CN116375938B - Preparation of imidazolium inner salt polymer catalyst and application of catalyst in preparation of hydrogen peroxide - Google Patents
Preparation of imidazolium inner salt polymer catalyst and application of catalyst in preparation of hydrogen peroxide Download PDFInfo
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- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 title claims abstract description 76
- 229920000642 polymer Polymers 0.000 title claims abstract description 41
- 150000003839 salts Chemical class 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 36
- RAXXELZNTBOGNW-UHFFFAOYSA-O Imidazolium Chemical compound C1=C[NH+]=CN1 RAXXELZNTBOGNW-UHFFFAOYSA-O 0.000 title claims abstract description 29
- 239000003054 catalyst Substances 0.000 title claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 31
- PFRGXCVKLLPLIP-UHFFFAOYSA-N diallyl disulfide Chemical compound C=CCSSCC=C PFRGXCVKLLPLIP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 9
- 239000003505 polymerization initiator Substances 0.000 claims abstract description 7
- PTZRYAAOQPNAKU-UHFFFAOYSA-N 2-[(1-carboxy-3-cyanobutyl)diazenyl]-4-cyanopentanoic acid Chemical compound N#CC(C)CC(C(O)=O)N=NC(C(O)=O)CC(C)C#N PTZRYAAOQPNAKU-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 238000002414 normal-phase solid-phase extraction Methods 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 8
- OSSNTDFYBPYIEC-UHFFFAOYSA-N 1-ethenylimidazole Chemical compound C=CN1C=CN=C1 OSSNTDFYBPYIEC-UHFFFAOYSA-N 0.000 claims description 6
- GAWAYYRQGQZKCR-UHFFFAOYSA-N 2-chloropropionic acid Chemical class CC(Cl)C(O)=O GAWAYYRQGQZKCR-UHFFFAOYSA-N 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 230000008961 swelling Effects 0.000 claims description 6
- 230000003213 activating effect Effects 0.000 claims description 5
- 238000011049 filling Methods 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 239000011541 reaction mixture Substances 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims 1
- ALVPFGSHPUPROW-UHFFFAOYSA-N dipropyl disulfide Chemical compound CCCSSCCC ALVPFGSHPUPROW-UHFFFAOYSA-N 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 27
- -1 salt derivative of N-vinyl imidazole Chemical class 0.000 abstract description 15
- 238000004519 manufacturing process Methods 0.000 abstract description 9
- 239000000178 monomer Substances 0.000 abstract description 7
- 230000003197 catalytic effect Effects 0.000 abstract description 6
- QOSATHPSBFQAML-UHFFFAOYSA-N hydrogen peroxide;hydrate Chemical compound O.OO QOSATHPSBFQAML-UHFFFAOYSA-N 0.000 abstract description 5
- 239000007800 oxidant agent Substances 0.000 abstract description 4
- 230000001590 oxidative effect Effects 0.000 abstract description 4
- 238000001308 synthesis method Methods 0.000 abstract description 3
- 238000006116 polymerization reaction Methods 0.000 abstract description 2
- 150000001735 carboxylic acids Chemical class 0.000 abstract 1
- 238000005481 NMR spectroscopy Methods 0.000 description 21
- 230000008569 process Effects 0.000 description 16
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical group [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 11
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 8
- 150000004056 anthraquinones Chemical class 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 239000002994 raw material Substances 0.000 description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 238000005868 electrolysis reaction Methods 0.000 description 6
- 238000005227 gel permeation chromatography Methods 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 4
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 4
- 238000004949 mass spectrometry Methods 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 239000002608 ionic liquid Substances 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- OSSNTDFYBPYIEC-UHFFFAOYSA-O 1-ethenylimidazole;hydron Chemical compound C=CN1C=C[NH+]=C1 OSSNTDFYBPYIEC-UHFFFAOYSA-O 0.000 description 2
- 241000400611 Eucalyptus deanei Species 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical group 0.000 description 2
- 239000013065 commercial product Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000002330 electrospray ionisation mass spectrometry Methods 0.000 description 2
- 239000013067 intermediate product Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- XIYUIMLQTKODPS-UHFFFAOYSA-M 1-ethyl-3-methylimidazol-3-ium;acetate Chemical compound CC([O-])=O.CC[N+]=1C=CN(C)C=1 XIYUIMLQTKODPS-UHFFFAOYSA-M 0.000 description 1
- QKSGIGXOKHZCQZ-UHFFFAOYSA-N 2-chloro-2-phenylacetic acid Chemical compound OC(=O)C(Cl)C1=CC=CC=C1 QKSGIGXOKHZCQZ-UHFFFAOYSA-N 0.000 description 1
- DDTJFSPKEIAZAM-UHFFFAOYSA-N 2-chloro-3-methylbutanoic acid Chemical compound CC(C)C(Cl)C(O)=O DDTJFSPKEIAZAM-UHFFFAOYSA-N 0.000 description 1
- CBQBIPRPIHIKPW-UHFFFAOYSA-N 2-chloro-4-methylpentanoic acid Chemical compound CC(C)CC(Cl)C(O)=O CBQBIPRPIHIKPW-UHFFFAOYSA-N 0.000 description 1
- PCFMUWBCZZUMRX-UHFFFAOYSA-N 9,10-Dihydroxyanthracene Chemical compound C1=CC=C2C(O)=C(C=CC=C3)C3=C(O)C2=C1 PCFMUWBCZZUMRX-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000003862 amino acid derivatives Chemical class 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000007844 bleaching agent Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000013043 chemical agent Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000000645 desinfectant Substances 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 150000004693 imidazolium salts Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910001867 inorganic solvent Inorganic materials 0.000 description 1
- 239000003049 inorganic solvent Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- 238000004451 qualitative analysis Methods 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 238000002798 spectrophotometry method Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- 229910000349 titanium oxysulfate Inorganic materials 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F226/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
- C08F226/06—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a heterocyclic ring containing nitrogen
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B15/00—Peroxides; Peroxyhydrates; Peroxyacids or salts thereof; Superoxides; Ozonides
- C01B15/01—Hydrogen peroxide
- C01B15/027—Preparation from water
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/70—Oxidation reactions, e.g. epoxidation, (di)hydroxylation, dehydrogenation and analogues
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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Abstract
Preparation of imidazolium inner salt type polymer catalyst and application thereof in preparation of hydrogen peroxide. The method takes a carboxylic acid inner salt derivative of N-vinyl imidazole as a polymerization monomer, diallyl disulfide as a cross-linking agent and azobis (4-cyano valeric acid) as a polymerization initiator, and the imidazolium inner salt polymer catalyst is prepared by a solvent-free two-step one-kettle synthesis method. The imidazolium inner salt polymer catalyst can be used for quickly and directly converting pure water into hydrogen peroxide water solution with certain concentration at normal temperature and normal pressure by taking air as an oxidant. The preparation method of the imidazolium inner salt polymer catalyst is simple and safe, and has extremely high catalytic efficiency and attractive application prospect in the green preparation and production fields of hydrogen peroxide.
Description
The technical field is as follows:
the invention relates to preparation of an imidazolium inner salt polymer catalyst and application thereof in preparation of hydrogen peroxide, in particular to preparation of an imidazolium inner salt polymer catalyst: the imidazolium inner salt polymer is prepared and used as a catalyst, and pure water is directly converted into a hydrogen peroxide aqueous solution with a certain concentration at normal temperature and normal pressure by taking air as an oxidant.
The background technology is as follows:
hydrogen peroxide is the most widely used chemical agent in daily life and chemical industry, and can be used as bleaching agent, preservative, detergent, sewage treatment additive, medical disinfectant, etc., and about 220 ten thousand tons is consumed every year worldwide. The traditional hydrogen peroxide preparation method is often complicated in steps, high in energy consumption, high in overall preparation cost and high in overall preparation cost, and a large amount of waste materials and byproducts are generated by using petroleum source raw materials. The invention aims to develop a hydrogen peroxide synthesis method which is more green, environment-friendly and simple compared with the traditional method, and has positive significance for reducing the synthesis cost of hydrogen peroxide and reducing the risk of environmental pollution in the preparation process.
A conventional industrial process for the preparation of hydrogen peroxide is electrochemical reduction based on oxygen. The process mainly comprises two methods: alkaline electrolysis and anthraquinone processes. In the alkaline electrolysis method, oxygen is dissolved in an aqueous sodium hydroxide solution, and a direct current is applied between electrodes immersed in the solution. The oxygen molecules are reduced to hydrogen peroxide at the cathode, and the hydrogen peroxide formed is then extracted and purified. In the anthraquinone process, an organic compound called anthraquinone is used as a catalyst to enhance the reduction of oxygen to hydrogen peroxide. The process involves oxidizing the anthraquinone in aqueous hydrogen peroxide and then reducing the anthrahydroquinone produced back to the anthraquinone. The reduction step also reduces the oxygen to hydrogen peroxide, and then extracts and purifies the hydrogen peroxide formed. Both methods are widely used for large-scale production of hydrogen peroxide, and are the main method for industrially preparing hydrogen peroxide. The choice of method depends on several factors, including the desired hydrogen peroxide purity and concentration, availability of raw materials, and production costs.
However, the above conventional industrial processes for preparing hydrogen peroxide have various disadvantages. The alkaline electrolysis method has the characteristics of high energy consumption and easy corrosion: the electrolysis process requires a large amount of energy, which increases production costs; the high concentration of hydrogen peroxide produced by the electrolysis process can corrode the electrodes and other components of the electrolyzer, resulting in reduced efficiency and increased maintenance costs, and can also result in the production of byproducts such as oxygen and hydroxides, which can affect the purity of the final product. The operation process of the anthraquinone process is complex: this method involves multiple steps and is difficult to control, thus making it less efficient and costly; a large amount of toxic and inflammable chemicals are also used in the anthraquinone process, so that extremely high risks are formed for workers and the environment, and the protection and environmental cost in the production process are correspondingly improved; the preparation process requires high pressures, which increases production costs and the risk of equipment failure. Furthermore, the final hydrogen peroxide yield of the anthraquinone process is low and the economy is relatively low compared to other processes. Meanwhile, almost all conventional hydrogen peroxide synthesis methods at present often need to form high-concentration hydrogen peroxide in the process of fractionating and extracting products, and the characteristics of high corrosiveness, explosiveness and easy decomposition have a certain danger for operators.
In the process of applying the imidazolium organic acid salt Ionic liquid for a long time, the inventor finds that the substances show special strong oxidizing ability, and can easily and rapidly oxidize mercapto groups in the compounds into sulfo groups (Ionic liquid 1-ethyl-3-methylimidazolium acetate: an attractive solvent for native chemical ligation, tetrahedron Lett.55 (2014) 3658-3662); meanwhile, compared with the conventional strong oxidizing agents such as peroxide or strong acid, the imidazolium organic acid ionic liquid has stable physicochemical properties, no volatilization, no inflammability and no explosion, has no corrosiveness, has higher biocompatibility, and has the potential of becoming an economic and environment-friendly oxidizing agent.
The invention comprises the following steps:
the invention provides an imidazolium inner salt polymer catalyst for the first time, which can realize the green preparation of hydrogen peroxide by taking water and air as raw materials. The imidazolium inner salt polymer is a compound polymerized by an N-terminal carboxylic acid derivative monomer of 1-vinyl imidazolium. The chemical general formula of the carboxylic acid derivative monomer of the 1-vinyl imidazolium isWherein R is preferably isopropyl, isobutyl or phenyl.
The preparation of the imidazolium inner salt polymer catalyst and the application thereof in the preparation of hydrogen peroxide comprise the following basic steps:
1) In a round-bottomed flask, 1.00 equivalent of N-vinylimidazole and preferably 1.00 equivalent of 2-chloropropionic acid derivative are mixed and heated to 70℃in an oil bath and stirred for reaction for 8 hours in the absence of light. The N-vinylimidazole refers to
The 2-chloropropionic acid derivative refers toWherein R is preferably isopropyl, isobutyl or phenyl.
2) 0.70 to 1.00 equivalent of diallyl disulfide as a crosslinking agent and 0.01 equivalent of azobis (4-cyanovaleric acid) as a polymerization initiator
Sequentially added to the mixture and slowly heated to 120 ℃ in an oil bath and reacted under stirring under nitrogen atmosphere for 72 hours.
3) After the reaction was completed, the reaction mixture was cooled to room temperature and 50ml of water was added to the flask at once.
4) Filtering the precipitated product, washing with water for three times, and vacuum drying for 1 hr to obtain crosslinked imidazolium inner salt polymer with simplified structural general formula
Wherein R is preferably isopropyl, isobutyl or phenyl.
5) Filling the obtained imidazolium inner salt polymer into an injector type solid phase extraction column with a hydrophilic sieve plate, repeatedly washing with pure water, swelling and activating.
6) About one third of the column volume of pure water is sucked into the syringe type solid phase extraction column, about two thirds of the volume of air is reserved, and after 30 seconds of shaking, the pushed liquid is 21-37% hydrogen peroxide water solution.
Compared with the prior art, the method for preparing hydrogen peroxide by using water and air as raw materials under the action of the imidazolium inner salt polymer catalyst has the following innovation and advantages:
1. compared with the traditional polymer preparation method, the preparation method of the imidazolium inner salt polymer catalyst does not need any organic or inorganic solvent, only involves simple mixing and heating in the two-step one-kettle reaction process, has almost no volatilization, and therefore, the preparation method has the advantages of simple process, low risk and commercial availability of preparation raw materials; meanwhile, all raw materials, cross-linking agents, polymerization initiators and byproducts possibly generated in the preparation method are water-soluble, so that the purification can be carried out by simple water washing after the polymerization reaction.
2. The preparation method of hydrogen peroxide provided by the invention is the simplest and simplest preparation method known at present; the whole process does not need electrolysis energy consumption, and does not need toxic and inflammable chemicals; the hydrogen peroxide aqueous solution with the concentration close to that of the commercial product is directly obtained, the steps of distilling and separating impurities, concentrating and then diluting are not needed, and the occurrence of production accidents is effectively avoided; the whole process only comprises mixing and vibrating of water, air and the catalyst, and is simple to operate, green, energy-saving, safe and reliable.
3. The imidazolium inner salt polymer is different from the conventional imidazolium polymer salt (poly-imidazolium salts), has no free ions and stable chemical properties, and therefore, can not exchange ions with other anions and cations in water when in use, is not easy to cause catalyst loss or reduce risk of catalytic capability after long-term use, and can not pollute products; imidazolium inner salt polymers used in the present invention; the imidazolium inner salt type polymer catalyst used as one of amino acid derivatives has high biocompatibility and durable catalytic effect, and is not easy to inactivate.
4. The imidazolium inner salt polymer provided by the invention has remarkable catalytic efficiency, and can catalyze pure water to generate high-purity hydrogen peroxide aqueous solution with concentration close to or even exceeding that of the commercial product at normal temperature and normal pressure only by tens of seconds; after experimental screening, the catalytic efficiency is highest when the monomer side chain R is preferably isopropyl, isobutyl or phenyl; the molecular design of the polymer crosslinked by disulfide bonds gives consideration to the separation capability of the polymer and the water phase and the rapid swelling capability in water, and ensures the hydrolysis resistance, high stability and durable catalytic efficiency of the imidazolium inner salt type polymer catalyst in the water phase under the oxidation environment.
The specific embodiment is as follows:
the experimental materials, reagents, etc. used in the examples described below are all commercially available or known experimental methods.
In the following examples, purification and qualitative and quantitative analysis of the target product or intermediate product were performed using electrospray mass spectrometry, nuclear magnetic resonance spectrometry and gel permeation chromatography. In the electrospray mass spectrometry, the intermediate product is dissolved in a mixed solvent of acetonitrile and water in a ratio of 1:1, and diluted by 10-100 times according to a proper proportion for mass spectrometry. 1 H NMR 13 The C NMR spectrum was obtained by Bruker ARX-500% 1 H：500MHz， 13 C:125 MHz) of the sample. Chemical shift (delta) is expressed in parts per million (ppm) for residual deuterated chloroform signals 1 H NMR at delta 7.27 ppm; for the following 13 C NMR at delta 77.23 ppm. Gel permeation chromatography was performed using tetrahydrofuran as solvent, and the flow rate was 1.0mL/min as determined by Agilent InfinityLab PlusPore series GPC chromatography column. The concentration of hydrogen peroxide was determined by titanyl sulfate spectrophotometry and quantitatively analyzed by a hydrogen peroxide refractometer.
Example 1 synthesis of disulfide-crosslinked internal salt polymers of 2- (N-vinylimidazolium-N' -yl) -3-methylbutyrate and their use in the preparation of hydrogen peroxide.
941.17mg of N-vinylimidazole and preferably 1365.75mg of 2-chloro-3-methylbutanoic acid are mixed in a 250mL round-bottomed flask and heated in an oil bath to 70℃and stirred for reaction for 8 hours in the absence of light; 1462.80mg (1.00 eq.) of the cross-linking agent diallyl disulfide and 28.03mg of the polymerization initiator azobis (4-cyanovaleric acid) were added sequentially to the mixture and heated slowly in an oil bath to 120℃and reacted under nitrogen with stirring for 72 hours; after the reaction was completed, the reaction mixture was cooled to room temperature and 50ml of water was added to the flask; the precipitated product was filtered and washed three times with water, and dried in vacuo for 1 hour to give 829.05mg of disulfide-crosslinked inner salt polymer of 2- (N-vinylimidazolium-N' -yl) -3-methylbutanoic acid; filling 500mg of the obtained imidazolium inner salt polymer into a syringe type solid-phase extraction column with a hydrophilic sieve plate, repeatedly washing with pure water, swelling and activating; about one third of the column volume of pure water is sucked into the syringe type solid phase extraction column, about two thirds of the volume of air is reserved, and after 30 seconds of shaking, the pushed liquid is 21% hydrogen peroxide water solution. The preparation process involves the following reaction formula:
the internal salt monomer of 2- (N-vinylimidazolium-N' -yl) -3-methylbutanoic acid (brown gum) was characterized by mass spectrometry and nuclear magnetic resonance spectroscopy (M/z [ M+H)] + ＝195.1052， 1 H NMR(500MHz,Chloroform-d)δ7.86,7.86,7.85,7.85,7.85,7.77,7.77,7.77,7.77,7.76,7.22,7.20,7.18,5.29,5.29,5.27,5.27,5.12,5.12,5.10,5.10,5.00,4.99,4.98,4.97,2.69,2.67,2.67,2.66,2.66,2.64,2.64,2.63,2.63,2.61,1.05,1.04. 13 C NMR (125 MHz, chlorine-d). Delta. 171.76,140.31,132.52,127.63,123.30,94.32,70.76,32.30,19.11.); disulfide-crosslinked internal salt polymers of 2- (N-vinylimidazolium-N' -yl) -3-methylbutanoic acid (black brown solid) are characterized by nuclear magnetic resonance spectroscopy and gel permeation chromatography (M) w ＝7609g/mol,M n ＝7926g/mol, 1 H NMR(500MHz,Chloroform-d)δ7.61,7.61,7.61,7.61,7.60,7.40,7.40,7.39,7.39,7.39,5.21,5.21,5.20,4.60,4.58,4.58,4.57,4.56,4.56,4.55,4.55,4.55,4.54,2.67,2.66,2.65,2.65,2.64,2.64,2.64,2.63,2.62,2.62,2.62,2.61,2.61,2.61,2.59,2.59,2.58,1.87,1.86,1.86,1.85,1.85,1.84,1.84,1.82,1.80,1.80,1.79,1.79,1.79,1.78,1.78,1.78,1.78,1.77,1.77,1.77,1.77,1.76,1.76,1.76,1.75,1.74,1.74,1.73,1.44,1.43,1.42,1.42,1.41,1.40,1.40,1.39,1.39,1.28,1.27,1.06,1.05,1.04,1.04,0.95,0.95,0.94,0.93,0.92,0.92. 13 C NMR(125MHz,Chloroform-d)δ171.77,137.62,126.33,123.76,70.93,53.35,41.88,38.71,37.83,32.28,26.69,21.48,19.06,11.30.)。
Example 2 synthesis of disulfide-crosslinked inner salt of 2- (N-vinylimidazolium-N' -yl) -4-methylpentanoic acid polymer and its use in the preparation of hydrogen peroxide.
941.17mg of N-vinylimidazole and preferably 1506.02mg of 2-chloro-4-methylpentanoic acid are mixed in a 250mL round bottom flask and heated in an oil bath to 70℃and stirred for 8 hours under light protection; 1462.80mg (1.00 eq.) of the cross-linking agent diallyl disulfide and 28.03mg of the polymerization initiator azobis (4-cyanovaleric acid) were added sequentially to the mixture and heated slowly in an oil bath to 120℃and reacted under nitrogen with stirring for 72 hours; after the reaction was completed, the reaction mixture was cooled to room temperature and 50ml of water was added to the flask; the precipitated product was filtered and washed three times with water, and dried in vacuo for 1 hour to give 870.49mg of disulfide-crosslinked inner salt polymer of 2- (N-vinylimidazolium-N' -yl) -4-methylpentanoic acid; filling 500mg of the obtained imidazolium inner salt polymer into a syringe type solid-phase extraction column with a hydrophilic sieve plate, repeatedly washing with pure water, swelling and activating; about one third of the column volume of pure water is sucked into the syringe type solid phase extraction column, about two thirds of the volume of air is reserved, and after shaking for 30 seconds, the pushed liquid is 30% concentration hydrogen peroxide water solution. The preparation process involves the following reaction formula:
the inner salt monomer of 2- (N-vinylimidazolium-N' -yl) -4-methylpentanoic acid (brown gum) was characterized by mass spectrometry and nuclear magnetic resonance spectroscopy (M/z [ M+H)] + ＝209.1248， 1 H NMR(500MHz,Chloroform-d)δ7.87,7.86,7.86,7.86,7.48,7.47,7.47,7.47,7.22,7.20,7.18,5.46,5.46,5.45,5.45,5.43,5.43,5.12,5.12,5.10,5.10,5.00,4.99,4.98,4.97,2.53,2.52,2.52,2.51,2.50,2.49,2.49,2.48,2.45,2.44,2.44,2.43,2.42,2.41,2.41,2.40,1.94,1.92,1.92,1.91,1.91,1.90,1.89,1.89,1.88,1.88,1.88,1.86,1.86,1.85,0.95,0.94. 13 C NMR (125 MHz, chlorine-d). Delta. 171.83,136.15,132.52,127.81,122.11,94.32,61.04,39.81,25.41,22.59.); disulfide-crosslinked inner salt of 2- (N-vinylimidazolium-N' -yl) -4-methylpentanoic acid polymer (black brown solid) was characterized by nuclear magnetic resonance spectroscopy and gel permeation chromatography (M) w ＝5820g/mol,M n ＝6017g/mol, 1 H NMR(500MHz,Chloroform-d)δ7.59,7.58,7.58,7.58,7.57,7.57,7.40,7.40,7.40,7.40,7.39,7.39,5.39,5.39,5.38,5.36,4.60,4.58,4.57,4.56,4.55,4.54,2.67,2.66,2.64,2.64,2.63,2.62,2.61,2.59,2.59,2.58,2.53,2.52,2.52,2.51,2.50,2.49,2.49,2.48,2.48,2.46,2.46,2.45,2.45,2.44,2.43,2.42,1.94,1.92,1.92,1.91,1.91,1.90,1.89,1.88,1.88,1.87,1.86,1.86,1.85,1.85,1.84,1.84,1.83,1.82,1.80,1.79,1.79,1.79,1.78,1.78,1.78,1.78,1.77,1.77,1.77,1.76,1.76,1.76,1.76,1.75,1.74,1.74,1.73,1.44,1.43,1.42,1.42,1.41,1.40,1.40,1.39,1.28,1.27,0.95,0.95,0.95,0.94,0.94,0.93,0.92,0.92. 13 C NMR(125MHz,Chloroform-d)δ171.97,136.41,126.47,123.52,61.12,53.40,41.88,39.83,38.71,37.83,26.69,25.42,22.59,21.48,11.30.)。
Example 3 synthesis of disulfide-crosslinked 2- (N-vinylimidazolium-N' -yl) -2-phenylacetic acid inner salt polymer and its use in the preparation of hydrogen peroxide.
941.17mg of N-vinylimidazole and preferably 1705.92mg of 2-chloro-2-phenylacetic acid are mixed in a 250mL round-bottomed flask and heated in an oil bath to 70℃and stirred in the absence of light for 8 hours; 1023.96mg (0.70 equivalent) of diallyl disulfide as a crosslinking agent and 28.03mg of azobis (4-cyanovaleric acid) as a polymerization initiator were sequentially added to the mixture and slowly heated to 120℃in an oil bath, and reacted under stirring under a nitrogen atmosphere for 72 hours; after the reaction was completed, the reaction mixture was cooled to room temperature and 50ml of water was added to the flask; the precipitated product was filtered and washed three times with water, and dried in vacuo for 1 hour to give 1180.37mg of disulfide-crosslinked inner salt polymer of 2- (N-vinylimidazolium-N' -yl) -2-phenylacetic acid; filling 500mg of the obtained imidazolium inner salt polymer into a syringe type solid-phase extraction column with a hydrophilic sieve plate, repeatedly washing with pure water, swelling and activating; about one third of the column volume of pure water is sucked into the syringe type solid phase extraction column, about two thirds of the volume of air is reserved, and after 30 seconds of shaking, the pushed liquid is 37% concentration hydrogen peroxide water solution. The preparation process involves the following reaction formula:
the inner salt monomer of 2- (N-vinylimidazolium-N' -yl) -2-phenylacetic acid (orange-yellow gum) was characterized by mass spectrometry and nuclear magnetic resonance spectroscopy (M/z [ M+H)] + ＝229.0935， 1 H NMR(500MHz,Chloroform-d)δ7.42,7.42,7.42,7.41,7.41,7.41,7.40,7.40,7.40,7.39,7.37,7.37,7.37,7.36,7.35,7.35,7.34,7.34,7.33,7.30,7.29,7.29,7.29,7.28,7.28,7.28,7.28,7.27,7.27,7.26,7.26,5.52,5.52,5.51. 13 C NMR (125 MHz, chlorine-d). Delta. 170.38,135.70,128.82,128.51,128.25,59.66.); disulfide-crosslinked inner salt polymers of 2- (N-vinylimidazolium-N' -yl) -2-phenylacetic acid (black brown solids) are characterized by nuclear magnetic resonance spectroscopy and gel permeation chromatography (M) w ＝9961g/mol,M n ＝10231g/mol, 1 H NMR(500MHz,Chloroform-d)δ7.59,7.59,7.59,7.59,7.58,7.58,7.58,7.58,7.57,7.57,7.57,7.57,7.57,7.56,7.51,7.50,7.50,7.49,7.49,7.47,7.47,7.47,7.41,7.41,7.41,7.40,7.40,7.40,7.38,7.38,7.37,7.37,7.37,7.36,7.36,7.36,7.36,7.35,7.35,7.34,6.69,6.69,6.69,4.59,4.59,4.58,4.57,4.57,4.57,4.56,4.56,4.56,4.55,4.55,4.54,2.67,2.66,2.64,2.64,2.63,2.62,2.61,2.59,2.58,1.87,1.86,1.86,1.85,1.85,1.84,1.84,1.83,1.82,1.80,1.80,1.80,1.79,1.79,1.79,1.78,1.78,1.78,1.78,1.77,1.77,1.77,1.77,1.76,1.76,1.76,1.76,1.75,1.75,1.74,1.74,1.73,1.44,1.43,1.42,1.42,1.41,1.40,1.40,1.39,1.39,1.28,1.27,0.95,0.95,0.94,0.93,0.92,0.92. 13 CNMR(125MHz,Chloroform-d)δ171.86,136.98,136.96,128.80,128.73,128.40,125.50,123.25,69.76,53.42,41.88,38.71,37.83,26.69,21.48,11.30.)。
The applicant states that the detailed method of the present invention is illustrated by the above examples, but the present invention is not limited to the detailed method described above, i.e. it does not mean that the present invention must be practiced in dependence upon the detailed method described above. It should be apparent to those skilled in the art that any modification of the present invention, equivalent substitution of raw materials for the product of the present invention, addition of auxiliary components, selection of specific modes, etc. are included in the scope of the present invention and the scope of disclosure.
Claims (2)
1. A preparation method of an imidazolium inner salt type polymer catalyst is characterized in that: mixing 1.00 equivalent of N-vinylimidazole and 1.00 equivalent of 2-chloropropionic acid derivative, heating to 70 ℃ by an oil bath, stirring and reacting for 8 hours in a dark place, sequentially adding the corresponding equivalent of cross-linking agent diallyl disulfide and 0.01 equivalent of polymerization initiator azobis (4-cyanovaleric acid) into the mixture, slowly heating to 120 ℃ by the oil bath, stirring and reacting for 72 hours under nitrogen atmosphere, cooling the reaction mixture to room temperature after the reaction is completed, adding water into a flask at one time, filtering and washing the precipitated product for three times, and vacuum drying to obtain the cross-linked imidazolium inner salt polymer; the structural formula of the 2-chloropropionic acid derivative is one of the following structural formulas:
wherein, when the 2-chloropropionic acid derivative is +.> In one of the above, the crosslinking agent dieneThe corresponding equivalent of propyldisulfide is 1.00; when the 2-chloropropionic acid derivative is +.>When the corresponding equivalent of the cross-linking agent diallyl disulfide is 0.70.
2. An application of an imidazolium inner salt type polymer catalyst in the preparation of hydrogen peroxide is characterized in that: filling the imidazolium inner salt polymer prepared by the preparation method of claim 1 into an injector type solid phase extraction column with a hydrophilic sieve plate, repeatedly washing with pure water, swelling and activating, sucking one third of column volume of pure water into the injector type solid phase extraction column, reserving two thirds of volume of air, and oscillating for 30 seconds, wherein the pushed liquid is hydrogen peroxide aqueous solution.
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| CN102688773A (en) * | 2012-04-25 | 2012-09-26 | 北京化工大学 | Catalyst for preparing hydrogen peroxide from alkyl arene through catalytic oxidation, and preparation method and application thereof |
| CN111987361A (en) * | 2020-08-17 | 2020-11-24 | 仲恺农业工程学院 | Imidazole polyion liquid electrolyte and preparation method and application thereof |
| WO2022246381A1 (en) * | 2021-05-20 | 2022-11-24 | Versum Materials Us, Llc | Imidazolium-based poly(ionic liquid)s and use therefore |
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| CN102688773A (en) * | 2012-04-25 | 2012-09-26 | 北京化工大学 | Catalyst for preparing hydrogen peroxide from alkyl arene through catalytic oxidation, and preparation method and application thereof |
| CN111987361A (en) * | 2020-08-17 | 2020-11-24 | 仲恺农业工程学院 | Imidazole polyion liquid electrolyte and preparation method and application thereof |
| WO2022246381A1 (en) * | 2021-05-20 | 2022-11-24 | Versum Materials Us, Llc | Imidazolium-based poly(ionic liquid)s and use therefore |
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