CN102140065B - Preparation method of diaryl carbonate - Google Patents
Preparation method of diaryl carbonate Download PDFInfo
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- CN102140065B CN102140065B CN 201010106252 CN201010106252A CN102140065B CN 102140065 B CN102140065 B CN 102140065B CN 201010106252 CN201010106252 CN 201010106252 CN 201010106252 A CN201010106252 A CN 201010106252A CN 102140065 B CN102140065 B CN 102140065B
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- promotor
- carbazole
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Abstract
The invention relates to a preparation method of diaryl carbonate, comprising the step of carrying out oxidative carbonylation on phenols and carbon monoxide and oxygen to synthesize diaryl carbonate, in particular to synthesize diphenyl carbonate by phenol. The method is characterized in that a catalytic system consisting of a metal halide catalyst together with one or more N-containing heterocyclic compounds used as a support catalyst is adopted, thereby increasing the conversion rate, selectivity and yield of the catalytic reaction.
Description
Technical field
The present invention relates to the method for making of diaryl carbonate, it carries out oxidation carbonylation and the carbonate synthesis diaryl ester by phenols and carbon monoxide and oxygen, particularly by the phenol diphenyl carbonate synthesis.
Background technology
Diphenyl carbonate (DPC) is little, the free of contamination organism of a kind of toxicity, and be the intermediate of important engineering plastics, can be used for the synthetic of many important organic compound and macromolecular material such as monoisocyanates, vulcabond, polycarbonate, poly methyl esters, poly-aryl carbonates etc., can also be as the softening agent of polymeric amide and polyester and solvent etc.
Along with the exploitation as the non-phosgene synthetic method of the synthetic high-quality polycarbonate (PC) of raw material of diphenyl carbonate and dihydroxyphenyl propane, diphenyl carbonate becomes noticeable especially compound in recent years.Produce polycarbonate adopts dihydroxyphenyl propane photoreactive gas or methyl-chloroformate to carry out polymeric method (or claiming the interface polymerization) in methylene dichloride-water two-phase system more, but phosgene and methyl-chloroformate are highly toxic substances, environment is caused very big pollution, also very big to the corrodibility of equipment.And come polycarbonate synthesis can avoid using deleterious solvent and chloride raw material by diphenyl carbonate, reduce the corrosion of equipment and the pollution of environment.
The method of diphenyl carbonate synthesis mainly contains three kinds at present, i.e. phosgenation, ester-interchange method and phenol oxidation carbonylation method.Phosgenation is the method for using the earliest, also is the main method of producing diphenyl carbonate in the past, but its complex process, cost height, quality are low, and phosgene has severe toxicity, serious environment pollution, and this method is eliminated abroad.Ester-interchange method uses methylcarbonate (United States Patent (USP) the 4th, 410, No. 464) or dimethyl oxalate (Japanese Patent 08-325207 number), can avoid using phosgene, but its equilibrium conversion is low, and homogeneous catalyst reclaims difficulty, and needs special reaction unit.The phenol oxidation carbonylation method is directly utilized carbon monoxide, oxygen and phenol one-step synthesis diphenyl carbonate, have that technology is simple, raw material is cheap, the advantage of environmentally safe, be the operational path of a very attractive, have good DEVELOPMENT PROSPECT and researching value.
The unusual company of the U.S. is at United States Patent (USP) the 4th, 096, the diaryl carbonate technology that discloses in No. 168 comprises uses phenol, carbon monoxide, alkali and as the oxidation state of the catalyzer compound greater than 0 VIIIB family metal, wherein alkali is to have sterically hindered amine.United States Patent (USP) the 4th, 096, also disclosing this reactive system in No. 169 can carry out under situation about existing without any solvent, as carrying out under the situation for reactant and solvent simultaneously at phenols, but also can carry out under the situation that has solvent to exist, more suitable solvent can be methylene dichloride, toluene, phenyl ether, Benzene Chloride and orthodichlorobenzene etc.The alkali that also discloses in addition in the catalysis system can be organic or inorganic alkali, as basic metal or alkaline-earth metal and oxyhydroxide, quaternary ammonium, quaternary phosphine, primary amine, secondary amine or tertiary amine etc.Above-mentioned catalysis system because of oxidation state greater than 0 VIIIB family metal along with after reaction is reduced into zeroth order, can't return previous oxidation valence mumber by reoxidation, make the stopping of reaction.And this technology with an organic solvent, has the suspicion of pollution.
United States Patent (USP) the 4th, 349, the diaryl carbonate technology that discloses for No. 485 is used phenol, carbon monoxide, alkali and the VIIIB family metal except that comprising, also comprises using oxygenant and as the tetradentate manganese (manganese tetradentate) of redox promotor.The form of tetradentate manganese is (L)
xMn, wherein L is two (beta-diketon) (C
14-20H
22-34O
4), oxygenant then is an air, and uses molecular sieve and Tetrabutylammonium bromide respectively as water-removal agent and consisting of phase-transferring agent.The reaction times of this technology is 80 hours, and phenol conversion reaches about 50%, and its reactivity is low excessively.
United States Patent (USP) the 5th, 132 then uses the homogeneous catalysis system of palladium/Cobaltous diacetate/Tetrabutylammonium bromide and adds benzoquinones, make the productive rate of diphenyl carbonate be increased to 26.1% from 15.2% under high pressure (top pressure reaches 2050psi) for No. 477.United States Patent (USP) the 5th, 284, find in the presence of organic promoter three pyridines for No. 964, with palladium as Primary Catalysts, 2-salicylic aldehyde-3,3 '-diamino-N-methyl dipropylamine cobalt (CoSMDPT) is as inorganic promotor, bromination tetra-allkylammonium or the bromination hexaalkylguanidium salts source as bromide, under high pressure (top pressure reaches 1600psi) introduces fixing carbon monoxide and the oxygen of forming, and can make the productive rate of diphenyl carbonate reach 45%.In order to obtain commercialization still acceptable response speed and selection rate, must under high pressure carry out this reaction, but under the situation that the reaction total pressure improves constantly, increase business-like facility investment expense greatly.
No. the 350th, 700, European patent as inorganic promotor, adds quinone or Resorcinol as the transfer transport catalyst with cobalt salt.But in this technology, remove the transfer transport catalyst and need spend sizable expense.2 hydroxyls that Resorcinol provides also can make phenol form the by product of carbonates, and the cost of removing this by product is big, and the transfer transport catalyst can't regenerate to reuse, and production of by-products makes selection rate descend, and economical load increases.
The technology that Japanese Patent discloses for 04-257546 number is carried out in distillation tower, and it adds the quaternary salt class as catalysis system with noble metal, and reaction water is removed by distillation.Because of the problem on the equipment, dead time is very short, makes that space time yield (STY) is very low, only 17.8g/l.h.And there are a large amount of halide-ionss in the employed catalysis system of this technology, have corrosion problems and take place.
United States Patent (USP) the 5th, 498, in No. 742 with palladium bromide/Tetrabutylammonium bromide/manganese acetylacetonate/sodium phenylate as catalysis system, because of its catalyzer needs activate with a large amount of carbon monoxide earlier, do not meet economic benefit yet.
Summary of the invention
In view of the above problems, main purpose of the present invention is to be provided at the method for preparing diaryl carbonate that has high reaction conversion ratio under the low reaction pressure.
Another object of the present invention is to provide the method for preparing diaryl carbonate with high reaction preference.
A further object of the present invention is to provide the method for preparing diaryl carbonate with high reaction conversion ratio.
Another purpose of the present invention is to provide has high reactive method for preparing diaryl carbonate.
The method for making of diaryl carbonate of the present invention is included under the existence of the catalysis system that the collocation of VIIIB family metal halide forms as one or more nitrogen-containing heterocycle compounds of organic promoter, carries out oxidation carbonylation and the carbonate synthesis diaryl ester by phenols and carbon monoxide and oxygen.
Especially, the catalysis system of the present invention by using the collocation of halogenation palladium catalyst to form, the oxidation carbonylation of catalysis of phenol and diphenyl carbonate synthesis as one or more nitrogen-containing heterocycle compounds of organic promoter.
Being characterized as of the method for making of diaryl carbonate of the present invention comprises following ingredients in its oxidation carbonylation: (1) metal halide catalyst, (2) phenol, (3) alkali, (4) inorganic promotor, (5) quaternary ammonium halides salt, (6) carbon monoxide, (7) oxygen, (8) organic promoter.Wherein, this metal halide catalyst can be halogenation palladium, for example Palladous chloride; And this organic promoter can be one or more nitrogen-containing heterocycle compounds that is expressed from the next:
In the following formula, R
1-R
8Can be hydrogen independently of one another, straight or branched C
1-12Alkyl, C
3-12Cycloalkyl, C
7-12Aralkyl, C
6-12Aryl, C
7-12Alkaryl, halogen, nitro, cyano group, amino contains the C of aerobic, sulphur, nitrogen or carboxyl
1-10Alkyl, C
7-10Aralkyl, C
3-10Cycloalkyl, C
6-10Aryl or C
7-10Alkaryl, or contain the salt group of aerobic, sulphur, nitrogen or carboxyl.
Especially, this organic promoter is the nitrogen-containing heterocycle compound of carbazoles, and the example of the organic promoter of this carbazoles comprises, but be not limited to, carbazole, 3,6-diamino carbazole, 3,6-dichloro carbazole, 3,6-dibromo carbazole, 2-acetyl carbazole and 2-hydroxy benzo [a] carbazole-3-carboxylic acid sodium salt.
According to the present invention, catalysis system is made up of as one or more nitrogen-containing heterocycle compounds of organic promoter metal halide (particularly halogenation palladium) collocation, and phenol carries out oxidation carbonylation and diphenyl carbonate synthesis in the 1L high-pressure reactor.The temperature range that this reaction is carried out is 60～140 ℃, is preferably 70～100 ℃, and pressure range is 5～80kg/cm
2, be preferably 6～12kg/cm
2, the promotor that collocation is added and the mol ratio of catalyzer are 10: 1 to 1: 10, are preferably 5: 1 to 1: 5, the catalyst metal concentration scope is 100～8000ppm, is preferably 200～2000ppm.
Below further specify characteristics of the present invention and effect by specific embodiment, but it is not to be used to limit the scope of the invention.
Embodiment
The transformation efficiency of being put down in writing in the specification sheets of the present invention, selection rate, and productive rate calculate according to following equation:
Phenol (the mol)/phenol inlet amount (mol) * 100% of transformation efficiency (%)=react away
The phenol (mol) * 100% of the DPC (mol) of selection rate (%)=2 * output/react away
Productive rate (%)=transformation efficiency (%) * selection rate (%) * 100%
Comparative example
Phenol 231.72 grams (2.4 moles), manganese acetylacetonate 0.35 gram (0.00139 mole), Tetrabutylammonium bromide 3.87 grams (0.012 mole), sodium hydroxide 0.35 gram (0.00878 mole) are placed the stainless steel high-pressure reactor with the 1L of agitator, and interpolation palladium chloride catalyst, making the palladium amount that contains in total reaction system is 265ppm, with the air in the mixed gas metathesis reactor of carbon monoxide and oxygen, then start agitator, build and be depressed into 10kg/cm
2And reactive system is warming up to 80 ℃, and the volume ratio of oxygen/carbon monoxide is 5/95 between the reaction period, reactor all maintains 10kg/cm
2Pressure, the reaction 60 minutes after the sampling, sample is analyzed with gas chromatograph, the results are shown in Table 1 for it.
Embodiment 1-5
Repeat the step of comparative example, but add different organic promoters, and to make the mol ratio of organic promoter and catalyzer be 1: 1, the result is as shown in table 1, when table 1 was presented at the different promotor of palladium chloride catalyst collocation, productive rate all had raising in various degree.
The table 1 Palladous chloride raising effect of different promotors of arranging in pairs or groups to the diphenyl carbonate productive rate
| Promotor | Transformation efficiency (%) | Selection rate (%) | Productive rate (%) | |
| Comparative example | Do not have | 5.9 | 98.9 | 5.8 |
| Embodiment 1 | Carbazole | 7.2 | 100.0 | 7.2 |
| Embodiment 2 | 3,6-dibromo carbazole | 10.3 | 99.1 | 10.2 |
| Embodiment 3 | 3,6-diamino carbazole | 10.4 | 100.0 | 10.4 |
| Embodiment 4 | The 2-acetyl carbazole | 8.4 | 99.3 | 8.3 |
| Embodiment 5 | 2-hydroxy benzo [a] carbazole-3-carboxylic acid sodium salt | 9.0 | 99.3 | 8.9 |
Embodiment 6-7
Repeat the step of comparative example, but use different Palladous chloride concentration, the promotor that is added is 3,6-dibromo carbazole, the mol ratio of itself and catalyzer is 1: 1, the result is as shown in table 2, and table 2 is presented under the different palladium chloride catalyst concentration, and promotor is all helpful to the generation of diphenyl carbonate.
The halogenation palladium of table 2 promotor collocation different concns influences the diphenyl carbonate synthetic
| Palladium concentration (ppm) | Transformation efficiency (%) | Selection rate (%) | Productive rate (%) | |
| Embodiment 2 | 265 | 10.3 | 99.1 | 10.2 |
| Embodiment 6 | 132 | 7.0 | 99.1 | 6.9 |
| Embodiment 7 | 1000 | 6.8 | 98.9 | 6.7 |
Embodiment 8
Repeat the step of comparative example, but react under different reaction pressures, the promotor that is added is 3,6-dibromo carbazole, the result is as shown in table 3, after table 3 is presented at and adds promotor of the present invention, under different pressure, still can keep the productive rate higher than original system.
The influence that table 3 pressure generates diphenyl carbonate
| Reaction pressure (kg/cm 2) | Transformation efficiency (%) | Selection rate (%) | Productive rate (%) | |
| Embodiment 2 | 10 | 10.3 | 99.1 | 10.2 |
| Embodiment 8 | 8 | 6.5 | 98.8 | 6.4 |
Embodiment 9
Repeat the step of comparative example, but react under different temperature of reaction, the promotor that is added is 3,6-dibromo carbazole, the result is as shown in table 4, after table 4 is presented at and adds promotor of the present invention, under higher relatively temperature, still can keep the productive rate higher than original system.
The influence that table 4 temperature generates diphenyl carbonate
| Temperature of reaction (℃) | Transformation efficiency (%) | Selection rate (%) | Productive rate (%) | |
| Embodiment 2 | 80 | 10.3 | 99.1 | 10.2 |
| Embodiment 9 | 90 | 7.5 | 99.0 | 7.4 |
Embodiment 10-11
Repeat the step of comparative example, but under different promotor/catalyst molar ratios, react, the promotor that is added is 3,6-dibromo carbazole, the result is as shown in table 5, table 5 is presented under the mol ratio of different promotors and catalyzer, still can obtain the diphenyl carbonate productive rate higher than original system.
The influence that the ratio of table 5 promotor and palladium catalyst generates diphenyl carbonate
| Promotor/palladium catalyst | Transformation efficiency (%) | Selection rate (%) | Productive rate (%) | |
| Comparative example | No promotor | 5.9 | 98.9 | 5.8 |
| Embodiment 2 | 1/1 | 10.3 | 99.1 | 10.2 |
| Embodiment 10 | 1/2 | 7.2 | 99.1 | 7.1 |
| Embodiment 11 | 2/1 | 7.9 | 99.2 | 7.8 |
Claims (13)
1. the method for making of diaryl carbonate, it carries out oxidation carbonylation and the carbonate synthesis diaryl ester by phenols and carbon monoxide and oxygen, it is characterized in that, the catalysis system that uses the metal halide catalyst collocation to form as one or more nitrogen-containing heterocycle compounds of promotor, wherein, this promotor is one or more nitrogen-containing heterocycle compounds that is expressed from the next:
In the following formula, R
1～R
8Be hydrogen independently of one another, straight or branched C
1-12Alkyl, C
3-12Cycloalkyl, C
7-12Aralkyl, C
6-12Aryl, C
7-12Alkaryl, halogen, nitro, cyano group, amino contains the C of aerobic, sulphur or nitrogen
1-10Alkyl, C
7-10Aralkyl, C
3-10Cycloalkyl, C
6-10Aryl or C
7-10Alkaryl perhaps contains the salt group of aerobic, sulphur or nitrogen.
2. the method for making of claim 1, wherein, this contains the C of aerobic
1-10Alkyl, C
7-10Aralkyl, C
3-10Cycloalkyl, C
6-10Aryl or C
7-10Alkaryl is the C that contains carboxyl
1-10Alkyl, C
7-10Aralkyl, C
3-10Cycloalkyl, C
6-10Aryl or C
7-10Alkaryl.
3. the method for making of claim 1, wherein, this salt group that contains aerobic is the salt group that contains carboxyl.
4. each method for making among the claim 1-3, wherein, this metal halide catalyst is the halogenation palladium.
5. each method for making among the claim 1-3, wherein, this promotor is for being selected from carbazole, 3,6-diamino carbazole, 3, the carbazole compound of 6-dibromo carbazole, 2-acetyl carbazole and 2-hydroxy benzo [a] carbazole-3-carboxylic acid sodium salt.
6. each method for making among the claim 1-3, wherein, the mol ratio of this promotor and this catalyzer is 10: 1 to 1: 10.
7. the method for making of claim 6, wherein, the mol ratio of this promotor and this catalyzer is 5: 1 to 1: 5.
8. each method for making among the claim 1-3, wherein, the concentration of metal in this catalyzer is 100～8000ppm.
9. the method for making of claim 8, wherein, the concentration of metal in this catalyzer is 200～2000ppm.
10. each method for making among the claim 1-3, wherein, this is reflected under 60～140 ℃ the temperature and carries out.
11. the method for making of claim 10, wherein, this is reflected under 70～100 ℃ the temperature and carries out.
12. each method for making among the claim 1-3, wherein, this is reflected at 5～80kg/cm
2Pressure under carry out.
13. the method for making of claim 12, wherein, this is reflected at 6～12kg/cm
2Pressure under carry out.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1358168A (en) * | 1999-06-30 | 2002-07-10 | 通用电气公司 | Catalyst composition and method for producing diaryl carbonates using nitrile as promoter |
| CN1698960A (en) * | 2005-04-18 | 2005-11-23 | 中国科学院成都有机化学有限公司 | Catalyst system for synthesis of diphenyl carbonate by ester exchange reaction |
| CN1775734A (en) * | 2005-12-06 | 2006-05-24 | 河北工业大学 | Method for synthesizing diphenyl carbonate from phenol oxidation carbonylation by environment friendly solvent process |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1358168A (en) * | 1999-06-30 | 2002-07-10 | 通用电气公司 | Catalyst composition and method for producing diaryl carbonates using nitrile as promoter |
| CN1698960A (en) * | 2005-04-18 | 2005-11-23 | 中国科学院成都有机化学有限公司 | Catalyst system for synthesis of diphenyl carbonate by ester exchange reaction |
| CN1775734A (en) * | 2005-12-06 | 2006-05-24 | 河北工业大学 | Method for synthesizing diphenyl carbonate from phenol oxidation carbonylation by environment friendly solvent process |
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