CN1412178A - Preparation method of methyl phenyl oxalate and phenostal - Google Patents
Preparation method of methyl phenyl oxalate and phenostal Download PDFInfo
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- CN1412178A CN1412178A CN02129214.0A CN02129214A CN1412178A CN 1412178 A CN1412178 A CN 1412178A CN 02129214 A CN02129214 A CN 02129214A CN 1412178 A CN1412178 A CN 1412178A
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Abstract
The present invention uses dimethyl oxalate and phenol as raw material, under the condition of that the raw material feeding mole ratio of dimethyl oxalate: phenol is 1:20-20:1, reaction time is 1-4 hr, reaction temp. is 170-190 deg.C, autoreaction pressure is 0-1.0 MPa and in the presence of catalyst the ester exchange reaction process is made, a it is characterized by that it catalyst is tin modified TS-1 molecular sieve, and the dose of said catalyst is 1/64-1/16 of total feeding amount.
Description
Technical field
The present invention relates to a kind of processing method that is used to prepare the raw material of diphenyl carbonate (DPC), specifically, the preparation method who relates to methyl phenyl oxalate (MPO) and phenyloxalate (DPO), be catalyzer with tin modification TS-1 molecular sieve in particular, by dimethyl oxalate (DMO) and phenol ester permutoid reaction, prepare methyl phenyl oxalate and phenyloxalate under the heterogeneous conditions.
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 of the system of dissolving in, promptly the transesterification reaction that will carry out to some extent be homogeneous reaction, thereby above-mentioned all patented technologies have all used complicated separation system or equipment that catalyzer is separated with reaction.
Summary of the invention
The object of the present invention is to provide a kind ofly with dimethyl oxalate and phenol, the raw material of diphenyl carbonate, the i.e. method of methyl phenyl oxalate and phenyloxalate are produced in preparation.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, is convenient to industrial applications.
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 1～4 hour, temperature of reaction is 170～190 ℃, spontaneous reaction pressure is under 0～1.0Mpa and the catalyzer existence 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 a tin modification TS-1 molecular sieve, catalyst consumption is 1/64～1/16 of total feed by weight percentage.
In the above-mentioned tin modification TS-1 molecular sieve catalyst, the Ti constituent content is preferably greater than 1.0% (weight).
In the above-mentioned tin modification TS-1 molecular sieve catalyst, the Sn constituent content is preferably greater than 0.5% (weight).
Above-mentioned catalyst consumption is preferably 1/35～1/30 (weight) with the ratio of total feed by weight percentage.
The invention has the advantages that, by adopting tin modification TS-1 molecular sieve catalyst, not only conversion of raw material and product selectivity all have and adopt homogeneous catalyst significantly to improve, and save separating technology process and equipment to the complexity of catalyzer and reaction system, 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, is 1.8 grams through the TS-1 of tin modification molecular sieve (Ti content 2.5%, down together) catalyst consumption, and the tin charge capacity is 1%.Add under normal pressure, 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]
The charge capacity that catalyzer is used Sn instead is 2% (weight) TS-1 molecular sieve, under other condition and embodiment 1 identical situation, carries out transesterification reaction, investigates reaction result.[embodiment 3]
The charge capacity that catalyzer is used Sn instead is 4% (weight) TS-1 molecular sieve, under other condition and embodiment 1 identical situation, carries out transesterification reaction, investigates reaction result.[embodiment 4]
The charge capacity that catalyzer is used Sn instead is 8% (weight) TS-1 molecular sieve, under other condition and embodiment 1 identical situation, carries out transesterification reaction, investigates reaction result.[embodiment 5-7]
The TS-1 molecular sieve of catalyzer without the Sn modification, the reaction times was respectively 1 hour, 3 hours, 4 hours, and is identical in other condition and embodiment 1, carries out transesterification reaction, forms embodiment 5, embodiment 6 and embodiment 7 respectively.
Reaction result is shown in Table 1.
Table 1: embodiment transesterification reaction result (weight percent)
DMO selectivity during the tin load-reaction, % yield, %
Embodiment
Amount; Between %; Hour conversion ratio, % methyl phenyl ethers anisole MPO DPO MPO DPO1 12 34.6 1.0 82.3 16.8 28.5 5.82 22 50.3 0.8 69.3 29.9 34.9 15.13 42 28.7 2.7 76.7 20.6 22.0 5.94 82 24.6 2.0 80.7 17.3 19.8 4.05 01 24.1 1.5 92.6 5.9 22.3 1.46 02 29.2 0.7 89.9 9.4 26.2 2.77 04 30.0 0.7 87.8 11.5 26.3 3.4
From above-mentioned reaction result as can be seen, when being transesterification catalyst with tin modification TS-1 molecular sieve in the processing method of the present invention, can obtain high purpose product selectivity, and when the charge capacity of Sn is fit to, have quite high feed stock conversion.Simultaneously, from embodiment 5-7 as can be seen, though the prolongation in reaction times helps promoting the carrying out that react, improve conversion of raw material and improve the yield of product, but the space-time yield of device purpose product the reaction times be 2 hours better, so consider that from the device economic performance reaction contact time is chosen as 2 hours.[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 identical operations and the feed conditions, carries out the homogeneous phase transesterification reaction.The reaction result of Comparative Examples is as shown in table 2.
Table 2: Comparative Examples transesterification reaction result
The DMO selectivity, % yield, % Comparative Examples catalyzer
Transformation efficiency % by product MPO DPO MPO DPO1 Zn (OAc)
228.1 43.5 53.9 2.6 16.4 0.12 Ti (OC
4H
9)
492.5 76.6 20.6 2.8 19.0 2.63 SnOBu
225.7 6.7 80.8 12.5 20.8 3.24 dibutyl tin laurates 54.1 65.3 21.0 13.7 11.4 7.4
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 tin modification TS-1 molecular sieve 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, from Comparative Examples 1～4 as can be seen, 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 tin modification TS-1 molecular sieve transesterification catalyst is the transesterification reaction of passing through dimethyl oxalate and phenol of feature, 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 preparation method of methyl phenyl oxalate and phenyloxalate, be to be raw material with dimethyl oxalate and phenol, at raw material raw materials components mole ratio dimethyl oxalate: phenol=1: 20～20: 1, reaction times is 1～4 hour, temperature of reaction is 170～190 ℃, spontaneous reaction pressure is under 0～1.0Mpa and the catalyzer existence condition, carry out the process of transesterification reaction, it is characterized in that, the catalyzer that is adopted is a tin modification TS-1 molecular sieve, and catalyst consumption is 1/64～1/16 of total feed by weight percentage.
2. according to the preparation method of described methyl phenyl oxalate of claim 1 and phenyloxalate, it is characterized in that the Ti constituent content is preferably greater than 1.0% (weight) in the above-mentioned tin modification TS-1 molecular sieve catalyst.
3. according to the preparation method of described methyl phenyl oxalate of claim 1 and phenyloxalate, it is characterized in that the Sn constituent content is preferably greater than 0.5% (weight) in the above-mentioned tin modification TS-1 molecular sieve catalyst.
4. according to the preparation method of described methyl phenyl oxalate of claim 1 and phenyloxalate, it is characterized in that the ratio of above-mentioned catalyst consumption and total feed is preferably 1/35～1/30 (weight).
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| CNB021292140A CN1164559C (en) | 2002-08-28 | 2002-08-28 | Preparation method of methyl phenyl oxalate and phenostal |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN103801393A (en) * | 2012-11-07 | 2014-05-21 | 中国石油化工股份有限公司 | Preparation method of catalyst for phenol preparation by benzene hydroxylation |
-
2002
- 2002-08-28 CN CNB021292140A patent/CN1164559C/en not_active Expired - Lifetime
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103801393A (en) * | 2012-11-07 | 2014-05-21 | 中国石油化工股份有限公司 | Preparation method of catalyst for phenol preparation by benzene hydroxylation |
| CN103801393B (en) * | 2012-11-07 | 2016-02-03 | 中国石油化工股份有限公司 | A kind of preparation method of benzene hydroxylation phenol catalyst |
| 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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| CN1164559C (en) | 2004-09-01 |
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