of a high molecular organic polymer material containing pyridazinone groups prepared in example 3 of the present invention;
FIG. 4 is a scanning electron microscope characterization diagram of a high molecular organic polymer material containing pyridazinone groups prepared in example 4 of the present invention.
Detailed Description
It should be noted that the following detailed description is exemplary and is intended to provide further explanation of the invention. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
As described in the background art, on one hand, research on an adsorbent material with a wide pH application range is needed to further improve the use efficiency of the adsorbent material as an adsorbent, and on the other hand, a new method for efficiently and conveniently preparing the adsorbent material with special functional groups is needed to be established. The invention designs a novel high molecular organic polymer material containing pyridazinone groups by using aldehyde, hydrazine and alkynyl ester as basic building blocks, increases binding sites, effectively improves the stability of the adsorption material and the adsorption performance of the adsorption material on fluoride dyes in water, and particularly utilizes three-component reaction to efficiently construct the high molecular organic polymer material containing the pyridazinone groups in one step, and has uniform functional site distribution and very wide application prospect.
In view of the above, the invention provides a high molecular organic polymer material containing pyridazinone groups, and a preparation method and application thereof.
In an exemplary embodiment of the present invention, there is provided a pyridazinone group-containing high molecular organic polymer material comprising the basic unit structure shown below:
in the basic unit structure, x=c, N.
The special functional group adsorption material is designed by adopting a multicomponent reaction technology to react aldehyde, hydrazine and alkynyl ester in one step to form a novel high molecular organic polymer material containing pyridazinone groups, and aims to increase binding sites, improve the distribution uniformity of the binding sites and improve the chemical stability and the application performance of the material.
The invention also provides a preparation method of the high molecular organic polymer material containing the pyridazinone group, which comprises the step of synthesizing the high molecular organic polymer material containing the pyridazinone group by one step through three-component reaction of aldehyde, hydrazine and alkynyl ester, wherein the structural formulas of the aldehyde, the hydrazine and the alkynyl ester are as follows:
In the structure of the alkynyl ester, X=C, N and R=CH 3、CH2CH3.
In some embodiments, the aldehyde, hydrazine, alkynyl ester is dissolved in a solvent, and the reaction is heated under vacuum sealing after the catalyst is added.
In some embodiments, the molar mass ratio of aldehyde, hydrazine, alkynyl ester is 1:1.0-1.2:3.5-4.5.
In one or more embodiments, the catalyst is a mixture of cuprous iodide and strontium carbonate.
In one or more embodiments, the catalyst is cuprous iodide and strontium carbonate in a molar mass ratio of 1:3-6.
In one or more embodiments, the catalyst is cuprous iodide and raw aldehyde in a molar mass ratio of 0.01-0.05:1.
In one or more embodiments, the solvent is acetonitrile, dioxane, toluene.
In one or more embodiments, the ratio of the mass of the solvent to the total mass of the reactants is 15-20:1.
In one or more embodiments, the heating reaction is at a temperature of 80 to 100 ℃ for a time of 24 to 36 hours.
In some embodiments, the purification process after the end of the reaction comprises washing followed by drying at room temperature.
In one or more embodiments, the washed solvents are acetone and tetrahydrofuran.
The third embodiment of the invention provides an application of the high molecular organic polymer material containing the pyridazinone group in removing fluoride pollutants in water.
In some embodiments, the fluoride contaminants that are eliminated from the water are perfluorooctane carboxylic acid, perfluorooctane sulfonic acid, perfluorobutane carboxylic acid, perfluoropentane carboxylic acid, perfluorohexane carboxylic acid, perfluoro (2-methyl-3-oxahexanoic acid), and the like.
In some embodiments, the mass ratio of the pyridazinone group-containing high molecular organic polymer material to the water sample is 0.1:400-0.1:500.
In a fourth embodiment of the present invention, there is provided an adsorbent for treating fluoride contaminants in sewage, wherein the adsorbent comprises the pyridazinone group-containing polymer material as an active ingredient.
In a fifth embodiment of the present invention, there is provided a method for treating fluoride contaminants in wastewater, comprising adding the above-mentioned pyridazinone group-containing polymer organic polymer material to the wastewater to be treated to treat the wastewater, and separating the treated pyridazinone group-containing polymer organic polymer material.
In some embodiments, the treatment time is 30-40 minutes. The treatment temperature is room temperature, and the room temperature refers to indoor environment temperature, and is generally 15-30 ℃.
The treatment process in the laboratory is stirring treatment, centrifugal separation or static precipitation re-separation after treatment.
The invention will now be described in further detail with reference to the following specific examples, which should be construed as illustrative rather than limiting.
Example 1
Synthesis of pyridazinone group-containing Polymer organic Polymer Material (X=C, R=CH 3 in the basic Unit) Material
(1) Preparation of materials
The raw material components are proportioned according to the following dosage proportion of 61mg of terephthalaldehyde, 69mg of terephthalyl dihydrazide, 560mg of methyl phenylpropionate, 2mg of catalyst cuprous iodide, 6mg of catalyst strontium carbonate and 12mL of solvent acetonitrile.
(2) Preparation of pyridazinone group-containing Polymer organic Polymer Material
Adding the prepared terephthalaldehyde, terephthalyl dihydrazide, methyl phenylpropionate and solvent acetonitrile into a thick-wall pressure-resistant pipe, uniformly mixing, adding cuprous iodide and strontium carbonate, vacuumizing and sealing, reacting at 80 ℃ for 24 hours, cooling, extracting with acetone and tetrahydrofuran Soxhlet for 6 hours respectively, and drying at room temperature to obtain 325mg of high molecular organic polymer material containing pyridazinone groups. The infrared spectrum is characterized as shown in figure 1.
(3) Elimination of fluoride contaminants in water samples
The industrial wastewater is detected to determine that the industrial wastewater contains perfluorohexane carboxylic acid and perfluoro (2-methyl-3-oxahexanoic acid), the concentration is 14.5 mug/L and 4.5 mug/L respectively, and the pH value of the industrial wastewater is 3.5. Adding 0.1g of the prepared high molecular organic polymer material containing the pyridazinone group into 400g of a water sample of industrial wastewater, stirring and adsorbing at room temperature for 30min, centrifuging, and detecting supernatant again to obtain 0.05 mug/L and 0.06 mug/L of perfluorohexane carboxylic acid and perfluoro (2-methyl-3-oxahexanoic acid) respectively, wherein the clearance rates are 99.6% and 98.7% respectively.
Example 2
Synthesis of pyridazinone group-containing Polymer organic Polymer Material (X=N, R=CH 2CH3 in the basic Unit) Material
(1) Preparation of materials
The raw material components are proportioned according to the following dosage proportion of 61mg of terephthalaldehyde, 69mg of terephthalyl dihydrazide, 700mg of 3- (4-pyridyl) ethyl propiolate, 2mg of catalyst cuprous iodide, 6mg of catalyst strontium carbonate and 16mL of solvent toluene.
(2) Preparation of pyridazinone group-containing Polymer organic Polymer Material
Adding the prepared terephthalaldehyde, terephthalyl dihydrazide, 3- (4-pyridyl) ethyl propiolate and solvent toluene into a thick-wall pressure-resistant pipe, uniformly mixing, adding cuprous iodide and strontium carbonate, vacuumizing and sealing, reacting for 24 hours at 100 ℃, cooling, respectively extracting for 6 hours by using acetone and tetrahydrofuran Soxhlet, and drying at room temperature to obtain 375mg of high molecular organic polymer material containing pyridazinone groups. The infrared spectrum is characterized as shown in figure 2.
(3) Elimination of fluoride contaminants in water samples
The industrial wastewater is detected to determine that the wastewater contains perfluorobutane carboxylic acid, the concentration is 9.8 mug/L, and the pH value of the industrial wastewater is detected to be 10.0. Adding 0.1g of the prepared high molecular organic polymer material containing the pyridazinone group into 500g of a water sample of industrial wastewater, stirring and adsorbing at room temperature for 35min, centrifuging, detecting supernatant again, and measuring the concentration of perfluorobutane carboxylic acid to be 0.35 mu g/L and the clearance to be 96.4%.
Example 3
Synthesis of pyridazinone group-containing Polymer organic Polymer Material (X=N, R=CH 3 in the basic Unit) Material
(1) Preparation of materials
The raw material components are proportioned according to the following dosage proportion of 61mg of terephthalaldehyde, 69mg of terephthalyl dihydrazide, 560mg of 3- (4-pyridyl) methyl propiolate, 2mg of catalyst cuprous iodide, 6mg of catalyst strontium carbonate and 15mL of solvent dioxane.
(2) Preparation of pyridazinone group-containing Polymer organic Polymer Material
Adding the prepared terephthalaldehyde, terephthalyl dihydrazide, 3- (4-pyridyl) methyl propiolate and solvent dioxane into a thick-wall pressure-resistant pipe, uniformly mixing, adding cuprous iodide and strontium carbonate, vacuumizing and sealing, reacting for 28 hours at 95 ℃, cooling, respectively extracting for 6 hours by using acetone and tetrahydrofuran, and drying at room temperature to obtain 337mg of high molecular organic polymer material containing pyridazinone groups. The scanning electron microscope characterization is shown in fig. 3.
(3) Elimination of fluoride contaminants in water samples
The method comprises the steps of selecting a standard adding solution as a water sample, wherein standard adding substances are perfluorooctane carboxylic acid, perfluorooctane sulfonic acid, perfluorobutane carboxylic acid, perfluoropentane carboxylic acid and perfluoro (2-methyl-3-oxahexanoic acid), the concentration of the standard adding substances is 40 mug/L, and the pH value of the water sample is regulated to 4.0 by hydrochloric acid. And adding 0.1g of the prepared high molecular organic polymer material containing the pyridazinone group into 500g of an experimental water sample, stirring and adsorbing at room temperature for 40min, centrifuging, and detecting supernatant again to obtain the concentration of perfluorooctanecarboxylic acid, perfluorooctanesulfonic acid, perfluorobutanecarboxylic acid, perfluoropentanecarboxylic acid and perfluoro (2-methyl-3-oxahexanoic acid) which are respectively 0.62 mu g/L, 0.66 mu g/L, 0.42 mu g/L, 0.54 mu g/L and 0.34 mu g/L, wherein the clearance rates are respectively 98.4%, 98.3%, 98.9%, 98.6% and 99.1%.
Example 4
Synthesis of pyridazinone group-containing Polymer organic Polymer Material (X=C, R=CH 2CH3 in the basic Unit) Material
(1) Preparation of materials
The raw material components are proportioned according to the following dosage proportion of 61mg of terephthalaldehyde, 69mg of terephthalyl dihydrazide, 750mg of ethyl phenylpropionate, 2mg of catalyst cuprous iodide, 6mg of catalyst strontium carbonate and 18mL of solvent toluene.
(2) Preparation of pyridazinone group-containing Polymer organic Polymer Material
Adding the prepared terephthalaldehyde, terephthalyl dihydrazide, ethyl benzene propiolate and toluene solvent into a thick-wall pressure-resistant pipe, uniformly mixing, adding cuprous iodide and strontium carbonate, vacuumizing and sealing, reacting at 90 ℃ for 30h, cooling, extracting with acetone and tetrahydrofuran Soxhlet for 6h respectively, and drying at room temperature to obtain 363mg of high-molecular organic polymer material containing pyridazinone groups. The scanning electron microscope characterization is shown in fig. 4.
(3) Elimination of fluoride contaminants in water samples
The method comprises the steps of selecting a standard adding solution as a water sample, wherein standard adding substances are perfluorooctane carboxylic acid, perfluorooctane sulfonic acid, perfluorobutane carboxylic acid, perfluoropentane carboxylic acid and perfluoro (2-methyl-3-oxahexanoic acid), the concentration of the standard adding substances is 40 mug/L, and the pH value of the water sample is regulated to 9.5 by ammonia water. Adding 0.1g of the prepared high molecular organic polymer material containing the pyridazinone group into 450g of experimental water sample, stirring and adsorbing at room temperature for 35min, centrifuging, and detecting supernatant again to obtain the concentration of perfluorooctanecarboxylic acid, perfluorooctanesulfonic acid, perfluorobutanecarboxylic acid, perfluoropentanecarboxylic acid and perfluoro (2-methyl-3-oxahexanoic acid) which are respectively 0.69 mug/L, 0.57 mug/L, 0.73 mug/L, 0.81 mug/L and 0.49 mug/L, wherein the clearance rates are respectively 98.2%, 98.6%, 98.2%, 98.0% and 98.8%.
Therefore, the pyridazinone group-containing high-molecular organic polymer material prepared by the method has good adsorption effect on fluoride pollutants in water within the pH range of 3.5-10, and has the advantages of high chemical stability, wide pH application range and strong adsorptivity.
The above description is only of the preferred embodiments of the present invention and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
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| DE3401911A1 (en) * | 1984-01-20 | 1985-08-01 | A. Nattermann & Cie GmbH, 5000 Köln | SUBSTITUTED 4,5-DIHYDRO-6-VINYL-3 (2H) -PYRIDAZINONE AND 6-VINYL-3 (2H) -PYRIDAZINONE AND METHOD FOR THE PRODUCTION THEREOF |
| WO2005028449A1 (en) * | 2003-06-26 | 2005-03-31 | Honeywell Specialty Chemicals Seelze Gmbh | Improved process for the manufacture of 1,2-disubstituted hexahydropyridazine-3-carboxylic acids and esters thereof |
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