CN109675622A - It is used to prepare the preparation and application of the catalyst of diphenyl carbonate - Google Patents
It is used to prepare the preparation and application of the catalyst of diphenyl carbonate Download PDFInfo
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- CN109675622A CN109675622A CN201710976942.7A CN201710976942A CN109675622A CN 109675622 A CN109675622 A CN 109675622A CN 201710976942 A CN201710976942 A CN 201710976942A CN 109675622 A CN109675622 A CN 109675622A
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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
- B01J31/0272—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing elements other than those covered by B01J31/0201 - B01J31/0255
- B01J31/0275—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing elements other than those covered by B01J31/0201 - B01J31/0255 also containing elements or functional groups covered by B01J31/0201 - B01J31/0269
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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
Abstract
The present invention relates to a kind of catalyst and preparation method thereof for preparing diphenyl carbonate for dimethyl carbonate and phenol ester exchange reaction, mainly solve the problems, such as that the activity of heterogeneous catalysis present in conventional art is lower and is easy to run off.Active component is immobilized on carrier by this catalyst by chemical bond, and catalyst is support type monodisperse titanium catalyst system catalyst, including carrier and titanate esters group, and the carrier is substrate, and the titanate esters group is activated centre.The technical solution of catalyst preferably solves phenol and dimethyl carbonate ester exchange synthesizing diphenyl carbonate reacting middle catalyst losing issue, can be used in the industrial production of diphenyl carbonate.
Description
Technical field
The present invention relates to one kind to prepare dipheryl carbonate ester catalyst with dimethyl carbonate transesterification for phenol, prepares and answers
With.
Background technique
Diphenyl carbonate (DPC) is the raw material that non-phosgene prepares polycarbonate, and traditional preparation methods are phosgenations, by
Environment is limited with keeping the safety in production potentially hazardous by policy in hypertoxic phosgene.By phenol (PhOH) and dimethyl carbonate
(DMC) synthesis of diphenyl carbonate by ester exchange reaction technique is carried out under the action of catalyst, is avoided using hypertoxic raw material phosgene, it is main
By-product carbinol is wanted also and can be recycled the synthesis for starting material dimethyl carbonate, is the friendly process road for most having industrial prospect
Line.
Currently, the ester exchange synthesizing diphenyl carbonate of dimethyl carbonate and phenol is mostly used homogeneous catalyst.[the H.Niu such as Niu
Et al., J.Mol.Catal.A 235 (2005) 240] use Cp2TiCl2As catalyst, under optimal conditions, phenol
Conversion ratio is 46.8%, and the selectivity of diphenyl carbonate is 54.9%.[H.Lee the et al., Catal.Today 87 such as H.Lee
(2003) 139] Bu is used2SnO is as catalyst, CF3SO3H is as auxiliary agent, with optimal conditions, the conversion ratio of dimethyl carbonate
It is 58.5%, the yield of diphenyl carbonate is 18.3%.There are many more using titanium system homogeneous catalyst process also achieve compared with
Good effect [D.Andre et al., US20100010252；P.Cao et al.,J.Mol.Catal.(China)24
(2010)492；J.Gao,Chin.J.Catal.22(2001)405].There is difficult ask is separated with product for homogeneous catalyst
Topic, is not easy to reuse, therefore heterogeneous catalysis is the Main way of the exploitation in future.Although heterogeneous catalysis and product
Separation is easy, and conversion ratio and selectivity can substantially achieve the effect that homogeneous catalyst, but catalyst is easy inactivation, it is difficult to weight
Multiple use is its main problem.W.Zhou etc. [W.Zhou, et al, Appl.Catal.A, 260 (2004) 19-24] is prepared for
Pb-Zn bi-metal oxide catalyst, in the ester exchange reaction of DMC and PhOH, the conversion ratio of PhOH and the yield difference of DPC
For 64.6% and 45.6%, but after catalyst is reused 4 times, the yield of DPC falls to 15% or so, the master of catalyst inactivation
It wants the reason is that Pb3O4The disappearance of crystal phase and the loss of Pb.[Y.T.Kim, the et al., Appl.Catal.A 356 such as Y.T.Kim
(2009) 211-215] MoO will be loaded3/SiO2And TiO2/SiO2Catalyst is for finding in the ester exchange reaction of DMC and PhOH
After catalyst is reused 5 times, the activity of catalyst has dropped 95% and 66% respectively.Author by deactivation cause be attributed to Mo,
The loss of Ti species, in the case where pyroreaction, such case is particularly acute.R.Tang etc. [R.Tang, et al.,
Chin.J.Catal., 35 (2014) 457-461] in order to avoid the loss of active constituent Ti, it is prepared for SiO2The TiO of cladding2Core
Shell catalyst.
Summary of the invention
It is active, selective low that the technical problem to be solved by the present invention is to heterogeneous catalysis present in conventional art
Problem, provides a kind of new catalyst that diphenyl carbonate is prepared for dimethyl carbonate and phenol, which has catalysis
Agent is low-consuming, active high and the characteristics of not easily run off.
In order to solve the above technical problems, The technical solution adopted by the invention is as follows:
A kind of catalyst for diphenyl carbonate preparation, the catalyst are that support type monodisperse titanium catalyst system is urged
Agent, including carrier and titanate esters group, the carrier are substrate, and the titanate esters group is activated centre, structural formula are as follows:
Wherein R1, R2, R3, R4 are alkyl or aromatic radical.
In above-mentioned technical proposal, it is preferable that the carrier is inert carrier.
In above-mentioned technical proposal, it is preferable that the content of titanium is 0.1~20% in the catalyst；It more preferably, is 1-
5%.
In above-mentioned technical proposal, it is preferable that described R2, R3, R4 are alkyl or aromatic radical；More preferably, described R2, R3
For methyl, ethyl, propyl；R4 is hydroxyl, methyl.
The present invention also provides a kind of preparation methods of above-mentioned catalyst, include the following steps:
1) one step of carrier surface is modified: carrier is added in solvent, after heating, amino silicone is added, it is cold after reflux
But, it filters, washing；
2) two step of carrier surface is modified: configuration hydroxycarboxylic acid dissolution is added in 1), heats, filter, washs, dry；
3) carrier titanium is handled: titanium precursors being dissolved in solvent, are added carrier is processed in 2), benzene is added in heating
It after phenol, filters, washs, it is dry, obtain catalyst.
In above-mentioned technical proposal, it is preferable that the heating time is 1~48h.
In above-mentioned technical proposal, preferably amino silicone is aminopropyl trimethoxysilane or aminopropyl-triethoxy silicon
Alkane.
In above-mentioned technical proposal, it is preferable that the amount of the carrier, amino silicone, hydroxycarboxylic acid, titanium precursors molar ratio
Example range is carrier: amino silicone: hydroxycarboxylic acid: titanium precursors 1:0.01~10:0.01~10:0.01~10.
In above-mentioned technical proposal, it is preferable that the amount of the carrier, amino silicone, hydroxycarboxylic acid, titanium precursors molar ratio
Example range are as follows: 1:0.01~1:0.1~10:0.1~10.
In above-mentioned technical proposal, it is preferable that the hydroxycarboxylic acid includes hydroxybenzoic acid or hydroxyl phenylacetic acid.Wherein, institute
Stating hydroxyl in hydroxycarboxylic acid replaces site that can be contraposition, ortho position or meta position.In above-mentioned technical proposal, it is preferable that the carrier
For the one or more of carbon material, silicon materials, ceramics, metal, metal oxide materials.Preferably, the silicon materials include oxygen
SiClx, molecular sieve.
In above-mentioned technical proposal, it is preferable that the amino silicone is aminopropyl methoxysilane.
In above-mentioned technical proposal, it is preferable that the solvent be alcohol for example methanol, ethyl alcohol, normal propyl alcohol, n-butanol, isobutanol or
One or more of the tert-butyl alcohol or toluene, methylene chloride, chloroform, amide, ether.In above-mentioned technical proposal, it is preferable that
The titanium precursors include being selected from one or more of titanium oxide, titanium chloride, titanium sulfate, titanate esters.More preferably, described
Titanate esters include tetramethoxy titanate ester, tetraethyl titanate, butyl titanate.
The present invention also provides one kind to prepare diphenyl carbonate method for dimethyl carbonate and phenol ester exchange reaction, uses
Above-mentioned catalyst.
In above-mentioned technical proposal, it is preferable that the temperature of reaction is 120~190 DEG C, the molar ratio of dimethyl carbonate and phenol
For 0.5~5:1, the reaction time is 5~50h, and the weight ratio of catalyst and phenol is 0.01~0.5:1.
In above-mentioned technical proposal, it is preferable that in two steps, the temperature of first step reaction is 140~180 DEG C, carbonic acid two for reaction
The molar ratio of methyl esters and phenol is 1~3:1, and dimethyl carbonate time for adding is 2~6h, and the reaction temperature of second step reaction is
140~180 DEG C, the reaction time is 5~20h, and the weight ratio of catalyst and phenol is 0.05~0.5:1.
The preparation method of catalyst is as shown below:
Wherein R1, R2, R3, R4 are alkyl or aromatic radical.
The method of the present invention, as catalyst, is a kind of heterogeneous catalysis using support type monodisperse titanium catalyst system catalyst
Quasi- homogeneousization of agent, active site is consistent with homogeneous catalyst, therefore maintains higher reactivity and selectivity, simultaneously
Active site is anchored by covalent bond in carrier, and interaction force is strong, avoids the loss of active site, has heterogeneous catalysis
Agent advantage, after reaction can from system quick separating.Therefore, which can solve while improving activity and selectivity
Certainly general heterogeneous catalyst is easy the problem of inactivation.
At 180 DEG C of first step reaction temperature, the molar ratio of dimethyl carbonate and phenol is 2, dimethyl carbonate time for adding
For 4h, second step reaction temperature is 180 DEG C, is reacted for 10h, in the case that the weight ratio of catalyst and phenol is 0.2:1, phenol
Conversion ratio be 45.5%, the selectivity of diphenyl carbonate is 78.5%, and the selectivity of methyl benzol carbonate is 21.2%, is urged
Agent is reused 10 times, and activity decline is unobvious, achieves preferable technical effect.
The present invention will be further described below by way of examples.It is necessarily pointed out that following embodiment is only used
In to further explanation of the invention, it should not be understood as limiting the scope of the invention.
Specific embodiment
[embodiment 1]
It takes the silicon oxide ball of 50g to be added in 500ml toluene, three ethoxy of 0.01mol aminopropyl is added after being heated to reflux
Base silane, after the 2h that flows back, cooling, filtering, dehydrated alcohol washing.The P-hydroxybenzoic acid solution of 0.1mol is configured, modification is added
Cross carrier, heating stirring 8h.It filters, after ethanol washing, after immersing the dimethyl carbonate solution of the butyl titanate containing 0.1mol, stirs
After mixing 4h, excessive phenol is added, filtering, after dimethyl carbonate washing, drying obtains reaction catalyst sample S1.
[embodiment 2]
It takes the active carbon of 50g to be added in 500ml ethyl alcohol, 0.01mol aminopropyl triethoxy is added after being heated to reflux
Silane, after the 2h that flows back, cooling, filtering, dehydrated alcohol washing.The septichen dissolution for configuring 0.1mol, is added modified
Carrier, heating stirring 8h.It filters, after ethanol washing, after immersing the dimethyl carbonate solution of the tetramethoxy titanate ester containing 0.1mol, stirring
After 4h, excessive phenol is added, filtering, after dimethyl carbonate washing, drying obtains reaction catalyst sample S2.
[embodiment 3]
It takes the silicon oxide ball of 50g to be added in 500ml methylene chloride, 0.01mol aminopropyl three is added after being heated to reflux
Ethoxysilane, after the 2h that flows back, cooling, filtering, methylene chloride washing.The P-hydroxybenzoic acid dissolution for configuring 0.1mol, is added
Modified carrier, heating stirring 8h.It filters, after ethanol washing, after immersing titanium sulfate aqueous solution containing 0.1mol, after stirring 4h, adds
Enter excessive phenol, filter, after dimethyl carbonate washing, drying obtains reaction catalyst sample S3.
[embodiment 4]
It takes the silica zeolite of 50g to be added in 500ml methylene chloride, 0.01mol aminopropyl is added after being heated to reflux
Triethoxysilane, after the 2h that flows back, cooling, filtering, methylene chloride washing.The p-hydroxyphenylaceticacid dissolution for configuring 0.1mol, adds
Enter modified carrier, heating stirring 8h.It filters, after ethanol washing, the dimethyl carbonate for immersing the tetraethyl titanate containing 0.1mol is molten
After liquid, after stirring 4h, excessive phenol is added, filtering, after dimethyl carbonate washing, drying obtains reaction catalyst sample S4.
[embodiment 5]
It takes the aluminium oxide of 50g to be added in 500ml methylene chloride, three second of 0.01mol aminopropyl is added after being heated to reflux
Oxysilane, after the 2h that flows back, cooling, filtering, methylene chloride washing.The p-hydroxyphenylaceticacid dissolution of 0.1mol is configured, addition is repaired
Adornd carrier, heating stirring 8h.It filters, after ethanol washing, after immersing the dimethyl carbonate solution of the tetraethyl titanate containing 0.1mol,
After stirring 4h, excessive phenol is added, filtering, after dimethyl carbonate washing, drying obtains reaction catalyst sample S5.
[comparative example 1]
The silicon oxide ball of 50g is taken to be added in 500ml toluene, the dimethyl carbonate for immersing the butyl titanate containing 0.1mol is molten
After liquid, after stirring 4h, excessive phenol is added, filtering, after dimethyl carbonate washing, drying obtains reaction catalyst sample S6.
[comparative example 2]
It takes the aluminium oxide of 50g to be added in 500ml methylene chloride, three second of 0.01mol aminopropyl is added after being heated to reflux
Oxysilane, after the 2h that flows back, cooling, filtering, methylene chloride washing.The dimethyl carbonate for immersing the tetraethyl titanate containing 0.1mol is molten
After liquid, after stirring 4h, excessive phenol is added, filtering, after dimethyl carbonate washing, drying obtains reaction catalyst sample S7.
[embodiment 6]
In being connected with gas-guide tube, temperature-control heat couple, constant pressure funnel and there-necked flask equipped with rectifying column, 10.0g is added
Catalyst S1 is passed through nitrogen, and phenol 50.0g is added, and after being heated to 175 DEG C, starts that 95.7g DMC, time for adding 4h is added dropwise,
Rate of addition is 25g/h, and dropwise addition while steams the azeotropic mixture of DMC and methanol by rectifying column.Continue after dripping at 180 DEG C
10h is reacted, disproportionation products DMC is steamed by rectifying column while reaction, chromatography is carried out after reaction, obtains phenol
Conversion ratio is greater than 45%, and the selectivity of diphenyl carbonate is 72.4%, and the selectivity of methyl benzol carbonate is 27.6%.
[embodiment 7]
By catalyst obtained by [embodiment 1-5] and comparative example [comparative example 1-2] for dimethyl carbonate and phenol
In reaction, remaining condition is identical as [embodiment 6], and obtained reaction result is as shown in table 1:
Table 1
[embodiment 8]
[embodiment 6] after reaction, isolates catalyst S1, with 12h is dried in 120 DEG C of baking ovens after ethanol washing, so
After re-start reaction, so apply 10 times, obtain that the results are shown in Table 2.
Table 2
| Apply number | Phenol conversion % | Diphenyl carbonate selectivity % | Methyl benzol carbonate selectivity % |
| 1 | 45.8 | 75.6 | 24.3 |
| 2 | 43.3 | 76.2 | 23.5 |
| 3 | 45.7 | 76.6 | 23.3 |
| 4 | 45.3 | 76.7 | 23.3 |
| 5 | 44.4 | 76.3 | 23.6 |
| 6 | 45.5 | 76.7 | 23.3 |
| 7 | 45.6 | 76.3 | 23.5 |
| 8 | 45.1 | 76.4 | 23.4 |
| 9 | 44.3 | 76.7 | 23.2 |
| 10 | 45.6 | 76.3 | 23.5 |
Claims (10)
1. a kind of catalyst for diphenyl carbonate preparation, which is characterized in that the catalyst is support type monodisperse titanium
Catalyst system catalyst, including carrier and titanate esters group, the carrier are substrate, and the titanate esters group is activated centre,
Its structural formula are as follows:
Wherein R2, R3, R4 are alkyl or aromatic radical.
2. catalyst according to claim 1, which is characterized in that the content of titanium is 0.1~20% in the catalyst.
3. catalyst according to claim 1, which is characterized in that described R2, R3 are methyl, ethyl or propyl；R4 is hydroxyl
Base or methyl.
4. a kind of preparation method of catalyst described in claim 1, which comprises the steps of:
1) one step of carrier surface is modified: carrier is added in solvent, is heated, amino silicone is added, it is cooling, and it filters, washing；
2) two step of carrier surface is modified: configuration hydroxycarboxylic acid dissolution is added in 1), heats, filter, washs, dry；
3) carrier titanium is handled: titanium precursors are dissolved in solvent, are added carrier is processed in 2), heating, after phenol is added,
Filtering is washed, dry, obtains catalyst.
5. the preparation method according to claim 4, which is characterized in that the hydroxycarboxylic acid includes hydroxybenzoic acid or hydroxyl
Phenylacetic acid.
6. the preparation method according to claim 4, which is characterized in that the carrier is carbon material, silicon materials, ceramics, gold
Belong to, the one or more of metal oxide materials；Solvent is one or more of toluene, chloroform, methylene chloride, alcohol.
7. the preparation method according to claim 4, which is characterized in that the titanium precursors include being selected from titanium oxide, chlorination
One or more of titanium, titanium sulfate, titanate esters.
8. one kind prepares diphenyl carbonate method for dimethyl carbonate and phenol ester exchange reaction, which is characterized in that carbonic acid two
Methyl esters and phenol ester exchange reaction prepare diphenyl carbonate, using catalyst described in claim 1.
9. method according to claim 8, which is characterized in that the reaction temperature of the reaction is 120~190 DEG C, carbonic acid two
The molar ratio of methyl esters and phenol is 0.5~5:1, and the reaction time is 5~50h, the weight ratio of catalyst and phenol is 0.01~
0.5:1.
10. according to the method described in claim 8, it is characterized in that, reaction in two steps, the first step reaction temperature be 140~
180 DEG C, the molar ratio of dimethyl carbonate and phenol is 1~3:1, and dimethyl carbonate time for adding is 2~6h, second step reaction
Reaction temperature is 140~180 DEG C, and the reaction time is 5~20h, and the weight ratio of catalyst and phenol is 0.05~0.5:1.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| 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 |
| CN112705183A (en) * | 2019-10-24 | 2021-04-27 | 中国石油化工股份有限公司 | Catalyst for preparing diphenyl carbonate and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| 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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