CN104860810A - Organic titanium catalyst for exchange reaction of dimethyl carbonate and phenol ester - Google Patents
Organic titanium catalyst for exchange reaction of dimethyl carbonate and phenol ester Download PDFInfo
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Abstract
The invention relates to an organic titanium catalyst for an exchange reaction of dimethyl carbonate and phenol ester. The catalyst is composed of titanium oxyacelate formed through coordination of titanium and an acetate radical, and a solvothermal method is adopted to solve the catalyst and mainly solves the problems of difficult catalyst separation and recovery and low ester exchange activity. The organic titanium catalyst prepared through the method has a high catalysis effect on a reaction for synthesizing diphenyl carbonate through an ester exchange process, and allows the phenol conversion rate to reach 47.8% and the ester exchange selectivity to reach above 99.9%. The catalyst has the advantages of cheap and easily available raw materials, simple preparation method, insolubility in a reaction system, easy separation and recovery from the reaction system after the reaction, and repeated use.
Description
Technical field
The present invention discloses a kind of organotitanium for methylcarbonate and phenol ester exchange synthesizing diphenyl carbonate.
Background technology
Diphenyl carbonate is a kind of important chemical intermediate, by halogenation, nitrated, hydrolysis and the many organic intermediates of Reactive Synthesis and the macromolecular material such as ammonia solution, particularly can substitute the phosgene of hypertoxicity and the excellent polycarbonate of bisphenol-a reaction synthesis performance.The synthetic method of current diphenyl carbonate mainly contains phosgenation, oxidation of phenol carbonyl process and ester-interchange method.Traditional phosgenation is due to the hypertoxicity of phosgene, and a large amount of hydrochloric acid of by-product can etching apparatus, there is great potential safety hazard and environmental problem, progressively eliminate by novel method.Although oxidation of phenol carbonyl process atom utilization is higher, because expensive catalyst, catalytic efficiency are not high, is only limitted to the laboratory study stage, there is not yet industrialized report.The ester-interchange method of methylcarbonate and phenol is considered to the most promising non-phosgene synthesis diphenyl carbonate method at present.But methylcarbonate and phenol ester permutoid reaction are thermodynamics reversible reactions, the equilibrium constant is very little (is 3 × 10 during 453K
-4), product and separation and recovery of catalyst difficulty in reaction time long, homogeneous reaction.Therefore, exploitation efficient, environmental friendliness, returnable heterogeneous catalyst is of great significance this reaction tool.
Although homogeneous catalyst has higher catalytic activity in transesterification reaction, difficult separation and recycling, contaminate environment.Therefore investigator more pays close attention to the research of efficient, eco-friendly heterogeneous catalyst.In JP 09-241217 document, author investigation is containing the heterogeneous microporous catalyst of IVB race metal, and the yield of methyl benzol carbonate and diphenyl carbonate is respectively 11.5% and 0.2%; In document JP 09-241218, author also adopts titanium, iron to make mixed oxide catalyst with IIIB race metal respectively, and the yield of methyl benzol carbonate and diphenyl carbonate is respectively 13.6% and 8.5%.
Ono etc. (Fu Z H, OnoY, J Mol Catal A:Chem, 1997,118 (3): 293-299) have studied the catalytic performance of Engineering of Supported Metal Oxide Catalysts to methylcarbonate and phenol ester permutoid reaction, have investigated MoO respectively
3, MoO
2, V
2o
5, PbO, MgO, Nd
2o
3, TiO
2, ZrO
2, NiO and Y
2o
3isoreactivity component, found that MoO
3/ SiO
2catalytic activity the highest, the yield of methyl benzol carbonate and diphenyl carbonate is respectively 17.1% and 0.2%.Won Bae Kim and Jae SungLee (W.S.Kim, J.S.Lee, Catal Lett, 1999,59 (1): 83-88) respectively with gac, silicon-dioxide and titanium dioxide for carrier, have studied the catalytic performance of loading type molybdenum, titanium, vanadium, chromium, tungsten metal oxidic catalyzer, wherein TiO
2/ SiO
2activity the highest, in gas-phase reaction, phenol conversion is up to 37.2%, and the yield of methyl benzol carbonate and diphenyl carbonate is respectively 31.7% and 1.7%.
Zhang Shudong etc. (fine chemistry industry, 2005,22 (2): 115-117) adopt titaniferous micro porous molecular sieve Ti-beta catalyst methylcarbonate and phenol ester exchange synthesizing diphenyl carbonate to react, and phenol conversion is 20.2%.(the Mei F M such as Li Guangxing, Pei Z, LiG X, Organ Process Res & Devel, 2004,8 (3): 372-375) adopt Mg-Al this transesterification reaction hydrotalcite catalyzed, found that the total recovery of diphenyl carbonate and methyl benzol carbonate is 26.3%, transesterify selectivity is 82.4%.In document CN 1128664, Wang Yanji etc. are with plumbous oxide-zinc oxide complex metal oxides for catalyzer is used for the transesterification reaction of methylcarbonate and phenol, and the yield of diphenyl carbonate reaches as high as 45.6%, but transesterify selectivity is only 72%.In CN101412674A, be catalyzer with heteroatom mesopore molecular sieve, especially on titanium-containing meso-porous molecular sieve, phenol conversion reaches 45.1%, and transesterify selectivity reaches 99.9%.In CN101254460A, Chen Tong etc. are with TiO
2/ SiO
2for catalyzer, phenol conversion can reach 48.1%, and transesterify selectivity is more than 99.5%.But above-mentioned heterogeneous catalyst all can not be reused.
Summary of the invention
The object of the invention is to provide a kind of organotitanium for methylcarbonate and phenol ester exchange synthesizing diphenyl carbonate, and the acetic acid oxygen titanium that catalyzer is formed by titanium and acetate moiety coordination forms, and adopts solvent-thermal method preparation.The organotitanium of preparation makes the transesterification reaction of methylcarbonate and phenol have high conversion and highly selective, is insoluble to reaction solution, is easy to be separated from reaction system in reaction process, reusable.
Technical scheme of the present invention: invent a kind of organotitanium for methylcarbonate and phenol ester permutoid reaction, the acetic acid oxygen titanium that catalyzer is formed by titanium and acetate moiety coordination forms, prepared by solvent-thermal method, the mol ratio of titanium and water is 0.2-5, and the mol ratio of titanium and organic acid or acid anhydrides is 0.05-2.
The preparation method of organotitanium of the present invention is as follows:
(1) under stirring at room temperature condition, the organic solution of titaniferous is mixed with organic acid or acid anhydrides;
(2) in above-mentioned solution, add distilled water, stir 0.5 hour;
(3) mixed solution is transferred in reactor, in 50-200 DEG C of reaction 5 hours;
(4) after being cooled to room temperature, by suspension filtered, washing, dry, then in 100-600 DEG C of roasting 5 hours.
The organic solvent adopted in method can be ethanol, Virahol, normal hexane, hexanaphthene, methyl alcohol or chloroform.
The titanium source adopted in method can be butyl (tetra) titanate, isopropyl titanate, titanium ethanolate, metatitanic acid methyl esters, titanium tetrachloride, titanium tetrafluoride, titanous chloride, cyclopentadienyl titanium dichloride or titanyl sulfate.
The organic acid adopted in method or acid anhydrides can be acetic acid, diacetyl oxide, Mono Chloro Acetic Acid or trifluoroacetic acid.
The present invention has following features:
1, the organotitanium raw material prepared of the inventive method is cheap and easy to get, and preparation method is simple, does not pollute the environment.
2, the organotitanium prepared of the inventive method is in the reaction of methylcarbonate and phenyl ester ester exchange synthesizing diphenyl carbonate, and under relatively mild liquid-phase reaction condition, phenol conversion can up to 47.8%, and transesterify selectivity is greater than 99.9%.
3, the organotitanium that prepared by the inventive method is insoluble to reaction system, and is easy to be separated from reaction system, reusable.
Embodiment
Embodiment 1
With butyl (tetra) titanate (0.05mol) and diacetyl oxide raw material, 50ml hexanaphthene is solvent, and the mol ratio of titanium and water is 1, and the mol ratio of titanium and acetic acid is 0.2, and reactor, in 90 DEG C of reactions, obtains catalyst sample 1 after 200 DEG C of roastings.
Embodiment 2
With butyl (tetra) titanate (0.05mol) and trifluoroacetic acid raw material, hexanaphthene is solvent, and the mol ratio of titanium and water is 1, and the mol ratio of titanium and trifluoroacetic acid is 0.2, and reactor, in 90 DEG C of reactions, obtains catalyst sample 2 after 200 DEG C of roastings.
Embodiment 3
With titanyl sulfate (0.05mol) and diacetyl oxide raw material, hexanaphthene is solvent, and the mol ratio of titanium and water is 1, and the mol ratio of titanium and diacetyl oxide is 0.2, and reactor, in 90 DEG C of reactions, obtains catalyst sample 3 after 200 DEG C of roastings.
Embodiment 4
With butyl (tetra) titanate (0.05mol) and diacetyl oxide raw material, hexanaphthene is solvent, and the mol ratio of titanium and water is 1, and the mol ratio of titanium and diacetyl oxide is 0.2, and reactor, in 60 DEG C of reactions, obtains catalyst sample 4 after 200 DEG C of roastings.
Embodiment 5
With butyl (tetra) titanate (0.05mol) and diacetyl oxide raw material, hexanaphthene is solvent, and the mol ratio of titanium and water is 1, and the mol ratio of titanium and diacetyl oxide is 0.075, and reactor, in 90 DEG C of reactions, obtains catalyst sample 5 after 200 DEG C of roastings.
Embodiment 6
With butyl (tetra) titanate (0.05mol) and diacetyl oxide raw material, hexanaphthene is solvent, and the mol ratio of titanium and water is 1, and the mol ratio of titanium and diacetyl oxide is 0.20, and reactor, in 90 DEG C of reactions, obtains catalyst sample 6 after 300 DEG C of roastings.
Embodiment 7
With butyl (tetra) titanate (0.05mol) and diacetyl oxide raw material, hexanaphthene is solvent, and the mol ratio of titanium and water is 1.5, and the mol ratio of titanium and diacetyl oxide is 0.2, and reactor, in 90 DEG C of reactions, obtains catalyst sample 7 after 200 DEG C of roastings.
Embodiment 8
The sample prepared with embodiment 1-7 is catalyzer, carries out the transesterification reaction of methylcarbonate and phenol.
1, be connected with nitrogen airway and thermometer, constant pressure funnel and be equipped with in the there-necked flask of rectifying column, adding catalyzer 0.1 gram;
2, under passing into nitrogen, phenol 15.0 grams is added;
When 3, being heated to 175 DEG C, starting to drip methylcarbonate, and start timing, the total amount of methylcarbonate is 13.5ml, reacts 9 hours, is constantly steamed the azeotrope of methyl alcohol and methylcarbonate in reaction process by rectifying column;
4, azeotropic cut and the reaction solution containing principal product methyl benzol carbonate and diphenyl carbonate all use Agilent 7820A chromatographic, and quantitative with correction normalization method, its catalytic performance is as table 1.
The catalytic performance of table 1 sample 1-7
MPC-methyl benzol carbonate, DPC-diphenyl carbonate; The overall selectivity of transesterify selectivity-(MPC+DPC)
Embodiment 9
By reacted for embodiment 7 catalyst filtration, clean with DMC, in baking oven, 200 DEG C of dryings obtain catalyst sample 8, and transesterification reaction is with embodiment 8, and its catalytic performance is as table 2.
Embodiment 10
By reacted for embodiment 9 catalyst filtration, clean with DMC, in baking oven, 200 DEG C of dryings obtain catalyst sample 9, and transesterification reaction is with embodiment 8, and its catalytic performance is as table 2.
The repeat performance of table 2 catalyzer
MPC-methyl benzol carbonate, DPC-diphenyl carbonate; The overall selectivity of transesterify selectivity-(MPC+DPC)
As can be seen from Table 2, after catalyzer uses at three times, its phenol conversion remains on more than 45.0%, and transesterify selectivity remains on more than 99.9%, shows that catalyzer has good repeat performance.
Claims (5)
1., for the preparation of a method for the organotitanium of methylcarbonate and phenol ester exchange synthesizing diphenyl carbonate, it is characterized in that the acetic acid oxygen titanium that this catalyzer is formed by titanium and acetate moiety coordination forms, concrete preparation process is as follows:
(1) under stirring at room temperature condition, the organic solution of titaniferous is mixed with organic acid or acid anhydrides;
(2) in above-mentioned solution, add distilled water, stir 0.5 hour;
(3) mixed solution is transferred in reactor, in 50-200 DEG C of reaction 5 hours;
(4) after being cooled to room temperature, by suspension filtered, washing, dry, then 100-600 DEG C of roasting 5 hours.
2. method according to claim 1, is characterized in that organic solvent used is the one in ethanol, Virahol, normal hexane, hexanaphthene, methyl alcohol, chloroform.
3. method according to claim 1, is characterized in that titanium source used is the one in butyl (tetra) titanate, isopropyl titanate, titanium ethanolate, metatitanic acid methyl esters, titanium tetrachloride, titanium tetrafluoride, titanous chloride, cyclopentadienyl titanium dichloride, titanyl sulfate.
4. method according to claim 1, is characterized in that organic acid used or acid anhydrides are the one in acetic acid, diacetyl oxide, Mono Chloro Acetic Acid, trifluoroacetic acid.
5. method according to claim 1, is characterized in that the mol ratio of titanium and water is 0.2-5, and the mol ratio of titanium and organic acid or acid anhydrides is 0.05-2.
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105461636A (en) * | 2015-12-30 | 2016-04-06 | 安徽美诺华药物化学有限公司 | Synthetic method for rosuvastatin methyl ester |
| CN107876092A (en) * | 2017-11-24 | 2018-04-06 | 华东理工大学 | The high stability titanium catalyst of ester exchange carbonate synthesis benzene methyl and diphenyl carbonate |
| KR20180078904A (en) * | 2016-12-30 | 2018-07-10 | 롯데첨단소재(주) | Method for manufacturing aromatic carbonate |
| CN108976125A (en) * | 2017-06-02 | 2018-12-11 | 中国科学院大连化学物理研究所 | A kind of method of dimethyl carbonate and ethyl alcohol generation preparing methyl ethyl carbonate by ester exchanging reaction |
| CN109675622A (en) * | 2017-10-19 | 2019-04-26 | 中国石油化工股份有限公司 | It is used to prepare the preparation and application of the catalyst of diphenyl carbonate |
| CN110642718A (en) * | 2019-09-06 | 2020-01-03 | 湖北三宁碳磷基新材料产业技术研究院有限公司 | Heterogeneous catalyst for synthesizing diphenyl carbonate and preparation method thereof |
| CN110975852A (en) * | 2019-12-24 | 2020-04-10 | 济南大学 | Titanium dioxide nanocluster @ carbon sphere multilevel composite structure material and preparation method and application thereof |
| CN112960684A (en) * | 2021-04-07 | 2021-06-15 | 长兴谐源化工助剂有限公司 | Preparation method of nano calcium hydroxide powder for accelerating flue gas desulfurization |
| CN114011459A (en) * | 2021-11-16 | 2022-02-08 | 沈阳工业大学 | Titanium series double-acid type ionic liquid catalyst, preparation method and application |
| CN114671886A (en) * | 2022-05-07 | 2022-06-28 | 江苏极易新材料有限公司 | Synthetic method of antioxidant GA80 |
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| S DOEUFF ET AL: "Sol-gel synthesis and characterization of titanium oxo-acetate polymers", 《MAT.RES.BULL.》 * |
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105461636A (en) * | 2015-12-30 | 2016-04-06 | 安徽美诺华药物化学有限公司 | Synthetic method for rosuvastatin methyl ester |
| KR20180078904A (en) * | 2016-12-30 | 2018-07-10 | 롯데첨단소재(주) | Method for manufacturing aromatic carbonate |
| KR102014584B1 (en) | 2016-12-30 | 2019-08-26 | 롯데첨단소재(주) | Method for manufacturing aromatic carbonate |
| CN108976125A (en) * | 2017-06-02 | 2018-12-11 | 中国科学院大连化学物理研究所 | A kind of method of dimethyl carbonate and ethyl alcohol generation preparing methyl ethyl carbonate by ester exchanging reaction |
| CN109675622A (en) * | 2017-10-19 | 2019-04-26 | 中国石油化工股份有限公司 | It is used to prepare the preparation and application of the catalyst of diphenyl carbonate |
| CN107876092B (en) * | 2017-11-24 | 2023-01-10 | 华东理工大学 | Application of titanium catalyst with cyclic structure as reaction catalyst for synthesizing benzyl carbonate or diphenyl carbonate by ester exchange |
| CN107876092A (en) * | 2017-11-24 | 2018-04-06 | 华东理工大学 | The high stability titanium catalyst of ester exchange carbonate synthesis benzene methyl and diphenyl carbonate |
| CN110642718A (en) * | 2019-09-06 | 2020-01-03 | 湖北三宁碳磷基新材料产业技术研究院有限公司 | Heterogeneous catalyst for synthesizing diphenyl carbonate and preparation method thereof |
| CN110975852A (en) * | 2019-12-24 | 2020-04-10 | 济南大学 | Titanium dioxide nanocluster @ carbon sphere multilevel composite structure material and preparation method and application thereof |
| CN112960684A (en) * | 2021-04-07 | 2021-06-15 | 长兴谐源化工助剂有限公司 | Preparation method of nano calcium hydroxide powder for accelerating flue gas desulfurization |
| CN114011459A (en) * | 2021-11-16 | 2022-02-08 | 沈阳工业大学 | Titanium series double-acid type ionic liquid catalyst, preparation method and application |
| CN114011459B (en) * | 2021-11-16 | 2023-12-26 | 沈阳工业大学 | Titanium double-acid ionic liquid catalyst and preparation method and application thereof |
| CN114671886A (en) * | 2022-05-07 | 2022-06-28 | 江苏极易新材料有限公司 | Synthetic method of antioxidant GA80 |
| CN114671886B (en) * | 2022-05-07 | 2023-01-31 | 江苏极易新材料有限公司 | Synthetic method of antioxidant GA80 |
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