CN110128274A - A kind of method of dimethyl carbonate ester exchange synthesizing diphenyl carbonate - Google Patents
A kind of method of dimethyl carbonate ester exchange synthesizing diphenyl carbonate Download PDFInfo
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- CN110128274A CN110128274A CN201910453461.7A CN201910453461A CN110128274A CN 110128274 A CN110128274 A CN 110128274A CN 201910453461 A CN201910453461 A CN 201910453461A CN 110128274 A CN110128274 A CN 110128274A
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- silicon oxide
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- mesopore silicon
- bismuth silicate
- dimethyl carbonate
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/18—Arsenic, antimony or bismuth
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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
- C07C68/065—Preparation of esters of carbonic or haloformic acids from organic carbonates from alkylene carbonates
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Abstract
The present invention relates to a kind of methods of dimethyl carbonate ester exchange synthesizing diphenyl carbonate, this method is using dimethyl carbonate and phenol as raw material, it is catalyst that mesopore silicon oxide, which loads bismuth silicate, the problems such as mesopore silicon oxide load bismuth silicate as catalyst is made of mesopore silicon oxide carrier and active component bismuth silicate, mainly solves separation and recovery of catalyst difficulty, cannot reuse.Mesopore silicon oxide used in the method for the present invention loads bismuth silicate diphenyl carbonate synthesis activity height, and selectivity is good, and for phenol conversion up to 42%, transesterification is selective up to 99.5%.It is a kind of heterogeneous catalyst that mesopore silicon oxide used in this method, which loads bismuth silicate, does not dissolve in reaction system, easily separates from system after reaction, reusable, is simply roasted and i.e. renewable is restored to initial activity.
Description
Technical field
The present invention relates to a kind of methods of dimethyl carbonate ester exchange synthesizing diphenyl carbonate.
Background technique
Diphenyl carbonate (diphenyl carbonate, abbreviation DPC) is a kind of important chemical intermediate, is mainly used for
In plastics industry, a most important purposes is exactly and bisphenol-A polycondensation reaction polycarbonate synthesis (PC).
The non-phosgene synthetic method of DPC mainly has oxidation carbonylation method and ester-interchange method.Wherein, oxidation carbonylation method with CO,
O2It is raw material with phenol, directly synthesizes DPC under the action of catalyst, the catalyst system that this method uses is complicated, and it is expensive,
The yield and selectivity of DPC be not high, and reaction condition more harshness limits its industrial applications.Dimethyl carbonate (DMC) and benzene
Phenolic ester exchange synthesis DPC is the non-phosgene DPC synthetic route for most having industrial prospect.It generallys use organotin and organic titanium is
Homogeneous catalyst.
In patent document CN1698960A, princes and dukes should be waited using luxuriant titanium class catalyst, and phenol conversion is up to 43%-
52%；Du etc. (Du Z P, Xiao Y H.Catal Commun, 2008,9:239-242) has studied urging for Dibutyltin oxide
Change performance, by adding Cu2O, the conversion ratio of dimethyl carbonate is up to 50.8%.Homogeneous catalyst activity is high, and selectivity is good.But
In the presence of being not easy to separate and recover from reaction system, cause product separation difficult.
Currently, the heterogeneous catalyst of dimethyl carbonate and phenol ester exchange synthesizing diphenyl carbonate is primarily present reuse
The bad problem of effect.Tong etc. (Tong D S, Yao J.J Mol Cal A:Chem, 2007,268:120-126) has studied
Catalytic performance of the metal oxide catalyst in dimethyl carbonate and phenol ester exchange reaction, the active component of investigation have
MoO3、V2O5、CuO、Nb2O5、Cr2O3、TiO2、Sb2O3Deng wherein V2O5Activity preferably, methyl benzol carbonate (MPC) and carbon
The yield of diphenyl phthalate is respectively 21.6% and 12.1%；Li et al. (Li Z H, Cheng B.J Mol Cal A:Chem, 2008,
289:100-105) by MoO3Load to SiO2、MCM-41、Al2O3、ZrO2On carrier, work as MoO3When loading on MCM-41, MPC
It is greatly improved with DPC yield, MPC and DPC yield is respectively 2.6% and 39.6%；(Ge Xin, Lee is green to wait chemistry quietly to Ge etc.
Journal, 2011,69:2328-2334) TiO is prepared for as carrier using the modified carbon nanotube of cetyl trimethylammonium bromide2/
CNT catalyst, wherein titanium dioxide exists in the form of unbodied.The phenol conversion of the catalyst is used up to 45.7%
35.2% is reduced to after four times；Wang etc. (Wang S L, Tang R Z.Chem Eng Sci, 2015,138:93-98) is used
The TiO of sol-gal process preparation2Phosphomolybdic acid catalyst is loaded, phenol conversion is reused 4 times up to 50.4%, phenol conversion
Rate is down to 29.5%.(Zhang Y Z, Xiao Z L.Res Chem Intermed, 2016,42 (9): 7213- such as Zhang
7222) the immobilized organotin catalysts Sn-SBA-15 of silica is prepared for using silanization method, phenol conversion up to 50.4%,
Reusability is investigated with 0.5g catalyst, is reused 5 times, phenol conversion will be down to 35% by 41.2%.
In document CN1803282A, using vanadium-copper composite oxides as catalyst, transesterification product yield is up to 30%.?
In CN191423476A, use heteropoly compound for catalyst, up to 30%, transesterification selectively reaches the yield of diphenyl carbonate
99.9%.In CN201010263740, Chen Tong etc. carries out transesterification conjunction by catalyst of carbon nanotube loaded titanium dioxide
At the reaction of diphenyl carbonate, the total recovery of diphenyl carbonate and alkylphenyl carbonate is up to 49.0%.
Summary of the invention
The purpose of the present invention is to provide a kind of methods of dimethyl carbonate and phenol ester exchange synthesizing diphenyl carbonate.It should
Mesopore silicon oxide used in method loads bismuth silicate using mesopore silicon oxide as carrier, and bismuth silicate is active component.Mesopore silicon oxide carries
Body can be inorganic mesoporous silicon, be also possible to organic mesopore silicon oxide, bismuth silicon mol ratio is 0.1-0.4, at 250 DEG C -500 DEG C
It is used after reason.
The beneficial effects of the present invention are:
(1) the method for the present invention is high-efficient.The method of the present invention uses mesopore silicon oxide load bismuth silicate to synthesize carbon for catalyst
Diphenyl phthalate effect is good, and phenol conversion is up to 41.5%, transesterification selectivity 99.5%.
(2) catalyst used in the method for the present invention is easily isolated and recycled.The load of mesopore silicon oxide used in the method for the present invention
Bismuth silicate is heterogeneous catalyst, and utilization can be separated and recovered from system by filtering.
(3) catalyst used in the method for the present invention is reusable.The mesopore silicon oxide that the present invention uses loads bismuth silicate
Catalyst is reusable, and using three times, activity slightly decline is fired i.e. renewable, recovery to initial activity after processing.
Specific embodiment
It in order to make the object, technical scheme and advantages of the embodiment of the invention clearer, below will be in the embodiment of the present invention
Technical solution be clearly and completely described.The person that is not specified actual conditions in embodiment, according to normal conditions or manufacturer builds
The condition of view carries out.Reagents or instruments used without specified manufacturer is the conventional production that can be obtained by commercially available purchase
Product.
Feature and performance of the invention are described in further detail with reference to embodiments.
Embodiment 1
Bismuth nitrate and inorganic mesoporous silica are mixed in the ratio of bismuth silicon mol ratio 0.1:1, grind after 60min 200 DEG C
Roasting 6h obtains inorganic mesoporous silica supported silicic acid bismuth catalyst, is denoted as sample 1.
Embodiment 2
Bismuth nitrate and inorganic mesoporous silica are dissolved in a certain amount of dehydrated alcohol by bismuth silicon mol ratio 0.3:1, stirred
Solvent is evaporated off in back spin for 24 hours, and obtained solid roasts 2h at 400 DEG C and obtains inorganic mesoporous silica supported silicic acid bismuth catalyst,
It is denoted as sample 2.
Embodiment 3
Bismuth nitrate and order mesoporous organosilicon are mixed in the ratio of bismuth silicon mol ratio 0.1:1, grind after 15min 300 DEG C
Roasting 5h obtains organic mesopore silicon oxide load silicic acid bismuth catalyst, is denoted as sample 3.
Embodiment 4
Bismuth nitrate and order mesoporous organosilicon are mixed in the ratio of bismuth silicon mol ratio 0.3:1, grind after 20min 400 DEG C
Roasting 4h obtains organic mesopore silicon oxide load silicic acid bismuth catalyst, is denoted as sample 4.
Embodiment 5
Bismuth nitrate and order mesoporous organosilicon are dissolved in a certain amount of dehydrated alcohol by bismuth silicon mol ratio 0.2:1, stirred
Solvent is evaporated off in 12h back spin, and obtained solid roasts 1h at 500 DEG C and obtains organic mesopore silicon oxide load silicic acid bismuth catalyst,
It is denoted as sample 5.
Embodiment 6
A kind of method for present embodiments providing dimethyl carbonate ester exchange synthesizing diphenyl carbonate, comprising: led being connected with
Tracheae, thermometer, constant pressure funnel and rectifying column three-necked flask in be added 0.6g sample 1, sample 2, sample 3, sample 4 or
Sample 5 is passed through nitrogen and 15g phenol is added, and when being heated to 175 DEG C, starts that DMC is added dropwise, the DMC total amount of addition is 14ml.From
Start that DMC clock reaction 9h is added dropwise, product gas chromatographic analysis after reaction corrects normalizing standard measure, as a result such as 1 institute of table
Show:
The catalytic performance of 1 mesoporous silicon of table load silicic acid bismuth catalyst
By table 1 the result shows that, using catalyst provided in an embodiment of the present invention (mesopore silicon oxide load bismuth silicate), phenol
Conversion ratio is up to 41.5%, and transesterification selectivity is up to 99.5%.
Embodiment 7
Sample 4 after embodiment 4 is reacted filters, and is washed with DMC, 120 DEG C of dryings obtain sample 4-1, according to embodiment
6 the step of, carries out ester exchange reaction.
Embodiment 8
Sample 4-1 filtering after embodiment 7 is reacted, is washed, 120 DEG C of dryings obtain sample 4-2, according to implementation with DMC
The step of example 6, carries out ester exchange reaction.
Embodiment 9
Sample 4-2 filtering after embodiment 8 is reacted, is washed, 120 DEG C of dryings obtain sample 4-3, according to implementation with DMC
The step of example 6, carries out ester exchange reaction.
Embodiment 10
Sample 4-3 filtering after embodiment 9 is reacted, is washed, 120 DEG C of dryings, 400 DEG C of roastings obtain sample 4- with DMC
4, ester exchange reaction is carried out according to the step of embodiment 6.
The reusability of 2 mesoporous silicon of table load silicic acid bismuth catalyst
By table 2, the result shows that, catalyst (mesopore silicon oxide load bismuth silicate) provided in an embodiment of the present invention not only can be with
It reuses, and reuse effect is good, reuse does not influence transesterification selectivity, although and active after a number of uses
Slightly decline, but it is fired i.e. renewable, recovery to initial activity after processing.
In conclusion using the method for dimethyl carbonate ester exchange synthesizing diphenyl carbonate provided by the invention, using this
Method, phenol conversion is up to 41.5%, and transesterification selectivity is up to 99.5%；And the reusable effect of catalyst is good.
The foregoing is only a preferred embodiment of the present invention, is not intended to restrict the invention, for the skill of this field
For art personnel, the invention may be variously modified and varied.All within the spirits and principles of the present invention, made any to repair
Change, equivalent replacement, improvement etc., should all be included in the protection scope of the present invention.
Claims (3)
1. a kind of method of dimethyl carbonate ester exchange synthesizing diphenyl carbonate, it is characterised in that be with dimethyl carbonate and phenol
Raw material, it is heterogeneous catalyst that mesopore silicon oxide, which loads bismuth silicate,.
2. according to the method described in claim 1, it is characterized in that mesopore silicon oxide used loads bismuth silicate by mesopore silicon oxide
Carrier and active component bismuth silicate composition, bismuth silicon mol ratio are 0.1-0.4；Mesopore silicon oxide carrier can be inorganic mesoporous oxidation
Silicon is also possible to organic mesopore silicon oxide.
3. according to the method described in claim 1, it is characterized in that mesopore silicon oxide loads bismuth silicate at 200-500 DEG C of roasting
It is used after reason.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110204444A (en) * | 2019-07-02 | 2019-09-06 | 滕州京腾鑫汇新材料科技有限公司 | Synthesis method of dimethyl carbonate |
| CN111589471A (en) * | 2020-05-20 | 2020-08-28 | 湖北三宁碳磷基新材料产业技术研究院有限公司 | Solid-supported metal organic catalyst for disproportionation reaction and preparation method thereof |
| US11123715B2 (en) * | 2019-11-22 | 2021-09-21 | King Fahd University Of Petroleum And Minerals | Mesoporous composite catalysts containing bismuth silicate and transition metal oxide |
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| CN1562957A (en) * | 2004-04-03 | 2005-01-12 | 宁夏大学 | Method for synthesizing methyl propyl carbonate and dipropyl carbonate through catalysis in gas phase and solid phase |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US11123715B2 (en) * | 2019-11-22 | 2021-09-21 | King Fahd University Of Petroleum And Minerals | Mesoporous composite catalysts containing bismuth silicate and transition metal oxide |
| CN111589471A (en) * | 2020-05-20 | 2020-08-28 | 湖北三宁碳磷基新材料产业技术研究院有限公司 | Solid-supported metal organic catalyst for disproportionation reaction and preparation method thereof |
| CN111589471B (en) * | 2020-05-20 | 2023-05-02 | 湖北三宁碳磷基新材料产业技术研究院有限公司 | Immobilized metal organic catalyst for disproportionation reaction and preparation method thereof |
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