CN114011459A - Titanium series double-acid type ionic liquid catalyst, preparation method and application - Google Patents
Titanium series double-acid type ionic liquid catalyst, preparation method and application Download PDFInfo
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- CN114011459A CN114011459A CN202111355776.1A CN202111355776A CN114011459A CN 114011459 A CN114011459 A CN 114011459A CN 202111355776 A CN202111355776 A CN 202111355776A CN 114011459 A CN114011459 A CN 114011459A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 67
- 239000002608 ionic liquid Substances 0.000 title claims abstract description 55
- 239000002253 acid Substances 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 150000003608 titanium Chemical class 0.000 title description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 34
- 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 27
- QWXYZCJEXYQNEI-OSZHWHEXSA-N intermediate I Chemical compound COC(=O)[C@@]1(C=O)[C@H]2CC=[N+](C\C2=C\C)CCc2c1[nH]c1ccccc21 QWXYZCJEXYQNEI-OSZHWHEXSA-N 0.000 claims abstract description 26
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 21
- 239000010936 titanium Substances 0.000 claims abstract description 19
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 16
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims abstract description 15
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 15
- 238000010992 reflux Methods 0.000 claims abstract description 13
- 238000001035 drying Methods 0.000 claims abstract description 10
- 229910052751 metal Inorganic materials 0.000 claims abstract description 10
- 239000002184 metal Substances 0.000 claims abstract description 10
- 238000003756 stirring Methods 0.000 claims abstract description 9
- 125000000524 functional group Chemical group 0.000 claims abstract description 7
- 239000007864 aqueous solution Substances 0.000 claims abstract description 6
- 239000002994 raw material Substances 0.000 claims abstract description 5
- 230000035484 reaction time Effects 0.000 claims abstract description 5
- 150000003839 salts Chemical class 0.000 claims abstract description 4
- 239000002841 Lewis acid Substances 0.000 claims abstract 2
- 150000007517 lewis acids Chemical class 0.000 claims abstract 2
- 150000001450 anions Chemical class 0.000 claims description 8
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- -1 alkyl imidazole Chemical compound 0.000 claims description 7
- 238000002390 rotary evaporation Methods 0.000 claims description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- 125000000542 sulfonic acid group Chemical group 0.000 claims description 4
- 150000001768 cations Chemical class 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical group CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims 1
- 239000000203 mixture Substances 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 11
- 230000002194 synthesizing effect Effects 0.000 abstract description 11
- 238000005809 transesterification reaction Methods 0.000 abstract description 5
- 229910003074 TiCl4 Inorganic materials 0.000 description 13
- 230000003197 catalytic effect Effects 0.000 description 11
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 11
- 150000002148 esters Chemical group 0.000 description 9
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 7
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical compound CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 description 6
- VILAVOFMIJHSJA-UHFFFAOYSA-N dicarbon monoxide Chemical compound [C]=C=O VILAVOFMIJHSJA-UHFFFAOYSA-N 0.000 description 5
- 239000004417 polycarbonate Substances 0.000 description 5
- 229920000515 polycarbonate Polymers 0.000 description 5
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical group ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 4
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 4
- 230000009471 action Effects 0.000 description 4
- 125000002091 cationic group Chemical group 0.000 description 4
- 239000012295 chemical reaction liquid Substances 0.000 description 4
- XTBFPVLHGVYOQH-UHFFFAOYSA-N methyl phenyl carbonate Chemical compound COC(=O)OC1=CC=CC=C1 XTBFPVLHGVYOQH-UHFFFAOYSA-N 0.000 description 4
- 230000002195 synergetic effect Effects 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 238000007036 catalytic synthesis reaction Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000000543 intermediate Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 230000007704 transition Effects 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- FSSPGSAQUIYDCN-UHFFFAOYSA-N 1,3-Propane sultone Chemical compound O=S1(=O)CCCO1 FSSPGSAQUIYDCN-UHFFFAOYSA-N 0.000 description 2
- 229910006069 SO3H Inorganic materials 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000013522 chelant Substances 0.000 description 2
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 description 2
- 229940106681 chloroacetic acid Drugs 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 2
- OFGDSGVGRWPQJQ-UHFFFAOYSA-N 1h-imidazol-1-ium;acetate Chemical class CC(O)=O.C1=CNC=N1 OFGDSGVGRWPQJQ-UHFFFAOYSA-N 0.000 description 1
- LYLDIIUFTYRPPK-UHFFFAOYSA-N 1h-imidazole-2-sulfonic acid Chemical class OS(=O)(=O)C1=NC=CN1 LYLDIIUFTYRPPK-UHFFFAOYSA-N 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- SZIFAVKTNFCBPC-UHFFFAOYSA-N 2-chloroethanol Chemical compound OCCCl SZIFAVKTNFCBPC-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 1
- 239000007806 chemical reaction intermediate Substances 0.000 description 1
- XENVCRGQTABGKY-ZHACJKMWSA-N chlorohydrin Chemical compound CC#CC#CC#CC#C\C=C\C(Cl)CO XENVCRGQTABGKY-ZHACJKMWSA-N 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- JGFBRKRYDCGYKD-UHFFFAOYSA-N dibutyl(oxo)tin Chemical compound CCCC[Sn](=O)CCCC JGFBRKRYDCGYKD-UHFFFAOYSA-N 0.000 description 1
- 238000007323 disproportionation reaction Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000006053 organic reaction Methods 0.000 description 1
- QIIPQYDSKRYMFG-UHFFFAOYSA-N phenyl hydrogen carbonate Chemical compound OC(=O)OC1=CC=CC=C1 QIIPQYDSKRYMFG-UHFFFAOYSA-N 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
- B01J31/0298—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature the ionic liquids being characterised by the counter-anions
-
- 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
- B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
- B01J31/0278—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre
- B01J31/0281—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre the nitrogen being a ring member
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
- B01J31/0278—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre
- B01J31/0285—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre also containing elements or functional groups covered by B01J31/0201 - B01J31/0274
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/40—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
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Abstract
本发明涉及一种酯交换法合成碳酸二苯酯的钛系双酸型离子液体催化剂及其制备方法与应用，本催化剂将Lewis酸性钛金属盐与功能化离子液体相结合；制备方法为将等摩尔量的烷基咪唑与带有功能基团的原料混合，反应温度60‑90℃，反应24h，用醋酸乙酯洗涤3‑4次，经旋蒸，80℃干燥6h后获得中间体I；N2保护下，向装有中间体I的反应器中加入TiCl4盐酸水溶液，加热搅拌溶解并冷凝回流，反应温度控制在50‑60℃，反应时间控制在12h，反应结束后用乙腈洗涤3‑4次，80℃干燥6h后分别获得不同种类的钛系双酸型离子液体催化剂。本发明解决酯交换法合成碳酸二苯酯所用传统催化剂的活性、稳定性、选择性不理想的问题。The invention relates to a titanium-based bis-acid type ionic liquid catalyst for synthesizing diphenyl carbonate by a transesterification method, and a preparation method and application thereof. The catalyst combines Lewis acid titanium metal salt and functionalized ionic liquid; the preparation method comprises the following steps: A molar amount of alkylimidazole is mixed with a raw material with a functional group, the reaction temperature is 60-90 ° C, the reaction is carried out for 24 h, washed with ethyl acetate 3-4 times, rotary-evaporated, and dried at 80 ° C for 6 h to obtain Intermediate I; Under the protection of N, add TiCl to the reactor equipped with the intermediate I hydrochloric acid aqueous solution, heat and stir to dissolve and condensate to reflux, the reaction temperature is controlled at 50-60 ℃, the reaction time is controlled at 12h, and the reaction is washed with acetonitrile 3 ‑4 times, and after drying at 80 °C for 6 h, different types of titanium-based bis-acid ionic liquid catalysts were obtained. The invention solves the problems of unsatisfactory activity, stability and selectivity of traditional catalysts used for synthesizing diphenyl carbonate by transesterification.
Description
Technical Field
The invention relates to the technical field of catalysts, and particularly relates to a titanium-based double-acid ionic liquid catalyst for synthesizing diphenyl carbonate by using an ester exchange method, and a preparation method and application thereof.
Technical Field
Polycarbonate (PC) is the only plastic with excellent transparency among five engineering plastics, has high transparency, strong toughness and excellent mechanical property, has certain flame retardant property, and has great demand in the field of infrastructure. The traditional preparation method of polycarbonate is phosgene method, but phosgene has huge toxicity, three wastes generated not only corrode equipment, but also pollute environment, the atom utilization rate is low, and the existing phosgene method for synthesizing polycarbonate also requires gradual upgrade.
Diphenyl carbonate (DPC) is an important organic reaction intermediate, and is used as a key raw material for synthesizing polycarbonate by substituting highly toxic phosgene and bisphenol A. The diphenyl carbonate synthesized by the ester exchange method does not produce three wastes, the atom utilization rate is up to 100 percent, and the source of the industrial chain is generated by the petrochemical industryPropylene oxide, a derivative of propylene, and the greenhouse gas CO2The final products thereof, polycarbonates and H2O, the three wastes are not generated at all, the prospect is broad, and the requirements of green economic development are completely met. However, the traditional catalysts used for synthesizing diphenyl carbonate by the ester exchange method, such as lewis metal salt, tetrabutyl titanate, dibutyltin oxide and the like, have unsatisfactory catalytic effects, so that the development of the catalyst with high activity, high stability and high selectivity is a key point.
Disclosure of Invention
The purpose of the invention is as follows:
the invention provides a titanium series double acid type ionic liquid catalyst, a preparation method and application thereof, and aims to solve the problems of unsatisfactory activity, stability and selectivity of a traditional catalyst for synthesizing diphenyl carbonate by an ester exchange method.
The technical scheme is as follows:
a titanium series double acid type ionic liquid catalyst combines Lewis acidic titanium metal salt and functional ionic liquid, and has the following structure:
R1＝CnH2n+1；
R2＝(CH2)3SO3H、CH2COO、(CH2)2OH；
X＝TiCl5。
further, the functional group of the functionalized ionic liquid is one of a sulfonic group, an acetic acid group or a hydroxyl group.
Further, the anion X is a coordination chelate formed by a coordination method with a cation-TiCl5。
A method for preparing a titanium series double acid type ionic liquid catalyst,
Further, the intermediate I in the step (2) is reacted with TiCl4The molar ratio is 1: 0.5-1.25.
Further, the intermediate I in the step (2) is reacted with TiCl4The molar ratio is 1:1.
An application of a titanium series double-acid type ionic liquid catalyst in preparing diphenyl carbonate.
The invention has the following characteristics:
(1) the titanium series double-acid ionic liquid catalyst prepared by the invention has high activity and good stability. The catalyst prepared by the invention has good catalytic activity for the ester exchange reaction of dimethyl carbonate and phenol, the total yield of diphenyl carbonate and methyl phenyl carbonate can reach more than 40%, and the selectivity of ester exchange can reach 70.01-99.91%.
(2) The double-acid ionic liquid catalyst has no saturated vapor pressure, so that the double-acid ionic liquid catalyst can be used for reaction under vacuum and high pressure conditions, is not easy to burn, explode or oxidize, and has better thermal stability and chemical stability.
(3) The titanium series double acid type ionic liquid catalyst of the invention is prepared by TiCl4The combination of high activity of the metal anion and high stability of the ionic liquid cation leads the metal anion and DMC to form a more stable transition state when participating in catalytic reaction, thereby being more beneficial to the reaction.
(4) During the transesterification reaction, TiCl4Under the action of macromolecular imidazole cationic group making TiCl4The electroabsorption capacity of the titanium atom in the DMC is obviously enhanced, the positron cloud of the cationic group of the macromolecular ionic liquid can also shift to the carbonyl carbon in the DMC, and the electron deficiency of the DMC carbonyl carbon is stronger and stronger under the synergistic action of anions and cationsIs beneficial to the attack of phenol oxygen anions, shortens the reaction time and improves the catalytic efficiency.
Drawings
FIG. 1 is a schematic diagram of catalyst synthesis;
FIG. 2 is a schematic diagram of the mechanism of diphenyl carbonate synthesis by titanium-based diacid ionic liquid catalyzed transesterification;
FIG. 3 is an infrared spectrum of a titanium-based bis-acid ionic liquid catalyst.
Detailed Description
The present invention will be described in further detail below with reference to examples. The features and advantages of the present invention will become more apparent from the description.
The ionic liquid has the characteristics of structural design, adjustable performance and the like and is applied to the field of catalysis, wherein researches on catalyzing and synthesizing ethylene carbonate and propylene carbonate are frequently repeated, but researches on catalyzing ester exchange reaction to synthesize diphenyl carbonate are not frequent. Therefore, based on the reaction mechanism of synthesizing diphenyl carbonate by ester exchange method and on the basis of traditional catalyst research, titanium series double-acid type ionic liquid is designed, so that the titanium series double-acid type ionic liquid has different acidity and specific functions, is used for catalyzing dimethyl carbonate and phenol to synthesize diphenyl carbonate, and overcomes the problems of low conversion rate, poor selectivity and the like of the traditional catalyst.
The invention uses the coordination method to combine TiCl with poor stability4The titanium series double-acid type ionic liquid catalyst is prepared by combining with the functional ionic liquid catalyst, on one hand, the high-activity TiCl is overcome4Poor stability, and on the other hand, the catalytic activity of the ionic liquid is further improved. The ionic liquid catalyst is characterized in that the acid site modification is carried out on the traditional ionic liquid structure, and then high-activity Lewis metal titanium is introduced to increase the acid sites, so that the mutual synergistic catalysis of double acid sites is realized, and the activity of the catalyst is further improved.
As shown in figure 1, the titanium series double acid type ionic liquid catalyst combines Lewis metal titanium and functionalized ionic liquid, and functional groups of the functionalized ionic liquid comprise: sulfonic acid group, acetic acid group, hydroxyl group, etc., and the anion X is formed by coordination with cationFormed coordination chelate-TiCl5. The modified functional cationic group can provide various states of acidity from strong acid to weak acid, so that the catalyst has the characteristic of adjustable acidity. The structure of the titanium series double-acid type ionic liquid catalyst is as follows:
R1＝CnH2n+1；
R2＝(CH2)3SO3H、CH2COO、(CH2)2OH；
X＝TiCl5。
a preparation method of a titanium series double-acid type ionic liquid catalyst for synthesizing diphenyl carbonate,
Mixing TiCl4Combining with functionalized ionic liquid, TiCl4The high activity of the catalyst is combined with the high stability of the functionalized ionic liquid, so that the high activity, high selectivity and high stability of the catalyst are realized, and the acidic group and the metal titanium have synergistic catalytic benefits and obtain better catalytic effect.
Firstly, weak acidic phenol in a solvent can be dehydrated to form phenoxide anions, meanwhile, the electron-withdrawing capability of a titanium atom is obviously enhanced under the action of macromolecular ionic liquid cationic groups and Lewis acidic titanium metal anions, and a positive electron cloud of the macromolecular ionic liquid cationic groups can also shift to DMC carbonyl carbon, so that the electron-deficiency property of the DMC carbonyl carbon is stronger under the synergistic action of anions and cations, the attack of the phenoxide anions is more facilitated, and an unstable transition state (1) is formed at the moment, and the transition state (1) is converted into a stable intermediate (2) under the action of the catalyst; at this time, under the action of phenol oxygen anions, carbonyl carbon C-O bonds are broken to form methyl phenyl carbonate and methanol, the methyl phenyl carbonate and phenol can generate diphenyl carbonate or two molecules of methyl phenyl carbonate can generate diphenyl carbonate through disproportionation reaction, and a catalyst can enter the next reaction step.
A titanium series double-acid type ionic liquid catalyst (infrared spectrum is shown in figure 3) is used for catalyzing the ester exchange reaction of synthesizing diphenyl carbonate by dimethyl carbonate and phenol as follows.
18.84g (0.2mol) of phenol is weighed, 36.03g (0.4mol) of dimethyl carbonate is weighed, mixed and added into a three-neck flask with a reflux condensing device, and N2Adding 0.5g of titanium series double acid type ionic liquid catalyst under protection, wherein the mass of the titanium series double acid type ionic liquid catalyst is about 1 percent of the total mass of reactants; stirring and heating the reaction system to 160-180 ℃, adjusting the reflux ratio to 3:1, cooling the reaction system to room temperature (25 ℃) after reacting for 7-9h, then carrying out reduced pressure distillation on the reaction liquid, detecting the purity of the product by using a gas chromatograph, and calculating the conversion rate, the selectivity and the yield.
Example 1
(1) Preparation of catalyst A intermediate I
Weighing a certain amount of N-methylimidazole in a reactor, slowly dropwise adding 1, 3-propane sultone with the molar weight equal to that of the N-methylimidazole at the speed of 10-100ml/s under reflux, controlling the reaction temperature at 60 ℃, after 24 hours of reaction, washing and filtering the reaction liquid with ethyl acetate for 3 times, and obtaining a white intermediate I after rotary evaporation and drying at 80 ℃ for 6 hours
(2) Preparation of catalyst A
N2Under protection, 0.1mol of intermediate I is heated to 50 ℃ and completely dissolved, and 0.1mol of TiCl is subsequently added4Refluxing and condensing hydrochloric acid aqueous solution at constant temperature, starting stirring, and reacting for 12h to obtain imidazole sulfonic acid series double-acid type ionic liquid catalyst A- [ (CH)2)3SO3H-mim]-TiCl5。
Example 2
(1) Preparation of catalyst B intermediate I
Weighing a certain amount of N-methylimidazole in a reactor, slowly dropwise adding chloroacetic acid with the molar quantity equal to that of the N-methylimidazole at the speed of 10-100ml/s under reflux, controlling the reaction temperature at 90 ℃, washing and filtering reaction liquid for 4 times by using diethyl ether after 24 hours of reaction, and obtaining a white intermediate I after rotary evaporation and drying at 80 ℃ for 6 hours.
(2) Preparation of catalyst B
N2Under protection, 0.1mol of intermediate I is heated to 55 ℃ and completely dissolved, and then 0.1mol of TiCl is added4Refluxing and condensing hydrochloric acid aqueous solution at constant temperature, starting stirring, and reacting for 12h to obtain imidazole acetic acid series double acid type ionic liquid catalyst B- [ CH2COO-mim]-TiCl5。
Example 3
(1) Preparation of catalyst C intermediate I
N2Under protection, weighing a certain amount of N-methylimidazole in a reactor, slowly dropwise adding chloroethanol with the same molar amount as the N-methylimidazole at the speed of 10-100ml/s under reflux, controlling the reaction temperature at 80 ℃, after 24 hours of reaction, washing and filtering the reaction liquid for 3 times by using acetonitrile, and obtaining a light yellow intermediate I after rotary evaporation and drying at 80 ℃ for 6 hours.
(2) Preparation of catalyst C
N2Under protection, 0.1mol of intermediate I is heated to 60 ℃ and completely dissolved, and 0.1mol of TiCl is subsequently added4Refluxing and condensing hydrochloric acid aqueous solution at constant temperature, starting stirring, and reacting for 12h to obtain the final productImidazole hydroxyl series double-acid type ionic liquid catalyst C- [ (CH)2)OH-mim]-TiCl5。
Example 4
Catalyst C and its catalytic Synthesis of Diphenyl carbonate the procedure of example 3 was followed, intermediate I being reacted with TiCl4The molar ratio of (A) was changed to 1:0.5, and the experimental results are shown in Table 2.
Example 5
Catalyst C and its catalytic Synthesis of Diphenyl carbonate the procedure of example 3 was followed, intermediate I being reacted with TiCl4The molar ratio of (A) was changed to 1:0.75, and the experimental results are shown in Table 2.
Example 6
Catalyst C and its catalytic Synthesis of Diphenyl carbonate the procedure of example 3 was followed, intermediate I being reacted with TiCl4The molar ratio of (A) was changed to 1:1.25, and the experimental results are shown in Table 2.
Using the samples of examples 1-3 as catalysts, the transesterification of dimethyl carbonate and phenol was catalyzed to synthesize diphenyl carbonate, and the catalytic effects are shown in Table 1, wherein MPC is monophenyl carbonate and DPC is diphenyl carbonate.
TABLE 1 titanium series bis-acid type ionic liquid catalyst Performance contrast
As can be seen from the data in table 1, the catalytic effect of the catalyst A, B with stronger acidity is significantly higher than that of the catalyst C with weak acidity, which indicates that the catalyst has better catalytic effect due to the increased acidity. Comparing the catalysts A and B, the acidity of the sulfonic acid group is higher than that of the acetic acid group, which shows that the strong acid has obvious inhibition effect on the side reaction, the selectivity is as high as 99.90%, but the acetic acid group has slightly poor selectivity, but the yield of the final product DPC is higher. The titanium ionic liquid containing sulfonic acid group has the best catalytic effect by combining the yields of MPC and DPC.
TABLE 2 different TiCl4Effect of the amount added on the catalytic Properties
As can be seen from Table 2, with TiCl4The addition of the catalyst is gradually increased, the reactivity is gradually increased, and the intermediate I and TiCl are gradually increased4At a molar ratio of 1:1, the conversion reaches a maximum, when the intermediate I and TiCl are present4When the molar ratio of (A) to (B) is 1:1.25, the conversion rate is rather lowered. The reason for this may be that the excessive titanium tetrachloride cannot form a stable coordination chelate with the intermediate I, and the excessive titanium tetrachloride overflows the reaction system with increasing temperature during the reaction to affect the participation thereof to provide the active site thereof.
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