CN116574214A - Polyion liquid catalyst and preparation method and application thereof - Google Patents
Polyion liquid catalyst and preparation method and application thereof Download PDFInfo
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- CN116574214A CN116574214A CN202310516460.9A CN202310516460A CN116574214A CN 116574214 A CN116574214 A CN 116574214A CN 202310516460 A CN202310516460 A CN 202310516460A CN 116574214 A CN116574214 A CN 116574214A
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- bisulfate
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- 239000003054 catalyst Substances 0.000 title claims abstract description 107
- 239000007788 liquid Substances 0.000 title claims abstract description 72
- 229920000831 ionic polymer Polymers 0.000 title claims abstract description 68
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 238000005886 esterification reaction Methods 0.000 claims abstract description 44
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 29
- -1 1-vinyl-3-butyl imidazole bisulfate Chemical compound 0.000 claims abstract description 24
- 239000000178 monomer Substances 0.000 claims abstract description 12
- 239000002253 acid Substances 0.000 claims abstract description 11
- 239000003999 initiator Substances 0.000 claims abstract description 8
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 54
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 51
- 238000006243 chemical reaction Methods 0.000 claims description 46
- 239000000047 product Substances 0.000 claims description 43
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 39
- 238000003756 stirring Methods 0.000 claims description 39
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 38
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 24
- 238000004821 distillation Methods 0.000 claims description 22
- 230000035484 reaction time Effects 0.000 claims description 20
- QAOWNCQODCNURD-UHFFFAOYSA-M hydrogensulfate Chemical compound OS([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-M 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 18
- 239000006228 supernatant Substances 0.000 claims description 18
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 15
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 15
- 238000001291 vacuum drying Methods 0.000 claims description 15
- OSSNTDFYBPYIEC-UHFFFAOYSA-N 1-ethenylimidazole Chemical compound C=CN1C=CN=C1 OSSNTDFYBPYIEC-UHFFFAOYSA-N 0.000 claims description 14
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 14
- 239000003960 organic solvent Substances 0.000 claims description 14
- FBOSFHSGNSJLLG-UHFFFAOYSA-N 1-butyl-3-ethenyl-1,2-dihydroimidazol-1-ium;chloride Chemical compound [Cl-].CCCC[NH+]1CN(C=C)C=C1 FBOSFHSGNSJLLG-UHFFFAOYSA-N 0.000 claims description 12
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 12
- VFWCMGCRMGJXDK-UHFFFAOYSA-N 1-chlorobutane Chemical compound CCCCCl VFWCMGCRMGJXDK-UHFFFAOYSA-N 0.000 claims description 10
- 239000012298 atmosphere Substances 0.000 claims description 10
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 10
- 230000001590 oxidative effect Effects 0.000 claims description 10
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 8
- ZNSMNVMLTJELDZ-UHFFFAOYSA-N Bis(2-chloroethyl)ether Chemical compound ClCCOCCCl ZNSMNVMLTJELDZ-UHFFFAOYSA-N 0.000 claims description 7
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 7
- 229930195729 fatty acid Natural products 0.000 claims description 7
- 239000000194 fatty acid Substances 0.000 claims description 7
- 150000004665 fatty acids Chemical class 0.000 claims description 7
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 claims description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 6
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 150000003841 chloride salts Chemical class 0.000 claims description 6
- PHTQWCKDNZKARW-UHFFFAOYSA-N isoamylol Chemical compound CC(C)CCO PHTQWCKDNZKARW-UHFFFAOYSA-N 0.000 claims description 6
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 6
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 5
- 235000019260 propionic acid Nutrition 0.000 claims description 5
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 5
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 claims description 4
- 230000032050 esterification Effects 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 239000001384 succinic acid Substances 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- 239000005711 Benzoic acid Substances 0.000 claims description 3
- 235000010233 benzoic acid Nutrition 0.000 claims description 3
- 125000001309 chloro group Chemical class Cl* 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 29
- 238000003786 synthesis reaction Methods 0.000 abstract description 23
- 230000015572 biosynthetic process Effects 0.000 abstract description 22
- 239000011973 solid acid Substances 0.000 abstract description 12
- 239000002608 ionic liquid Substances 0.000 abstract description 11
- 238000006555 catalytic reaction Methods 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract description 3
- 229920000642 polymer Polymers 0.000 abstract description 3
- 238000011084 recovery Methods 0.000 abstract description 3
- 238000004064 recycling Methods 0.000 abstract description 3
- 238000005265 energy consumption Methods 0.000 abstract description 2
- GEMITLJMEMBDKW-UHFFFAOYSA-N hydrogen sulfate;1h-imidazol-3-ium Chemical compound C1=CNC=N1.OS(O)(=O)=O GEMITLJMEMBDKW-UHFFFAOYSA-N 0.000 abstract 1
- 238000006116 polymerization reaction Methods 0.000 abstract 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N butyl acetate Chemical compound CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 22
- 230000000052 comparative effect Effects 0.000 description 18
- 238000000926 separation method Methods 0.000 description 17
- 239000012530 fluid Substances 0.000 description 16
- 239000002904 solvent Substances 0.000 description 15
- 238000001035 drying Methods 0.000 description 9
- 239000012299 nitrogen atmosphere Substances 0.000 description 9
- 229910000831 Steel Inorganic materials 0.000 description 8
- 239000010959 steel Substances 0.000 description 8
- 239000011541 reaction mixture Substances 0.000 description 7
- 230000007797 corrosion Effects 0.000 description 6
- 238000005260 corrosion Methods 0.000 description 6
- 239000002244 precipitate Substances 0.000 description 6
- 238000003860 storage Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 150000001804 chlorine Chemical class 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 4
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 3
- 150000001733 carboxylic acid esters Chemical class 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 150000007522 mineralic acids Chemical class 0.000 description 3
- 238000002390 rotary evaporation Methods 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- FZXRXKLUIMKDEL-UHFFFAOYSA-N 2-Methylpropyl propanoate Chemical compound CCC(=O)OCC(C)C FZXRXKLUIMKDEL-UHFFFAOYSA-N 0.000 description 2
- 239000004971 Cross linker Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000003377 acid catalyst Substances 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- MTZQAGJQAFMTAQ-UHFFFAOYSA-N ethyl benzoate Chemical compound CCOC(=O)C1=CC=CC=C1 MTZQAGJQAFMTAQ-UHFFFAOYSA-N 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- XAOGXQMKWQFZEM-UHFFFAOYSA-N isoamyl propanoate Chemical compound CCC(=O)OCCC(C)C XAOGXQMKWQFZEM-UHFFFAOYSA-N 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- HNAGHMKIPMKKBB-UHFFFAOYSA-N 1-benzylpyrrolidine-3-carboxamide Chemical compound C1C(C(=O)N)CCN1CC1=CC=CC=C1 HNAGHMKIPMKKBB-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- MUXOBHXGJLMRAB-UHFFFAOYSA-N Dimethyl succinate Chemical compound COC(=O)CCC(=O)OC MUXOBHXGJLMRAB-UHFFFAOYSA-N 0.000 description 1
- 244000137852 Petrea volubilis Species 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 159000000032 aromatic acids Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- OBNCKNCVKJNDBV-UHFFFAOYSA-N butanoic acid ethyl ester Natural products CCCC(=O)OCC OBNCKNCVKJNDBV-UHFFFAOYSA-N 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- BEPAFCGSDWSTEL-UHFFFAOYSA-N dimethyl malonate Chemical compound COC(=O)CC(=O)OC BEPAFCGSDWSTEL-UHFFFAOYSA-N 0.000 description 1
- YPLYFEUBZLLLIY-UHFFFAOYSA-N dipropan-2-yl butanedioate Chemical compound CC(C)OC(=O)CCC(=O)OC(C)C YPLYFEUBZLLLIY-UHFFFAOYSA-N 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 125000002883 imidazolyl group Chemical group 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229940090181 propyl acetate Drugs 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- JAELLLITIZHOGQ-UHFFFAOYSA-N tert-butyl propanoate Chemical compound CCC(=O)OC(C)(C)C JAELLLITIZHOGQ-UHFFFAOYSA-N 0.000 description 1
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- 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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
-
- 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
- B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
- B01J2231/49—Esterification or transesterification
-
- 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
Abstract
The invention discloses a polyionic liquid catalyst and a preparation method and application thereof, and belongs to the technical field of catalyst material synthesis for esterification reaction. The polyion liquid catalyst combining the advantages of solid acid, ionic liquid and polymer is obtained by carrying out polymerization reaction on a 1-vinyl-3-butyl imidazole bisulfate monomer and an imidazole bisulfate cross-linking agent under the action of an initiator. The polyion liquid catalyst disclosed by the invention not only can solve the problems of low efficiency, high energy consumption, serious secondary pollution, strong corrosiveness to equipment and the like of the traditional organic and inorganic strong acid catalytic esterification reaction, but also can well overcome the problems of difficult recovery, easy loss and the like of the ion liquid catalyst, and has the characteristics of wide application range, high catalytic activity, recycling of the catalyst, environment friendliness, high selectivity and the like, thereby truly realizing the efficient green catalysis of the esterification reaction.
Description
Technical Field
The invention belongs to the technical field of catalyst material synthesis for esterification reaction, and particularly relates to a polyion liquid catalyst 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.
Organic carboxylic esters have wide application in the production of high value-added products such as perfumes, plasticizers, polymers and the like, and are very important intermediates and products. The esterification reaction of carboxylic acid and alcohol is an exothermic reversible reaction, and liquid homogeneous inorganic acid is commonly used as a catalyst, including boric acid, concentrated sulfuric acid, hydrochloric acid, phosphoric acid and other acids, but when the above substances are used as the catalyst for catalyzing the esterification reaction, the problems of corrosion, difficult separation of homogeneous reaction catalysts and the like exist. As a novel functional material, the ionic liquid has good performance in the field of catalysis, has the characteristics of difficult volatilization, strong stability, designability and the like, and also has certain catalytic activity in the esterification synthesis reaction. However, although the ionic liquid has a plurality of advantages, the ionic liquid also has the problems of serious loss, difficult recovery and the like in the actual use process, so that the application of the ionic liquid is severely restricted.
Currently, supported solid acid catalysts and non-solid, which are easily separated from the productHeterogeneous catalysts such as supported solid acid catalysts are also receiving great attention, for example, chinese patent CN 114602512A discloses a preparation method of a supported solid acid catalyst for esterification reaction, which adopts sulfonated biochar as a carrier to load MnO 2 /SO 4 2- The solid acid is used as a catalyst for esterification reaction, has the characteristics of high catalytic activity and high alcohol acid esterification conversion rate, and has good catalytic performance, but the immobilized solid acid catalyst has the problems that active substances are easy to run off, the catalyst is difficult to reuse and the like in the application process. Chinese patent CN 102898598A discloses a doped SO for esterification reaction 4 2- /ZrO 2 －Fe 2 O 3 －SiO 2 The preparation method of the solid acid catalyst can obviously improve the acid strength, stabilize and increase the acid center quantity, and can be repeatedly used, but has the defects of low activity, narrow application range, strong corrosiveness and the like.
Therefore, the novel esterification catalyst which has high catalytic activity, easy separation of the catalyst, environmental friendliness and safety is found.
Disclosure of Invention
In order to solve the defects of the prior art, the invention aims to provide a novel polyion liquid catalyst for esterification reaction, and a preparation method and application thereof.
In order to achieve the above purpose, the technical scheme of the invention is as follows:
in a first aspect of the present invention, there is provided a method for preparing a polyionic liquid catalyst, comprising the steps of:
step 1: dissolving 1-vinyl imidazole and 1-chlorobutane in an organic solvent A, and stirring and reacting at 50-80 ℃ in a non-oxidizing atmosphere to obtain 1-vinyl-3-butylimidazole chloride;
dissolving 1-vinyl-3-butyl imidazole chloride in an organic solvent B, slowly dropwise adding concentrated sulfuric acid at a low temperature, slowly heating to room temperature after dropwise adding, and stirring for reaction under the protection of a non-oxidizing atmosphere to obtain a 1-vinyl-3-butyl imidazole bisulfate monomer;
step 2: dissolving bis (2-chloroethyl) ether and 1-vinylimidazole in an organic solvent A, and carrying out violent stirring reaction at 50-80 ℃ in a non-oxidizing atmosphere to obtain a chloride salt crosslinking agent;
dissolving a chloride salt crosslinking agent in an organic solvent B, slowly dropwise adding concentrated sulfuric acid at a low temperature, slowly heating to room temperature after the dropwise adding is finished, and stirring for reaction under the protection of a non-oxidizing atmosphere to obtain a bisulfate crosslinking agent;
step 3: 1-vinyl-3-butyl imidazole bisulfate monomer and bisulfate cross-linking agent are taken to be dissolved in organic solution C, and then initiator is added, and the mixture is stirred vigorously to react under non-oxidizing atmosphere at 50-80 ℃ to obtain the polyion liquid catalyst.
In some embodiments of the invention, the organic solvent a comprises acetonitrile, dichloroethane, acetone, tetrahydrofuran, toluene, ethyl acetate, glycerol, and methyl tert-butyl ether, preferably acetonitrile.
In some embodiments of the invention, the organic solvent B comprises absolute ethanol, isopropanol, acetonitrile, tetrahydrofuran, and dichloromethane, preferably dichloromethane.
In some embodiments of the invention, the organic solvent C comprises anhydrous methanol, anhydrous ethanol, anhydrous n-propanol, anhydrous n-butanol, and isopropanol, preferably anhydrous methanol.
The synthetic route of the step 1 of the invention is as follows:
in some embodiments of the invention, in step 1, the molar ratio of 1-vinylimidazole to 1-chlorobutane is 1:1 to 1.5, preferably 1:1.2.
in some embodiments of the invention, in step 1, the molar ratio of concentrated sulfuric acid to 1-vinyl-3-butylimidazole chloride salt is 1:1.
in some embodiments of the invention, in step 1, the low temperature is 0 to 5 ℃, preferably 0 ℃;
preferably, the temperature during the dropping of the concentrated sulfuric acid is not more than 5 ℃.
The synthetic route of the step 2 of the invention is as follows:
in some embodiments of the invention, in step 2, the molar ratio of bis (2-chloroethyl) ether to 1-vinylimidazole is from 1:2 to 2.5, preferably 1:2.3.
in some embodiments of the invention, in step 2, the molar ratio of concentrated sulfuric acid to chlorine salt crosslinker is 1:1.
in some embodiments of the invention, in step 2, the low temperature is 0 to 5 ℃, preferably 0 ℃;
preferably, the temperature during the dropping of the concentrated sulfuric acid is not more than 5 ℃.
The synthetic route of the step 3 of the invention is as follows:
in some embodiments of the invention, in step 3, the molar ratio of 1-vinyl-3-butylimidazole bisulfate monomer to bisulfate crosslinker is 1:0.2-0.4.
In some embodiments of the invention, in step 3, the mole number of initiator is 1 to 5% of the 1-vinyl-3-butylimidazole bisulfate monomer.
In some embodiments of the invention, in step 3, the stirring rate of the vigorous stirring is 300-500r/min, and more preferably 400r/min.
In a second aspect of the invention, a polyionic liquid catalyst is provided, which is obtained by the preparation method.
In a third aspect of the invention, there is provided an application of the polyionic liquid catalyst, which is used in the esterification reaction of acid and alcohol, wherein the dosage of the polyionic liquid catalyst is 2-6wt% of the acid, the reaction temperature is 60-100 ℃, and the reaction time is 3-10 h.
In a fourth aspect of the invention, there is provided a method of catalyzing an esterification reaction comprising the steps of:
sequentially adding fatty acid or aromatic acid and linear chain alcohol or branched chain alcohol into a reaction container, simultaneously adding the polyion liquid catalyst according to claim 8, controlling the reaction temperature to be 60-70 ℃, and stirring and reacting for 3-6 h; and (3) centrifugally separating the obtained product, distilling supernatant fluid under pre-reduced pressure, removing unreacted alcohol and generated water to obtain an esterified product, and drying the centrifugally collected catalyst in vacuum for repeated use.
In some embodiments of the invention, the acid to alcohol molar ratio is 1:2.
In some embodiments of the invention, the polyionic liquid catalyst is added in an amount of 2% to 6% of the mass of the fatty acid or aromatic acid.
In some embodiments of the invention, the fatty acid is acetic acid, propionic acid, butyric acid, malonic acid or succinic acid.
In some embodiments of the invention, the aromatic acid is benzoic acid.
In some embodiments of the invention, the linear alcohol is methanol, ethanol, propanol, or n-butanol.
In some embodiments of the invention, the branched alcohol is isopropanol, isobutanol, t-butanol, isoamyl alcohol.
In some embodiments of the invention, the vacuum drying temperature is 60-70 ℃.
The beneficial effects of the invention are as follows:
(1) The polyion liquid catalyst designed and synthesized by the invention not only can solve the problems of low efficiency, high energy consumption, serious secondary pollution, strong corrosiveness to equipment and the like of the traditional organic and inorganic strong acid catalytic esterification reaction, but also can well overcome the problems of difficult recovery, easy damage and the like of the ion liquid catalyst.
(2) The designed and synthesized polyion liquid catalyst combines the advantages of solid acid, ion liquid and polymer, improves the catalytic activity and stability, and simultaneously can reduce the loss of the catalyst and realize the repeated recycling.
(3) According to the invention, the imidazole group, the ether group and other groups are simultaneously introduced into the polyion liquid, so that the catalytic activity of the catalyst can be obviously improved, and the stability of the catalyst is enhanced.
(4) The polyion liquid catalyst designed and synthesized by the invention is used for esterification reaction, and has the characteristics of wide application range, high catalytic activity, recyclable catalyst, environment friendliness, high selectivity and the like, and the high-efficiency green catalysis of the esterification reaction is truly realized.
Detailed Description
In order to enable those skilled in the art to more clearly understand the technical scheme of the present invention, the technical scheme of the present invention will be described in detail with reference to specific embodiments.
Example 1
(1) Synthesis of polyionic liquid catalyst
1) Synthesis of 1-vinyl-3-butylimidazole bisulfate monomer:
18.8g of 1-vinylimidazole and 22.2g of 1-chlorobutane were weighed into a 250mL three-necked flask, 10mL of acetonitrile was added, then the temperature was raised to 75 ℃ and stirred under nitrogen atmosphere for 24 hours, after the stirring was completed, the 1-chlorobutane and acetonitrile were removed by rotary evaporation at 70 ℃ using a rotary evaporator, then the mixture was washed 3 times with ethyl acetate, and finally the mixture was placed into a vacuum drying oven and dried at 65 ℃ for 12 hours to obtain 1-vinyl-3-butylimidazole chloride.
18.6g of 1-vinyl-3-butyl imidazole chloride salt and 30mL of solvent dichloroethane are weighed and placed in a 250mL three-neck flask, 10g of concentrated H with the mass fraction of 98% are slowly added dropwise at the temperature of 0 DEG C 2 SO 4 The temperature in the dropping process is not more than 5 ℃. The reaction mixture was then slowly warmed to room temperature and stirred for a further 10h, during which N was introduced 2 And (5) protecting. Removing solvent dichloromethane by reduced pressure distillation, and drying at 65 ℃ for 16 hours in a vacuum drying oven to obtain the 1-vinyl-3-butylimidazole bisulfate, wherein the 1-vinyl-3-butylimidazole bisulfate is quickly transferred to a glove box for storage after preparation.
2) Preparation of bisulfate crosslinking agent:
6.2g of bis (2-chloroethyl) ether and 9.4g of 1-vinylimidazole are weighed and dissolved in 20mL of acetonitrile, placed in a 250mL three-necked flask, vigorously stirred for 24 hours under a nitrogen atmosphere at 65 ℃ to obtain a large amount of white precipitate, the white precipitate is washed with acetonitrile for 3 times to remove unreacted substances, and placed in a vacuum drying oven at 65 ℃ for 12 hours to obtain a chloride salt crosslinking agent.
16.6g of the chlorine salt crosslinking agent and 26mL of solvent dichloroethane are weighed and placed in a three-necked flask, 5g of concentrated H with the mass fraction of 98% is slowly added dropwise at 0 DEG C 2 SO 4 The temperature in the dropping process is not more than 5 ℃. The reaction mixture was then slowly warmed to room temperature and stirred for a further 10h, during which N was introduced 2 And (5) protecting. Removing solvent dichloromethane through reduced pressure distillation, and then placing the solvent dichloromethane into a vacuum drying oven to be dried for 18 hours at 65 ℃ to obtain the bisulfate cross-linking agent, and rapidly transferring the bisulfate cross-linking agent into a glove box for storage after preparation.
3) Synthesis of polyionic liquid catalyst:
adding 4.5g of 1-vinyl-3-butylimidazole bisulfate and 1.3g of bisulfate crosslinking agent into a 250mL three-neck flask respectively, adding methanol for dissolution, adding 0.1g of initiator azodiisobutyronitrile, maintaining the temperature of 70 ℃ under a nitrogen atmosphere, vigorously stirring for 15h at a stirring speed of 400rpm/min, washing the product with methanol and deionized water after the reaction is finished, centrifuging, and drying in vacuum at 65 ℃ for 24h to obtain the polyion liquid catalyst.
(2) Catalytic esterification reaction
40.2g of acetic acid (n=0.67 mol) and 99.2g of n-butanol (n=1.34 mol) were accurately weighed and sequentially added into a 250mL round bottom flask, 0.8g of the prepared polyionic liquid catalyst was simultaneously added, the reaction temperature was 60 ℃, the stirring rate was 400r/min, and the reaction time was 3 hours. And (3) carrying out centrifugal separation on the obtained product, and removing unreacted alcohol and water generated by removing supernatant through pre-reduced pressure distillation to obtain an esterified product n-butyl acetate.
Example 2
(1) Synthesis of polyionic liquid catalyst
1) Synthesis of 1-vinyl-3-butylimidazole bisulfate monomer:
18.8g of 1-vinylimidazole and 22.2g of 1-chlorobutane are weighed and added into a 250mL three-neck flask, acetonitrile with the mass fraction of 10mL is added, then the temperature is raised to 75 ℃ and the mixture is stirred for 24 hours under the nitrogen atmosphere, after the stirring is finished, the 1-chlorobutane and the acetonitrile are removed by rotary evaporation at 70 ℃ by using a rotary evaporator, the mixture is washed for 3 times by ethyl acetate, and finally the mixture is dried for 12 hours at 65 ℃ in a vacuum drying oven, so as to obtain the 1-vinyl-3-butylimidazole chloride.
18.6g of 1-vinyl-3-butyl imidazole chloride salt and 30mL of solvent dichloroethane are weighed and placed in a 250mL three-neck flask, 10g of concentrated H with the mass fraction of 98% are slowly added dropwise at the temperature of 0 DEG C 2 SO 4 The temperature in the dropping process is not more than 5 ℃. The reaction mixture was then slowly warmed to room temperature and stirred for a further 10h, during which N was introduced 2 And (5) protecting. Removing solvent dichloromethane by reduced pressure distillation, and drying at 65 ℃ for 16 hours in a vacuum drying oven to obtain the 1-vinyl-3-butylimidazole bisulfate, wherein the 1-vinyl-3-butylimidazole bisulfate is quickly transferred to a glove box for storage after preparation.
2) Preparation of bisulfate crosslinking agent:
6.2g of bis (2-chloroethyl) ether and 9.4g of 1-vinylimidazole are weighed and dissolved in 20mL of acetonitrile, placed in a 250mL three-necked flask, vigorously stirred for 24 hours in a nitrogen atmosphere at 65 ℃ to obtain a large amount of white precipitate, the white precipitate is washed with acetonitrile for 3 times to remove unreacted substances, and placed in a vacuum drying oven at 65 ℃ for 12 hours to obtain the chlorine salt polymeric cross-linking agent.
16.6g of the chlorine salt crosslinking agent and 26mL of solvent dichloroethane are weighed and placed in a three-necked flask, 5g of concentrated H with the mass fraction of 98% is slowly added dropwise at 0 DEG C 2 SO 4 The temperature in the dropping process is not more than 5 ℃. The reaction mixture was then slowly warmed to room temperature and stirred for a further 10h, during which N was introduced 2 And (5) protecting. Removing solvent dichloromethane through reduced pressure distillation, and then placing the solvent dichloromethane into a vacuum drying oven to be dried for 18 hours at 65 ℃ to obtain the bisulfate cross-linking agent, and rapidly transferring the bisulfate cross-linking agent into a glove box for storage after preparation.
3) Synthesis of polyionic liquid catalyst:
adding 4.5g of 1-vinyl-3-butylimidazole bisulfate and 1.9g of bisulfate crosslinking agent into a 250mL three-neck flask respectively, adding methanol for dissolution, adding 0.1g of initiator azodiisobutyronitrile, maintaining the temperature of 70 ℃ under a nitrogen atmosphere, vigorously stirring for 15h at a stirring speed of 400rpm/min, washing the product with methanol and deionized water after the reaction is finished, centrifuging, and drying in vacuum at 65 ℃ for 24h to obtain the polyion liquid catalyst.
(2) Catalytic esterification reaction
40.2g of acetic acid (n=0.67 mol) and 99.2g of n-butanol (n=1.34 mol) were accurately weighed and sequentially added into a 250mL round bottom flask, 0.8g of the prepared polyionic liquid catalyst was simultaneously added, the reaction temperature was 60 ℃, the stirring rate was 400r/min, and the reaction time was 3 hours. And (3) carrying out centrifugal separation on the obtained product, and carrying out pre-reduced pressure distillation on supernatant fluid to remove unreacted alcohol and water generated by the removal to obtain an esterified product n-butyl acetate.
Example 3
(1) Synthesis of polyionic liquid catalyst
1) Synthesis of 1-vinyl-3-butylimidazole bisulfate monomer:
18.8g of 1-vinylimidazole and 22.2g of 1-chlorobutane are weighed and added into a 250mL three-neck flask, acetonitrile with the mass fraction of 10mL is added, then the temperature is raised to 75 ℃ and the mixture is stirred for 24 hours under the nitrogen atmosphere, after the stirring is finished, the 1-chlorobutane and the acetonitrile are removed by rotary evaporation at 70 ℃ by using a rotary evaporator, the mixture is washed for 3 times by ethyl acetate, and finally the mixture is dried for 12 hours at 65 ℃ in a vacuum drying oven, so as to obtain the 1-vinyl-3-butylimidazole chloride.
18.6g of 1-vinyl-3-butyl imidazole chloride salt and 30mL of solvent dichloroethane are weighed and placed in a 250mL three-neck flask, 10g of concentrated H with the mass fraction of 98% are slowly added dropwise at the temperature of 0 DEG C 2 SO 4 The temperature in the dropping process is not more than 5 ℃. The reaction mixture was then slowly warmed to room temperature and stirred for a further 10h, during which N was introduced 2 And (5) protecting. Removing solvent dichloromethane by reduced pressure distillation, and drying at 65 ℃ for 16 hours in a vacuum drying oven to obtain the 1-vinyl-3-butylimidazole bisulfate, wherein the 1-vinyl-3-butylimidazole bisulfate is quickly transferred to a glove box for storage after preparation.
2) Preparation of bisulfate crosslinking agent:
6.2g of bis (2-chloroethyl) ether and 9.4g of 1-vinylimidazole are weighed and dissolved in 20mL of acetonitrile, placed in a 250mL three-necked flask, vigorously stirred for 24 hours under a nitrogen atmosphere at 65 ℃ to obtain a large amount of white precipitate, the white precipitate is washed with acetonitrile for 3 times to remove unreacted substances, and placed in a vacuum drying oven at 65 ℃ for 12 hours to obtain a chloride salt crosslinking agent.
16.6g of the chlorine salt crosslinking agent and 26mL of solvent dichloroethane are weighed and placed in a three-necked flask, 5g of concentrated H with the mass fraction of 98% is slowly added dropwise at 0 DEG C 2 SO 4 The temperature in the dropping process is not more than 5 ℃. The reaction mixture was then slowly warmed to room temperature and stirred for a further 10h, during which N was introduced 2 And (5) protecting. Removing solvent dichloromethane through reduced pressure distillation, and then placing the solvent dichloromethane into a vacuum drying oven to be dried for 18 hours at 65 ℃ to obtain the bisulfate cross-linking agent, and rapidly transferring the bisulfate cross-linking agent into a glove box for storage after preparation.
3) Synthesis of polyionic liquid catalyst:
adding 4.5g of 1-vinyl-3-butylimidazole bisulfate and 2.6g of bisulfate crosslinking agent into a 250mL three-neck flask respectively, adding methanol for dissolution, adding 0.1g of initiator azodiisobutyronitrile, maintaining the temperature of 70 ℃ under a nitrogen atmosphere, vigorously stirring for 15h at a stirring speed of 400rpm/min, washing the product with methanol and deionized water after the reaction is finished, centrifuging, and drying in vacuum at 65 ℃ for 24h to obtain the polyion liquid catalyst.
(2) Catalytic esterification reaction
40.2g of acetic acid (n=0.67 mol) and 99.2g of n-butanol (n=1.34 mol) were accurately weighed and sequentially added into a 250mL round bottom flask, 0.8g of the prepared polyionic liquid catalyst was simultaneously added, the reaction temperature was 60 ℃, the stirring rate was 400r/min, and the reaction time was 3 hours. And (3) carrying out centrifugal separation on the obtained product, and carrying out pre-reduced pressure distillation on supernatant fluid to remove unreacted alcohol and water generated by the removal to obtain an esterified product n-butyl acetate.
Example 4
(1) Synthesis of polyionic liquid catalyst same as in example 1
(2) Catalytic esterification reaction
40.2g of acetic acid (n=0.67 mol) and 99.2g of n-butanol (n=1.34 mol) were accurately weighed and sequentially added into a 250mL round bottom flask, 1.6g of the prepared polyionic liquid catalyst was simultaneously added, the reaction temperature was 60 ℃, the stirring rate was 400r/min, and the reaction time was 3 hours. And (3) carrying out centrifugal separation on the obtained product, and carrying out pre-reduced pressure distillation on supernatant fluid to remove unreacted alcohol and water generated by the removal to obtain an esterified product n-butyl acetate.
Example 5
(1) Synthesis of polyionic liquid catalyst same as in example 1
(2) Catalytic esterification reaction
40.2g of acetic acid (n=0.67 mol) and 99.2g of n-butanol (n=1.34 mol) were accurately weighed and sequentially added into a 250mL round bottom flask, 2.4g of the prepared polyionic liquid catalyst was simultaneously added, the reaction temperature was 60 ℃, the stirring rate was 400r/min, and the reaction time was 3 hours. And (3) carrying out centrifugal separation on the obtained product, and carrying out pre-reduced pressure distillation on supernatant fluid to remove unreacted alcohol and water generated by the removal to obtain an esterified product n-butyl acetate.
Example 6
(1) Synthesis of polyionic liquid catalyst same as in example 1
(2) Catalytic esterification reaction
40.2g of acetic acid (n=0.67 mol) and 80.4g of propanol (n=1.34 mol) were accurately weighed into a 250mL round bottom flask, 0.8g of the prepared polyionic liquid catalyst was added simultaneously, the reaction temperature was 60 ℃, the stirring rate was 400r/min, and the reaction time was 3 hours. And (3) carrying out centrifugal separation on the obtained product, carrying out pre-reduced pressure distillation on supernatant fluid, removing unreacted alcohol and removing generated water to obtain an esterified product propyl acetate.
Example 7
(1) Synthesis of polyionic liquid catalyst same as in example 1
(2) Catalytic esterification reaction
49.6g of propionic acid (n=0.67 mol) and 99.2g of isobutanol (n=1.34 mol) were accurately weighed and sequentially added into a 250mL round bottom flask, 1.0g of the prepared polyionic liquid catalyst was added at the same time, the reaction temperature was 60 ℃, the stirring rate was 400r/min, and the reaction time was 3 hours. And (3) carrying out centrifugal separation on the obtained product, and carrying out pre-reduced pressure distillation on supernatant fluid to remove unreacted alcohol and generated water to obtain an esterified product isobutyl propionate.
Example 8
(1) Synthesis of polyionic liquid catalyst same as in example 1
(2) Catalytic esterification reaction
49.6g of propionic acid (n=0.67 mol) and 99.2g of tert-butanol (n=1.34 mol) were accurately weighed into a 250mL round bottom flask, 1.0g of the prepared polyionic liquid catalyst was added simultaneously, the reaction temperature was 60 ℃, the stirring rate was 400r/min, and the reaction time was 3 hours. And (3) carrying out centrifugal separation on the obtained product, and carrying out pre-reduced pressure distillation on supernatant fluid to remove unreacted alcohol and water generated by the supernatant fluid to obtain the esterified product tert-butyl propionate.
Example 9
(1) Synthesis of polyionic liquid catalyst same as in example 1
(2) Catalytic esterification reaction
49.6g of propionic acid (n=0.067 mol) and 117.9g of isoamyl alcohol (n=1.34 mol) are accurately weighed and sequentially added into a 250mL round bottom flask, 1.0g of the prepared polyion liquid catalyst is added, the reaction temperature is 60 ℃, the stirring speed is 400r/min, and the reaction time is 3h. And (3) carrying out centrifugal separation on the obtained product, carrying out pre-reduced pressure distillation on supernatant fluid, removing unreacted alcohol and removing generated water to obtain an esterified product isoamyl propionate.
Example 10
(1) Synthesis of polyionic liquid catalyst same as in example 1
(2) Catalytic esterification reaction
69.8g malonic acid (n=0.67 mol) and 85.8g methanol (n=2.68 mol) were weighed accurately and added sequentially to a 250mL round bottom flask, 1.4g of the prepared polyionic liquid catalyst was added simultaneously, the reaction temperature was 60 ℃, the stirring rate was 400r/min, and the reaction time was 3h. And (3) carrying out centrifugal separation on the obtained product, and carrying out pre-reduced pressure distillation on supernatant fluid to remove unreacted alcohol and water generated by the removal to obtain an esterified product dimethyl malonate.
Example 11
(1) Synthesis of polyionic liquid catalyst same as in example 1
(2) Catalytic esterification reaction
58.9g of butyric acid (n=0.67 mol) and 61.6g of ethanol (n=1.34 mol) were weighed accurately, added in sequence to a 250mL round bottom flask, 1.2g of the prepared polyionic liquid catalyst was added at the same time, the reaction temperature was 60 ℃, the stirring rate was 400r/min, and the reaction time was 3h. And (3) carrying out centrifugal separation on the obtained product, and carrying out pre-reduced pressure distillation on supernatant fluid to remove unreacted alcohol and generated water to obtain an esterified product ethyl butyrate.
Example 12
(1) Synthesis of polyionic liquid catalyst same as in example 1
(2) Catalytic esterification reaction
79.2g of succinic acid (n=0.67 mol) and 42.9g of methanol (n=1.34 mol) were accurately weighed into a 250mL round bottom flask, 1.6g of the prepared polyionic liquid catalyst was added simultaneously, the reaction temperature was 60 ℃, the stirring rate was 400r/min, and the reaction time was 3 hours. And (3) carrying out centrifugal separation on the obtained product, and carrying out pre-reduced pressure distillation on supernatant fluid to remove unreacted alcohol and water generated by the removal of the unreacted alcohol to obtain an esterified product dimethyl succinate.
Example 13
(1) Synthesis of polyionic liquid catalyst same as in example 1
(2) Catalytic esterification reaction
79.2g of succinic acid (n=0.67 mol) and 80.4g of isopropanol (n=1.34 mol) are accurately weighed and sequentially added into a 250mL round bottom flask, 1.6g of the prepared polyionic liquid catalyst is added, the reaction temperature is 60 ℃, the stirring rate is 400r/min, and the reaction time is 3h. And (3) carrying out centrifugal separation on the obtained product, and carrying out pre-reduced pressure distillation on supernatant fluid to remove unreacted alcohol and water generated by the removal to obtain an esterified product diisopropyl succinate.
Example 14
(1) Synthesis of polyionic liquid catalyst same as in example 1
(2) Catalytic esterification reaction
81.7g of benzoic acid (n=0.67 mol) and 61.6g of ethanol (n=1.34 mol) were weighed accurately and added sequentially to a 250mL round bottom flask, 1.6g of the prepared polyionic liquid catalyst was added simultaneously, the reaction temperature was 60 ℃, the stirring rate was 400r/min, and the reaction time was 3h. And (3) carrying out centrifugal separation on the obtained product, and carrying out pre-reduced pressure distillation on supernatant fluid to remove unreacted alcohol and generated water to obtain an esterified product ethyl benzoate.
Comparative example 1
(1) The preparation process of the catalyst in which the polyion liquid is replaced by the ionic liquid 1-vinyl-3-butylimidazole bisulfate and the 1-vinyl-3-butylimidazole bisulfate is the same as that of example 1.
(2) Catalytic esterification reaction
40.2g of acetic acid (n=0.67 mol) and 99.2g of n-butanol (n=1.34 mol) were accurately weighed into a 250mL round bottom flask, 0.8g of 1-vinyl-3-butylimidazole bisulfate was added simultaneously, the reaction temperature was 60 ℃, the stirring rate was 400r/min, and the reaction time was 3h. And standing the mixture after the reaction is finished, distilling the reaction solution under a pre-reduced pressure to remove unreacted alcohol and water generated by the removal, adding water into the rest reaction solution, standing for layering, and taking an upper organic phase to obtain n-butyl acetate. The ionic liquid catalyst at the lower layer is recycled after being dehydrated.
Comparative example 2
(1) The catalyst is replaced by concentrated sulfuric acid by polyion liquid.
(2) Catalytic esterification reaction
40.2g of acetic acid (n=0.67 mol) and 99.2g of n-butanol (n=1.34 mol) were accurately weighed into a 250mL round bottom flask, 0.8g of concentrated sulfuric acid was slowly added dropwise at 0 ℃, and the temperature during the addition did not exceed 5 ℃. The reaction mixture was then slowly warmed to 60℃and stirred at a rate of 400r/min for a reaction time of 3h. And standing the mixture after the reaction is finished, distilling the reaction solution under a pre-reduced pressure to remove unreacted alcohol and water generated by the removal, adding water into the rest reaction solution, standing for layering, and taking an upper organic phase to obtain n-butyl acetate.
Comparative example 3
(1) The catalyst is replaced by a polyion liquid to a commercially available solid acid catalyst SO 4 2- /ZrO 2 。
(2) Catalytic esterification reaction
Accurately weighing 40.2g acetic acid (n=0.67 mol) and 99.2g n-butanol (n=1.34 mol) were sequentially added to a 250mL round bottom flask, while adding 0.8g solid acid catalyst SO 4 2- /ZrO 2 The reaction temperature is 60 ℃, the stirring speed is 400r/min, and the reaction time is 3h. And (3) carrying out centrifugal separation on the obtained product, and carrying out pre-reduced pressure distillation on supernatant fluid to remove unreacted alcohol and water generated by the removal of the unreacted alcohol to obtain n-butyl acetate.
Performance test:
(1) Corrosiveness test:
preparing a plurality of steel ball samples with the diameter of 10mm, grinding the samples by using abrasive cloth or sand paper conforming to the regulations of GB/T2481.1 and GB/T2481.2, washing the samples by using a detergent (non-chloride) after finishing grinding, washing the samples by using distilled water, drying the samples, measuring the size, weighing the samples by using a vernier caliper, recording the measured size and the weighed weight, and adding the steel ball samples into a reaction bottle for esterification reaction before starting esterification reaction.
And after the esterification reaction is finished, taking out the stainless steel balls, cleaning, drying and weighing. The mass difference before and after the reaction of each steel ball is recorded, and then the corrosion rate of the steel ball in the reaction is calculated according to a formula.
Corrosion rate formula:
where ν represents corrosion rate (in mm/a, millimeter per year), ρ represents density of steel balls (g/cm 3 ) T represents the reaction time (h), S represents the surface area (cm) of the steel ball 2 ) W1 and W2 represent the mass (g) of the steel ball before and after the reaction.
(2) Repeatability test:
the reproducibility of the corresponding catalysts was tested using the esterification reaction conditions in the examples and comparative examples, each of which was performed separately. The recovered catalyst was put into the reaction again, the reaction conditions were unchanged, and the reaction was repeated 9 times. The reproducibility was judged in terms of yield and purity.
Test results:
(1) The product yields and purities of the examples and comparative examples are shown in Table 1.
Table 1 yield and purity of examples and comparative products
Examples 1 and 6-14 are respectively organic carboxylic acid esters synthesized by different fatty acids or aromatic acids and different linear alcohols or branched alcohols, and the synthesized organic carboxylic acid esters have higher yield and purity, which indicates that the novel polyion liquid catalyst has a certain adaptability to esterification reaction.
The comparison of example 1 with comparative examples 1-3 shows that the yield and purity of n-butyl acetate prepared in example 1 are far higher than those of n-butyl acetate prepared in comparative examples 1-3, and the novel polyionic liquid catalyst has higher catalytic activity compared with the existing catalysts such as ionic liquid catalyst, inorganic acid catalyst, solid acid catalyst and the like.
(2) The catalysts of example 1, comparative example 2, comparative example 3 were subjected to corrosion tests according to the esterification reaction conditions of example 1, comparative example 2, comparative example 3, respectively. The test results are shown in table 2:
TABLE 2 corrosion rates of the catalysts of examples and comparative examples on steel balls
Example 1 is compared with comparative examples 1-3, the corrosiveness of the novel polyionic liquid catalyst and the ionic liquid catalyst is compared with that of the inorganic acid catalyst and the solid acid catalyst, and the corrosiveness to the reactor is greatly reduced.
(3) The catalysts of example 1 and comparative example 1 were subjected to repeated experiments according to the esterification reaction conditions of example 1 and comparative example 1, respectively.
TABLE 3 repeatability test product yield and purity
In comparison with comparative example 1, the polyionic liquid catalyst prepared in example 1 has higher yield and purity after being reused for 9 times, and the ionic liquid catalyst prepared in comparative example 1, which catalyzes the synthesized n-butyl acetate, has the yield and purity of the product continuously reduced with the increase of the number of times of the reuse of the catalyst, particularly the yield and purity of the product are drastically reduced after being reused for 5 times. Compared with the ionic liquid catalyst, the polyionic liquid catalyst prepared by the method can improve the catalytic activity and stability of the polyionic liquid catalyst, reduce the loss of the catalyst and realize repeated recycling.
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.
Claims (10)
1. The preparation method of the polyionic liquid catalyst is characterized by comprising the following steps of:
step 1: dissolving 1-vinyl imidazole and 1-chlorobutane in an organic solvent A, and stirring and reacting at 50-80 ℃ in a non-oxidizing atmosphere to obtain 1-vinyl-3-butylimidazole chloride;
dissolving 1-vinyl-3-butyl imidazole chloride in an organic solvent B, slowly dropwise adding concentrated sulfuric acid at a low temperature, slowly heating to room temperature after dropwise adding, and stirring for reaction under the protection of a non-oxidizing atmosphere to obtain a 1-vinyl-3-butyl imidazole bisulfate monomer;
step 2: dissolving bis (2-chloroethyl) ether and 1-vinylimidazole in an organic solvent A, and carrying out violent stirring reaction at 50-80 ℃ in a non-oxidizing atmosphere to obtain a chloride salt crosslinking agent;
dissolving a chloride salt crosslinking agent in an organic solvent B, slowly dropwise adding concentrated sulfuric acid at a low temperature, slowly heating to room temperature after the dropwise adding is finished, and stirring for reaction under the protection of a non-oxidizing atmosphere to obtain a bisulfate crosslinking agent;
step 3: 1-vinyl-3-butyl imidazole bisulfate monomer and bisulfate cross-linking agent are taken to be dissolved in organic solution C, and then initiator is added, and the mixture is stirred vigorously to react under non-oxidizing atmosphere at 50-80 ℃ to obtain the polyion liquid catalyst.
2. The preparation method according to claim 1, wherein the organic solvent a comprises acetonitrile, dichloroethane, acetone, tetrahydrofuran, toluene, ethyl acetate, glycerol and methyl tert-butyl ether, preferably acetonitrile;
preferably, the organic solvent B comprises absolute ethanol, isopropanol, acetonitrile, tetrahydrofuran and dichloromethane, preferably dichloromethane;
preferably, the organic solvent C includes anhydrous methanol, anhydrous ethanol, anhydrous n-propanol, anhydrous n-butanol, and isopropanol, and preferably, anhydrous methanol.
3. The method according to claim 1, wherein in step 1, the molar ratio of 1-vinylimidazole to 1-chlorobutane is 1:1 to 1.5, preferably 1:1.2;
preferably, the molar ratio of concentrated sulfuric acid to 1-vinyl-3-butylimidazole chloride salt is 1:1.
4. the method of claim 1, wherein in step 1, the low temperature is 0 to 5 ℃, preferably 0 ℃;
preferably, the temperature during the dropping of the concentrated sulfuric acid is not more than 5 ℃.
5. The process according to claim 1, wherein in step 2 the molar ratio of bis (2-chloroethyl) ether to 1-vinylimidazole is from 1:2 to 2.5, preferably 1:2.3;
preferably, the molar ratio of concentrated sulfuric acid to chlorine salt crosslinking agent is 1:1.
6. the method of claim 1, wherein in step 2, the low temperature is 0-5 ℃, preferably 0 ℃;
preferably, the temperature during the dropping of the concentrated sulfuric acid is not more than 5 ℃.
7. The method according to claim 1, wherein in step 3, the molar ratio of the 1-vinyl-3-butylimidazole bisulfate monomer to the bisulfate crosslinking agent is 1:0.2-0.4;
preferably, the mole number of the initiator is 1-5% of the 1-vinyl-3-butylimidazole bisulfate monomer;
preferably, the stirring rate of the vigorous stirring is 300-500r/min, and more preferably 400r/min.
8. A polyionic liquid catalyst obtainable by the process of any one of claims 1 to 7.
9. Use of the polyionic liquid catalyst according to claim 8, wherein the polyionic liquid catalyst is used in the esterification of an acid and an alcohol in an amount of 2 to 6wt% of the acid at a reaction temperature of 60 to 100 ℃ for a reaction time of 3 to 10 hours.
10. A method of catalyzing an esterification reaction, comprising the steps of:
sequentially adding fatty acid or aromatic acid and linear chain alcohol or branched chain alcohol into a reaction container, simultaneously adding the polyion liquid catalyst according to claim 8, controlling the reaction temperature to be 60-70 ℃, and stirring and reacting for 3-6 h; centrifugally separating the obtained product, performing pre-reduced pressure distillation on supernatant, removing unreacted alcohol and generated water to obtain an esterified product, and performing vacuum drying on a centrifugally collected catalyst for repeated use;
preferably, the molar ratio of acid to alcohol is 1:2;
preferably, the adding amount of the polyion liquid catalyst is 2-6% of the mass of fatty acid or aromatic acid;
preferably, the fatty acid is acetic acid, propionic acid, butyric acid, malonic acid or succinic acid;
preferably, the aromatic acid is benzoic acid;
preferably, the linear alcohol is methanol, ethanol, propanol or n-butanol;
preferably, the branched alcohol is isopropanol, isobutanol, tertiary butanol, isoamyl alcohol;
preferably, the temperature of the vacuum drying is 60-70 ℃.
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| CN116920939A (en) * | 2023-09-15 | 2023-10-24 | 山东海化集团有限公司 | Polyion liquid-loaded silicon dioxide catalyst and preparation method and application thereof |
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2023
- 2023-05-09 CN CN202310516460.9A patent/CN116574214A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116920939A (en) * | 2023-09-15 | 2023-10-24 | 山东海化集团有限公司 | Polyion liquid-loaded silicon dioxide catalyst and preparation method and application thereof |
| CN116920939B (en) * | 2023-09-15 | 2023-12-29 | 山东海化集团有限公司 | Polyion liquid-loaded silicon dioxide catalyst and preparation method and application thereof |
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