CN113087740B - Preparation method and application of organotin ionic liquid catalyst - Google Patents
Preparation method and application of organotin ionic liquid catalyst Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 63
- 239000002608 ionic liquid Substances 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- ROORDVPLFPIABK-UHFFFAOYSA-N diphenyl carbonate Chemical compound C=1C=CC=CC=1OC(=O)OC1=CC=CC=C1 ROORDVPLFPIABK-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 21
- 238000001914 filtration Methods 0.000 claims abstract description 16
- 238000007323 disproportionation reaction Methods 0.000 claims abstract description 15
- 238000000926 separation method Methods 0.000 claims abstract description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 45
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 32
- 238000006243 chemical reaction Methods 0.000 claims description 29
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 25
- 229910052757 nitrogen Inorganic materials 0.000 claims description 16
- -1 imidazole compound Chemical class 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 12
- XTBFPVLHGVYOQH-UHFFFAOYSA-N methyl phenyl carbonate Chemical compound COC(=O)OC1=CC=CC=C1 XTBFPVLHGVYOQH-UHFFFAOYSA-N 0.000 claims description 11
- 238000010992 reflux Methods 0.000 claims description 11
- 230000002194 synthesizing effect Effects 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 10
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 9
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 9
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 8
- 239000000706 filtrate Substances 0.000 claims description 7
- 238000002390 rotary evaporation Methods 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 7
- LWTIGYSPAXKMDG-UHFFFAOYSA-N 2,3-dihydro-1h-imidazole Chemical compound C1NC=CN1 LWTIGYSPAXKMDG-UHFFFAOYSA-N 0.000 claims description 6
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 6
- 239000012263 liquid product Substances 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- 150000001450 anions Chemical class 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 239000013335 mesoporous material Substances 0.000 claims description 5
- 229920000642 polymer Polymers 0.000 claims description 5
- 238000003786 synthesis reaction Methods 0.000 claims description 5
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 4
- 230000015572 biosynthetic process Effects 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- SLLDUURXGMDOCY-UHFFFAOYSA-N 2-butyl-1h-imidazole Chemical compound CCCCC1=NC=CN1 SLLDUURXGMDOCY-UHFFFAOYSA-N 0.000 claims description 3
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 3
- WBUSESIMOZDSHU-UHFFFAOYSA-N 3-(4,5-dihydroimidazol-1-yl)propyl-triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN1CCN=C1 WBUSESIMOZDSHU-UHFFFAOYSA-N 0.000 claims description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- GCTFWCDSFPMHHS-UHFFFAOYSA-M Tributyltin chloride Chemical compound CCCC[Sn](Cl)(CCCC)CCCC GCTFWCDSFPMHHS-UHFFFAOYSA-M 0.000 claims description 3
- 238000004440 column chromatography Methods 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 239000000110 cooling liquid Substances 0.000 claims description 3
- 239000012043 crude product Substances 0.000 claims description 3
- 238000001514 detection method Methods 0.000 claims description 3
- 239000000835 fiber Substances 0.000 claims description 3
- 239000002071 nanotube Substances 0.000 claims description 3
- 230000007935 neutral effect Effects 0.000 claims description 3
- 229920005989 resin Polymers 0.000 claims description 3
- 239000011347 resin Substances 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 239000000725 suspension Substances 0.000 claims description 3
- PQAMFDRRWURCFQ-UHFFFAOYSA-N 2-ethyl-1h-imidazole Chemical compound CCC1=NC=CN1 PQAMFDRRWURCFQ-UHFFFAOYSA-N 0.000 claims description 2
- MKBBSFGKFMQPPC-UHFFFAOYSA-N 2-propyl-1h-imidazole Chemical compound CCCC1=NC=CN1 MKBBSFGKFMQPPC-UHFFFAOYSA-N 0.000 claims description 2
- KSCAZPYHLGGNPZ-UHFFFAOYSA-N 3-chloropropyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)CCCCl KSCAZPYHLGGNPZ-UHFFFAOYSA-N 0.000 claims description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 2
- 150000007513 acids Chemical class 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 150000002500 ions Chemical class 0.000 claims 1
- 238000005809 transesterification reaction Methods 0.000 abstract description 8
- 239000002994 raw material Substances 0.000 abstract description 7
- 239000000047 product Substances 0.000 abstract description 6
- 238000011084 recovery Methods 0.000 abstract description 4
- 239000006227 byproduct Substances 0.000 abstract description 3
- 239000002815 homogeneous catalyst Substances 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 230000035484 reaction time Effects 0.000 abstract description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 5
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 5
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 5
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000005349 anion exchange Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000005832 oxidative carbonylation reaction Methods 0.000 description 2
- 239000004417 polycarbonate Substances 0.000 description 2
- 229920000515 polycarbonate Polymers 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000010025 steaming Methods 0.000 description 2
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- NSPMIYGKQJPBQR-UHFFFAOYSA-N 4H-1,2,4-triazole Chemical compound C=1N=CNN=1 NSPMIYGKQJPBQR-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 150000002148 esters Chemical group 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 150000005677 organic carbonates Chemical class 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 150000003606 tin compounds Chemical class 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/22—Tin compounds
- C07F7/2284—Compounds with one or more Sn-N linkages
-
- 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
- B01J31/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
- B01J31/122—Metal aryl or alkyl compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C68/00—Preparation of esters of carbonic or haloformic acids
- C07C68/06—Preparation of esters of carbonic or haloformic acids from organic carbonates
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C68/00—Preparation of esters of carbonic or haloformic acids
- C07C68/08—Purification; Separation; Stabilisation
-
- 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
- B01J2231/42—Catalytic cross-coupling, i.e. connection of previously not connected C-atoms or C- and X-atoms without rearrangement
- B01J2231/4277—C-X Cross-coupling, e.g. nucleophilic aromatic amination, alkoxylation or analogues
- B01J2231/4288—C-X Cross-coupling, e.g. nucleophilic aromatic amination, alkoxylation or analogues using O nucleophiles, e.g. alcohols, carboxylates, esters
-
- 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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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a preparation method and application of an organotin ionic liquid catalyst, and belongs to the field of application chemistry. The organotin ionic liquid catalyst adopted by the invention has the advantages of simple preparation method, stable structure, low-cost and easily obtained raw materials, convenient operation, environmental protection and high atom economy; the catalyst solves the problems of low yield of diphenyl carbonate products, difficult separation and recovery of homogeneous catalysts and the like in the disproportionation step in the transesterification process. The catalyst has the advantages of less consumption, no byproducts, short reaction time, higher yield and selectivity of the product, and good application prospect, and the catalyst is recycled through centrifugal separation or filtration separation, so that the loss is avoided.
Description
Technical Field
The invention relates to a preparation method of an organotin ionic liquid catalyst and application thereof in synthesizing diphenyl carbonate, belonging to the technical field of organic synthesis.
Background
The diphenyl carbonate (DPC) compound is an important organic carbonate and has important research and application values in the fields of pharmacy, fine chemical engineering, material synthesis and the like. In the field of engineering plastics, the compounds can also be used as important intermediates for the synthesis of Polycarbonates (PC). At present, the synthesis method of DPC mainly comprises a phosgene method, an oxidative carbonylation method and an ester exchange method. The phosgene method uses highly toxic phosgene as a starting material, and a large amount of waste acid and waste liquid discharged in the production process corrodes equipment and severely pollutes the environment, so that the method has the defects of potential safety hazard, low atomic economy and the like and is eliminated. Although the oxidative carbonylation method has high atom utilization rate, the noble metal Pd catalyst is used, the production cost is high, the activity is low, the service life is short, and the phenol is easy to oxidize, so that the method is still in the laboratory research stage. The transesterification method is a synthetic method taking phenol as a raw material, wherein the dimethyl carbonate (DMC) and phenol transesterification method uses nontoxic and pollution-free DMC as the raw material to replace toxic phosgene for transesterification reaction, the toxicity and corrosiveness of the whole process are obviously reduced, the byproduct methanol can be recycled for synthesizing the initial raw material DMC, the requirement of sustainable development of green chemistry is met, and the other reaction raw material phenol is a bulk chemical product, and the cost is low; therefore, the method is considered to be a green, economical and clean synthetic route which has the most development prospect for synthesizing DPC instead of phosgene.
The process of synthesizing DPC by transesterification of DMC and phenol is divided into two reaction steps of transesterification and disproportionation, the previous research mainly aims at the first transesterification reaction step, the activity of the catalyst is calculated according to the total yield of Methyl Phenyl Carbonate (MPC) and DPC, however, the research discovers that the second MPC disproportionation reaction can not be thoroughly carried out, and the generation of the target product DPC is greatly restricted. In addition, the research results also show that the catalyst suitable for the first-step transesterification reaction does not necessarily have a good catalytic effect on the disproportionation reaction. Therefore, it is also very important and urgent to study the catalyst required for the disproportionation reaction. Wang Songlin et al studied the catalytic properties of tin compounds and showed that homogeneous organotin is unfavorable for recovery, while the product contains tin residues, affecting product purity, polluting the environment (university chemistry report, 2014, 35:2177-2181); metal oxide catalysts have also been developed, but have relatively low catalytic activity and are difficult to use industrially (mol. Catalyst., 2019, 468:117-124).
In view of the above, development of a high-efficiency catalyst is a key point for synthesizing high-quality DPC in the disproportionation step, and thus, development of a novel disproportionation catalyst is still required.
Disclosure of Invention
The invention aims to solve the problems of large dosage of homogeneous catalyst, difficult separation and recovery and low DPC yield in the prior art, and provides an organotin ionic liquid catalyst for synthesizing DPC by MPC disproportionation reaction and a preparation method thereof.
The invention provides a preparation method of an organotin ionic liquid catalyst, which has the following structural formula:
wherein: r is-H, -CH 3 、-CH 2 CH 3 、-CH 2 CH 2 CH 3 or-CH 2 CH 2 CH 2 CH 3 The method comprises the steps of carrying out a first treatment on the surface of the X is OH - 、BF 4 - 、PF 6 - 、HSO 4 - Or PhSO 3 - 。
The preparation method of the organotin ionic liquid catalyst comprises the following steps: the nano mesoporous material, imidazole compound and tributyltin chloride are used as raw materials and synthesized by a chemical bond grafting method.
Further, in the above technical scheme, the specific preparation steps of the organotin ionic liquid catalyst are as follows:
the first step: under the protection of nitrogen, adding an imidazole compound into toluene, stirring, heating for dissolving, then dropwise adding gamma-chloropropyl triethoxysilane, carrying out reflux reaction after the dropwise adding, and synthesizing to obtain the imidazole silane compound grafted by chemical bonds after the TLC detection reaction is finished; then triethylamine is dripped, and the reaction is continued after the dripping is finished, so as to obtain a silanized N- [3- (triethoxysilyl) propyl ] -4, 5-dihydroimidazole synthetic solution; cooling the synthetic solution to room temperature, filtering, washing with toluene, performing reduced pressure rotary evaporation on the filtrate, adding diethyl ether, filtering, washing, performing reduced pressure rotary evaporation on the filtrate again, and obtaining a pale yellow crude product; finally separating by neutral aluminium oxide column chromatography, and performing rotary evaporation under reduced pressure to obtain colorless viscous liquid product;
and a second step of: adding mesoporous materials into toluene under the protection of nitrogen, uniformly dispersing by ultrasonic, dropwise adding the colorless viscous liquid product obtained in the first step, stirring, heating and refluxing, filtering and separating after the reaction is completed, washing with absolute ethyl alcohol, extracting white solid by adopting dichloromethane solvent, carrying out Soxhlet reflux extraction, and then carrying out vacuum drying at 60 ℃ to finally obtain the chemical bond grafted dihydroimidazole sub-liquid compound;
and a third step of: under the protection of nitrogen, adding the dihydroimidazole liquid compound obtained in the second step into toluene, uniformly dispersing by ultrasonic to form suspension, dropwise adding tributyl tin chloride, heating and stirring, refluxing after the dropwise adding, filtering a cooling liquid after the reaction is finished, washing by toluene, and then drying in vacuum at 60 ℃ to obtain the organotin ionic liquid catalyst;
fourth step: under the protection of nitrogen, the organic tin ionic liquid catalyst obtained in the third step is subjected to ion exchange with different types of acid or alkali, so that the organic tin ionic liquid catalyst with different anion types can be prepared.
Further, in the above technical scheme, in the first step, the imidazole compound is imidazole, 2-methylimidazole, 2-ethylimidazole, 2-propylimidazole, 2-butylimidazole or 1,2, 4-triazole.
Further, in the above technical solution, in the second step, the mesoporous material is SiO 2 MCM-41, SBA-15, nanotubes, polymers, resins or fibers.
Further, in the above technical scheme, in the third step, the content of the organotin is 1 to 40%.
Further, in the above technical scheme, in the fourth step, the different types of acids are H 2 SO 4 、TMAOH、HBF 4 、HPF 6 HBr or PhSO 3 H。
The invention also provides application of the organotin ionic liquid catalyst in synthesizing DPC through disproportionation reaction.
Further, in the technical scheme, under the protection of nitrogen, the MPC and the organotin ionic liquid catalyst are added into a round bottom flask with a rectifying column for mixing, and the temperature is slowly increased for reaction.
Further, in the technical scheme, after the reaction is finished, the catalyst can be recycled through centrifugal separation or filtering separation, so that Sn loss is avoided.
The invention has the beneficial effects that:
the invention discloses a preparation method and application of an organotin ionic liquid catalyst, which mainly solve the problems of low DPC yield, difficult separation and recovery of a homogeneous catalyst and the like in the second-step MPC disproportionation reaction. The catalyst has the advantages of simple preparation method, stable structure, low-cost and easily-obtained raw materials, convenient operation, environmental protection, high atom economy, less catalyst consumption, no byproducts in disproportionation reaction, short reaction time, higher yield and selectivity of DPC, and capability of avoiding loss by centrifugal separation or filtering separation, recycling and recycling of the catalyst.
Detailed Description
Example 1
Under the protection of nitrogen, adding 4.5g of imidazole into 100mL of dry toluene, stirring, heating, dissolving, slowly dripping 16.1g of gamma-chloropropyl triethoxysilane compound, carrying out a reflux reaction for 24 hours after dripping, synthesizing a chemical bond grafted imidazole silane compound, carrying out detection reaction by TLC, slowly dripping 6.7g of triethylamine, and carrying out a reaction for 2 hours after dripping to obtain a silanized N- [3- (triethoxysilyl) propyl ] -4, 5-dihydroimidazole synthetic solution; cooling the synthetic solution to room temperature, filtering and washing the synthetic solution by adopting dry toluene for three times, decompressing and steaming the filtrate, filtering and washing the filtrate by adopting dry diethyl ether for three times, decompressing and steaming the filtrate again to obtain a pale yellow crude product; finally, separating by neutral aluminium oxide column chromatography, and performing rotary evaporation under reduced pressure to obtain colorless viscous liquid product.
Under the protection of nitrogen, 1.0g of synthesized or purchased mesoporous SiO 2 Adding one of materials such as nanotube, polymer, resin, and fiber into dry toluene, ultrasonic dispersing for 30min, dripping 2.0g of colorless viscous liquid product synthesized in the first step, stirring, heating and refluxing for reaction for 24 hrAfter completion, filtering and separating, washing with absolute ethyl alcohol for three times, reflux-extracting the obtained white solid with a Soxhlet extractor with dichloromethane as a solvent for 12 hours, and then vacuum-drying at 60 ℃ for 24 hours to finally obtain the dihydroimidazole ionic liquid compound.
Under the protection of nitrogen, adding 1.0g of the dihydroimidazole ionic liquid compound synthesized in the second step into 50mL of dry toluene, uniformly dispersing by ultrasonic to form suspension, then dropwise adding 2.4g of tributyltin chloride organic compound, heating and stirring, carrying out reflux reaction for 24 hours after the dropwise adding is finished, filtering cooling liquid after the reaction is finished, washing with dry toluene for multiple times, and then drying in vacuum at 60 ℃ for 24 hours to obtain the organotin ionic liquid catalyst.
Under the protection of nitrogen, the organotin ionic liquid catalyst synthesized in the third step is subjected to ion exchange with different types of acid or alkali, so that organotin ionic liquid catalysts with different anion types can be prepared.
Example 2
The preparation process of the catalyst is the same as that of example 1, imidazole is changed into 2-methylimidazole, and the organotin ionic liquid catalyst containing methyl is prepared.
Example 3
The preparation process of the catalyst is the same as that of example 1, imidazole is changed into 2-butylimidazole, and the organotin ionic liquid catalyst containing butyl is prepared.
Example 4
The procedure of example 1 was followed, except that SBA-15 was replaced by mesoporous SiO 2 SiO is prepared 2 A solid-supported organotin ionic liquid catalyst.
Example 5
The preparation process of the catalyst is the same as that of example 1, SBA-15 is changed into a high molecular polymer, and the polymer immobilized organotin ionic liquid catalyst is prepared.
Example 6
The procedure for the preparation of the catalyst was as in example 1, using H 2 SO 4 Anion exchange reaction is carried out to obtain the anion HSO 4 - An organotin ionic liquid catalyst.
Example 7
The procedure for the preparation of the catalyst was as in example 1, using HBF 4 Performing anion exchange reaction to obtain BF 4 - An organotin ionic liquid catalyst.
Example 8
The catalyst was prepared in the same manner as in example 1 using PhSO 3 H is subjected to anion exchange reaction to prepare the anion SO 3 H - An organotin ionic liquid catalyst.
Example 9
The catalysts prepared in examples 1-8 were used in the reaction of MPC disproportionation to synthesize DPC.
(1) In a three-neck flask equipped with a rectifying column, a thermometer and a nitrogen conduit, air in the apparatus was replaced with high-purity nitrogen, and then MPC and an organotin ionic liquid catalyst were added.
(2) Slowly heating to 150-200 ℃ for reaction, collecting fraction DMC through a rectifying column, and reacting for 1-3 h.
(3) After the reaction, the catalyst was subjected to centrifugal separation, and a proper amount of the reaction solution was diluted with an acetone solvent, and then corrected and normalized to a quantitative analysis was performed by a gas chromatograph of Shanghai Tianmei 7980, and the catalytic performances of the catalysts prepared in examples 1 to 8 are shown in table 1.
Table 1 catalytic performance of organotin ionic liquid catalysts of examples 1 to 8
MPC: methyl phenyl carbonate; DPC: diphenyl carbonate.
The foregoing embodiments illustrate the basic principles, principal features and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the above-described embodiments, and that the above-described embodiments and descriptions are merely illustrative of the principles of the present invention, and various changes and modifications may be made without departing from the scope of the principles of the invention, which are defined in the appended claims.
Claims (5)
1. The preparation method of the organotin ionic liquid catalyst is characterized by comprising the following steps of:
the first step: under the protection of nitrogen, adding an imidazole compound into toluene, stirring, heating for dissolving, then dropwise adding gamma-chloropropyl triethoxysilane, carrying out reflux reaction after the dropwise adding, and synthesizing to obtain the imidazole silane compound grafted by chemical bonds after the TLC detection reaction is finished; then triethylamine is dripped, and the reaction is continued after the dripping is finished, so as to obtain a silanized N- [3- (triethoxysilyl) propyl ] -4, 5-dihydroimidazole synthetic solution; cooling the synthetic solution to room temperature, filtering, washing with toluene, performing reduced pressure rotary evaporation on the filtrate, adding diethyl ether, filtering, washing, performing reduced pressure rotary evaporation on the filtrate again, and obtaining a pale yellow crude product; finally separating by neutral aluminium oxide column chromatography, and performing rotary evaporation under reduced pressure to obtain colorless viscous liquid product; the imidazole compound is selected from imidazole, 2-methylimidazole, 2-ethylimidazole, 2-propylimidazole or 2-butylimidazole;
and a second step of: adding mesoporous materials into toluene under the protection of nitrogen, uniformly dispersing by ultrasonic, dropwise adding the colorless viscous liquid product obtained in the first step, stirring, heating and refluxing, filtering and separating after the reaction is completed, washing with absolute ethyl alcohol, extracting white solid by adopting dichloromethane solvent and Soxhlet reflux, and then drying in vacuum at 60 ℃ to finally obtain the chemical bond grafted dihydroimidazole liquid compound;
and a third step of: adding the dihydroimidazole liquid compound obtained in the second step into toluene under the protection of nitrogen, uniformly dispersing by ultrasonic to form suspension, dropwise adding tributyltin chloride, heating and stirring, refluxing after the dropwise adding, filtering a cooling liquid after the reaction is finished, washing by toluene, and then drying in vacuum at 60 ℃ to obtain the organotin ionic liquid catalyst; wherein the content of the organic tin in the step is 1-40%;
fourth step: under the protection of nitrogen, the organic tin ionic liquid catalyst obtained in the third step is subjected to ion with different types of acidExchanging to prepare organotin ionic liquid catalysts with different anion types; the different types of acids are selected from H 2 SO 4 、HBF 4 、HBr、HPF 6 Or PhSO 3 H；
The organic tin ionic liquid catalyst has the structure that:
2. the method for preparing the organotin ionic liquid catalyst according to claim 1, wherein the method comprises the following steps: in the second step, the mesoporous material is SiO 2 MCM-41, SBA-15, nanotubes, polymers, resins or fibers.
3. The use of the organotin ionic liquid catalyst prepared by the method of claim 1 in synthesizing diphenyl carbonate by disproportionation reaction.
4. The use of an organotin ionic liquid catalyst according to claim 3 for the synthesis of diphenyl carbonate by disproportionation reaction, wherein: under the protection of nitrogen, methyl phenyl carbonate and an organotin ionic liquid catalyst are added into a round bottom flask with a rectifying column for mixing, and the temperature is slowly increased for reaction.
5. The use of the organotin ionic liquid catalyst according to claim 4 in the synthesis of diphenyl carbonate by disproportionation reaction, wherein the organotin ionic liquid catalyst is characterized in that: after the reaction is finished, the catalyst can be recycled through centrifugal separation or filtration separation, so that Sn loss is avoided.
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| CN102171177A (en) * | 2008-09-30 | 2011-08-31 | 拜尔技术服务有限责任公司 | Method for producing diphenylcarbonate having catalyst comprising ionic fluids |
| CN107308984A (en) * | 2016-04-27 | 2017-11-03 | 中国科学院成都有机化学有限公司 | It is a kind of to be used for dimethyl carbonate and the immobilized organotin catalysts of silica and preparation method of phenol ester exchange |
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| CN102171177A (en) * | 2008-09-30 | 2011-08-31 | 拜尔技术服务有限责任公司 | Method for producing diphenylcarbonate having catalyst comprising ionic fluids |
| CN107308984A (en) * | 2016-04-27 | 2017-11-03 | 中国科学院成都有机化学有限公司 | It is a kind of to be used for dimethyl carbonate and the immobilized organotin catalysts of silica and preparation method of phenol ester exchange |
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