CN1562952A - Method for catalyzer synthesizing methyl-phenyl-oxalate and phenostal - Google Patents
Method for catalyzer synthesizing methyl-phenyl-oxalate and phenostal Download PDFInfo
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- CN1562952A CN1562952A CN 200410018842 CN200410018842A CN1562952A CN 1562952 A CN1562952 A CN 1562952A CN 200410018842 CN200410018842 CN 200410018842 CN 200410018842 A CN200410018842 A CN 200410018842A CN 1562952 A CN1562952 A CN 1562952A
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- catalyzer
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- phenyloxalate
- methyl phenyl
- barkite
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Abstract
In this invention process, dimethyl oxalate and phenol are used as raw materials with molar ratio of 1:20 to 20:1, reaction time 1-5 hours, temp. of 170-190 deg.C, pressure 0-1.0 MPa, under the presence of catalyst to proceed ester exchange. The characteristics are: catalyst being of supporting type molybdenum trioxide, and taking the ratio of total feed of 1/64 to 1/16. Advantages are: mild reaction condition, short reaction time, high yield, catalyst being easily separated from reaction system, easily to achieve continuous prodn.
Description
Technical field
The present invention relates to a kind of catalytic synthesis of methyl phenyl barkite and phenyloxalate method, belong to the methyl phenyl oxalate of the raw material for preparing diphenyl carbonate (DPC) and the processing method of phenyloxalate.
Background technology
With dimethyl oxalate and phenol is that feedstock production methyl phenyl oxalate and phenyloxalate are that all are the gordian technique of feedstock production diphenyl carbonate with dimethyl oxalate and phenol.The reactions steps of this gordian technique experience is as follows:
Or
With this gordian technique is that the dpc production technology of core occurred in the nineties, but development rapidly, particularly Ri Ben Ube company is devoted to the research of this respect always, and applied for many patents, as EP1013633A1, US5811573, CN1164529A, TW438765, US5834615, EP0832872A1, US5922827, EP0832910A2 etc.But in above-mentioned all patents, relating to the dimethyl oxalate is raw material prepares diphenyl carbonate synthesis by transesterify raw material, when being methyl phenyl oxalate or phenyloxalate, though used transesterification catalyst is brought in constant renewal in, variation is also perfect, can be basic metal, cadmium, zirconium, plumbous, iron, copper, zn cpds or organo-tin compound, aluminium, titanium, the organic acid compound of vanadium etc., but be the homogeneous catalyst that dissolves in reaction system, promptly all transesterification reactions that will carry out are homogeneous reaction, thereby above-mentioned all patented technologies have all used complicated separation system or equipment that catalyzer is separated with reaction product.
Summary of the invention
The object of the present invention is to provide the method for a kind of catalytic synthesis of methyl phenyl barkite and phenyloxalate.The selectivity height of the transformation efficiency of DMO and MPO, DPO not only in this procedure, and process save complex separations technology and equipment to catalyzer, and therefore, this technological process is simple.
For achieving the above object, the present invention is realized by following technical proposals, with dimethyl oxalate and phenol is raw material, at raw material raw materials components mole ratio DMO: phenol=1: 20～20: 1, reaction times is 1～5 hour, temperature of reaction is 170～190 ℃, reaction pressure is that 0～1.0MPa reaches under the heterogeneous catalysis condition, carry out transesterification reaction, raw material MPO or the DPO of DPC produced in preparation, it is characterized in that, the catalyzer that is adopted is the loading type molybdic oxide, the carrier of this catalyzer is a gac, Alpha-alumina or gama-alumina, silica gel, molecular sieve, zirconic one or both, the content of molybdenum is 1-20wt%, the weight ratio of catalyst consumption and total feed is 1/64～1/16.
The content of above-mentioned activity of such catalysts component molybdenum is 1-8wt%.
The carrier of above-mentioned catalyzer is a silica gel.
The part by weight of above-mentioned catalyst consumption and total feed is 1/35-1/30.
The invention has the advantages that, by adopting the loading type molybdenum trioxide catalyst, not only conversion of raw material and product selectivity all are significantly improved than the employing homogeneous catalyst, and have save separating technology process and equipment to the complexity of catalyzer and reaction system, have reduced production cost.
Come the present invention is further specified below by specific embodiment, but do not limit the present invention.
Embodiment
[embodiment 1]
The present invention is to be that the enforcement of feedstock production methyl phenyl oxalate and phenyloxalate processing method is investigated with dimethyl oxalate and phenol under the heterogeneous catalytic reaction condition, in 250 milliliters there-necked flask, carry out, the heating of heat collecting type induction stirring is furnished with thermometer, to show the reactive system temperature.The consumption of technical grade DMO is 0.1 mole, and the amount of chemical pure phenol is 0.5 mole, metal oxide supporting catalyst MoO
3/ SiO
2Consumption be 1.8 grams, under normal pressure, add, wherein the charge capacity of metal molybdenum is 1% (weight, down with).Stir and heat up, temperature of reaction is controlled at 180.0 ± 2 ℃, and the reaction times is 2 hours.The reaction equilibrium constant in each step of reaction (1)-(3) is all minimum, for breaking the restriction of thermodynamic(al)equilibrium, improve conversion of raw material, mouth is equipped with the reflux condensing tube of the thermostatical circulating water that feeds 70 ℃ (a little more than boiling points of methyl alcohol) in the flask, the methyl alcohol that reaction generates can constantly steam from the reaction mixture system, and collects overhead product in cold-trap.After reaction finished, the mode by suction filtration was to simple the separating of reaction mass and catalyzer, and promptly available gas-chromatography is analyzed reaction result.With the transformation efficiency of DMO, the selectivity of MPO, DPO is index, investigates reactivity worth.
The data processing of reaction result is calculated as follows:
[embodiment 2-9]
Change metal oxide supporting catalyst MoO
3/ SiO
2The charge capacity of middle molybdenum is respectively 1%, 2%, 4%, 6%, 8%, 10%, 12%, 14%, 16%, under other condition and embodiment 1 identical situation, carries out transesterification reaction, forms embodiment 2-9 respectively, investigates reaction result.
Table 1:MoO
3/ SiO
2Catalyst series catalyzed transesterification result (weight percentage)
The DMO selectivity, % yield, %
Embodiment molybdenum charge capacity, %
Transformation efficiency %
Methyl-phenoxide MPO DPO MPO DPO
1 1 54.6 0.4 74.2 25.4 40.5 13.9
2 2 43.7 0.8 80.9 18.3 35.4 8.0
3 4 44.4 0.8 84.3 14.9 37.4 6.6
4 6 41.8 0.8 87.1 12.1 36.4 5.1
5 8 54.4 0.8 81.7 17.5 44.4 9.5
6 10 39.0 0.9 88.2 10.9 34.4 4.2
7 12 33.3 1.3 88.4 10.3 29.4 3.4
8 14 42.5 1.1 89.3 9.6 37.9 4.1
9 16 51.8 1.0 83.4 15.6 43.2 8.1
[embodiment 10-13]
It is 4% SnO that catalyzer is used tin content respectively instead
2/ SiO
2Catalyzer, molybdenum content are 8% MoO
3/ MgO catalyzer, molybdenum content are 8% MoO
3/ Al
2O
3Catalyzer, molybdenum content are 8% MoO
3/ ZrO
2Catalyzer under other condition and embodiment 1 identical situation, carries out transesterification reaction, forms embodiment 10-13 respectively, investigates reaction result.
Table 2: different metal different carriers catalyzer transesterification reaction result (weight percentage)
The DMO selectivity, % yield, %
The embodiment catalyzer
Transformation efficiency %
Methyl-phenoxide MPO DPO MPO DPO
10 SnO
3/SiO
2 45.2 0.7 78.8 20.6 35.6 9.3
11 MoO
3/ZrO
2 53.7 0.7 85.9 8.4 46.1 4.5
12 MoO
3/MgO 60.2 20.9 64.5 12.6 38.8 7.6
13 MoO
3/Al
2O
3 62.7 35.4 53.9 5.9 33.7 3.7
[embodiment 14-18]
Use silica gel to do carrier, employing molybdenum content is 8% MoO
3/ SiO
2Catalyzer, and the reaction times carried out respectively 1 hour, 2 hours, 3 hours, 4 hours, 5 hours, under other condition and embodiment 1 identical situation, carry out transesterification reaction, investigate reaction result, form embodiment 14-18 respectively.
Table 3: embodiment 14-18 transesterification reaction result (weight percentage)
The DMO selectivity, % yield, %
The embodiment reaction times, hour
Transformation efficiency %
Methyl-phenoxide MPO DPO MPO DPO
14 1 35.9 0.7 91.1 8.2 32.7 2.9
15 2 54.4 0.8 81.7 17.5 44.4 9.5
16 3 55.6 1.6 81.1 17.4 45.1 9.6
17 4 67.8 1.8 72.7 25.5 49.3 17.3
18 5 65.0 2.1 75.3 17.5 48.9 11.3
From the foregoing description reaction result as can be seen, when making catalyzer with the loading type molybdic oxide in the processing method of the present invention, reaction result preferably can both be arranged.Wherein, for all active metal components, with SiO
2For the catalyzer of carrier has embodied higher selectivity; In the middle of different metals, load on SiO
2On the catalyzer of suitable Mo content shown the highest activity and selectivity; The different metal combined preparation that loads on the suitable carrier forms to such an extent that catalyzer also can demonstrate higher activity and purpose selectivity of product.
[Comparative Examples 1-4]
Adopt Zn (OAc) respectively
2, Ti (OC
4H
9)
4, SnOBu
2Make transesterification catalyst with dibutyl tin laurate, the loadings of catalyzer is 0.01mol, in identical reaction unit, under the identical operation and feed conditions, carries out the homogeneous phase transesterification reaction.The reaction result of Comparative Examples is as shown in table 4.
Table 4: Comparative Examples transesterification reaction result
The DMO selectivity, % yield, %
The Comparative Examples catalyzer
Transformation efficiency %
By product MPO DPO MPO DPO
1 Zn(OAc)
2 28.1 43.5 53.9 2.6 16.4 0.1
2 Ti(OC
4H
9)
4 92.5 76.6 20.6 2.8 19.0 2.6
3 SnOBu
2 25.7 6.7 80.8 12.5 20.8 3.2
4 dibutyl tin laurates 54.1 65.3 21.0 13.7 11.4 7.4
[Comparative Examples 5-8]
Catalyzer is used V instead
2O
5/ SiO
2Catalyst series, wherein the charge capacity of vanadium is respectively 1%, 4%, 8%, 12%, and under other condition and the embodiment 1 identical situation, carries out transesterification reaction, forms Comparative Examples 5-8 respectively, investigates reaction result.
Table 5:V
2O
5/ SiO
2Catalyst series catalyzed transesterification result (weight percentage)
The DMO selectivity, % yield, %
Embodiment vanadium charge capacity, %
Transformation efficiency %
Methyl-phenoxide MPO DPO MPO DPO
1 1 5.4 3.4 93.5 3.1 5.0 1.7
2 4 8.7 2.3 84.9 4.0 7.4 0.3
3 8 8.5 7.8 77.8 4.7 6.6 0.4
4 12 16.2 1.1 74.8 7.0 12.1 1.1
From embodiment and Comparative Examples as can be seen, be in the technology of feedstock production diphenyl carbonate with dimethyl oxalate and phenol, gordian technique wherein, be in the step of dimethyl oxalate and phenol ester exchange preparation methyl phenyl oxalate and phenyloxalate, if adopting the loading type molybdic oxide is catalyzer, the purpose product selectivity exceeds the selectivity in the Comparative Examples far away, and its activity is also higher, thereby higher purpose product yield is arranged.And if with traditional transesterification catalyst, as be widely used as organic zinc, organic titanium and the organic tin compound as catalyst of transesterification catalyst, except that Dibutyltin oxide, the purpose selectivity of product of other catalyzer is all extremely low; And Dibutyltin oxide is when making catalyzer, and except that costing an arm and a leg, Dibutyltin oxide decomposes voluntarily and forms homogeneous phase with system, outside catalyzer can not reclaim, also needs complicated separation system and equipment.
To sum up, with the loading type molybdic oxide is the transesterification reaction of passing through dimethyl oxalate and phenol of feature as transesterification catalyst, synthetic methyl phenyl oxalate and the phenyloxalate that is used to prepare diphenyl carbonate, for by being raw material with dimethyl oxalate and phenol, elder generation's synthesis of methyl phenyl barkite and phenyloxalate, by further preparing diphenyl carbonate, provide more favourable key core technology then with phenol ester exchange and/or direct de-carbonyl reaction.
The invention is not restricted to above embodiment, present patent application personnel can make various changes and distortion according to the present invention, only otherwise break away from spirit of the present invention, all should belong to scope of the present invention.
Claims (4)
1. the method for catalytic synthesis of methyl phenyl barkite and phenyloxalate, this method is a raw material with dimethyl oxalate and phenol, at raw material raw materials components mole ratio DMO: phenol=1: 20～20: 1, reaction times is 1～5 hour, temperature of reaction is 170～190 ℃, reaction pressure is that 0～1.0MPa reaches under the heterogeneous catalysis condition, carry out transesterification reaction, raw material MPO or the DPO of DPC produced in preparation, it is characterized in that: the catalyzer that is adopted is the loading type molybdic oxide, the carrier of this catalyzer is a gac, Alpha-alumina or gama-alumina, silica gel, molecular sieve, zirconic one or both, the content of molybdenum is 1-20wt%, and the weight ratio of catalyst consumption and total feed is 1/64～1/16.
2. according to the method for described catalytic synthesis of methyl phenyl barkite of claim 1 and phenyloxalate, it is characterized in that: the content of activity of such catalysts component molybdenum is 1-8wt%.
3. according to the method for described catalytic synthesis of methyl phenyl barkite of claim 1 and phenyloxalate, it is characterized in that: the carrier of catalyzer is a silica gel.
4. according to the method for described catalytic synthesis of methyl phenyl barkite of claim 1 and phenyloxalate, it is characterized in that: the part by weight of catalyst consumption and total feed is 1/35-1/30.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102408334A (en) * | 2010-09-21 | 2012-04-11 | 中国科学院福建物质结构研究所 | Method for synthesizing p-fluorophenyl acetate through ester exchange |
| CN102451698A (en) * | 2010-10-18 | 2012-05-16 | 上海焦化有限公司 | Catalyst for synthesis of methylphenylacetate, and preparation method thereof |
| CN103122061A (en) * | 2011-11-11 | 2013-05-29 | 中国科学院成都有机化学有限公司 | Method for directly preparing porous carbon material filling conducting polyester composite material |
| CN103524341A (en) * | 2013-08-26 | 2014-01-22 | 中建安装工程有限公司 | Application of Br phi nsted acid ion liquid to preparation of diphenyl oxalate |
-
2004
- 2004-04-08 CN CN 200410018842 patent/CN1562952A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102408334A (en) * | 2010-09-21 | 2012-04-11 | 中国科学院福建物质结构研究所 | Method for synthesizing p-fluorophenyl acetate through ester exchange |
| CN102451698A (en) * | 2010-10-18 | 2012-05-16 | 上海焦化有限公司 | Catalyst for synthesis of methylphenylacetate, and preparation method thereof |
| CN102451698B (en) * | 2010-10-18 | 2013-06-12 | 上海焦化有限公司 | Catalyst for synthesis of methylphenylacetate, and preparation method thereof |
| CN103122061A (en) * | 2011-11-11 | 2013-05-29 | 中国科学院成都有机化学有限公司 | Method for directly preparing porous carbon material filling conducting polyester composite material |
| CN103524341A (en) * | 2013-08-26 | 2014-01-22 | 中建安装工程有限公司 | Application of Br phi nsted acid ion liquid to preparation of diphenyl oxalate |
| CN103524341B (en) * | 2013-08-26 | 2014-12-24 | 中建安装工程有限公司 | Application of Br phi nsted acid ion liquid to preparation of diphenyl oxalate |
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