CN102557949B - Process for producing diaryl carbonate - Google Patents
Process for producing diaryl carbonate Download PDFInfo
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- CN102557949B CN102557949B CN201110113251.7A CN201110113251A CN102557949B CN 102557949 B CN102557949 B CN 102557949B CN 201110113251 A CN201110113251 A CN 201110113251A CN 102557949 B CN102557949 B CN 102557949B
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- diazosulfide
- metal halide
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- -1 diaryl carbonate Chemical compound 0.000 title claims abstract description 22
- 238000000034 method Methods 0.000 title abstract description 15
- 230000008569 process Effects 0.000 title description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000002360 preparation method Methods 0.000 claims abstract description 18
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 13
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000001301 oxygen Substances 0.000 claims abstract description 12
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 12
- 239000003054 catalyst Substances 0.000 claims description 18
- 230000003647 oxidation Effects 0.000 claims description 11
- 238000007254 oxidation reaction Methods 0.000 claims description 11
- 229910001507 metal halide Inorganic materials 0.000 claims description 10
- 150000005309 metal halides Chemical class 0.000 claims description 10
- 230000015572 biosynthetic process Effects 0.000 claims description 9
- 238000006555 catalytic reaction Methods 0.000 claims description 9
- 238000003786 synthesis reaction Methods 0.000 claims description 9
- 230000006315 carbonylation Effects 0.000 claims description 8
- 238000005810 carbonylation reaction Methods 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical group Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- ROORDVPLFPIABK-UHFFFAOYSA-N diphenyl carbonate Chemical compound C=1C=CC=CC=1OC(=O)OC1=CC=CC=C1 ROORDVPLFPIABK-UHFFFAOYSA-N 0.000 abstract description 17
- 150000002989 phenols Chemical class 0.000 abstract description 6
- 230000002194 synthesizing effect Effects 0.000 abstract 2
- 238000005832 oxidative carbonylation reaction Methods 0.000 abstract 1
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 24
- 238000006243 chemical reaction Methods 0.000 description 22
- 230000000052 comparative effect Effects 0.000 description 9
- 229910052763 palladium Inorganic materials 0.000 description 9
- 230000009466 transformation Effects 0.000 description 7
- 239000003513 alkali Substances 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 230000026030 halogenation Effects 0.000 description 4
- 238000005658 halogenation reaction Methods 0.000 description 4
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 4
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 230000027756 respiratory electron transport chain Effects 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- HYZQBNDRDQEWAN-LNTINUHCSA-N (z)-4-hydroxypent-3-en-2-one;manganese(3+) Chemical compound [Mn+3].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O HYZQBNDRDQEWAN-LNTINUHCSA-N 0.000 description 2
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 2
- CXHHBNMLPJOKQD-UHFFFAOYSA-M methyl carbonate Chemical compound COC([O-])=O CXHHBNMLPJOKQD-UHFFFAOYSA-M 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 125000006652 (C3-C12) cycloalkyl group Chemical group 0.000 description 1
- DRLGIZIAMHIQHL-UHFFFAOYSA-N 2,1,3-benzothiadiazol-4-amine Chemical compound NC1=CC=CC2=NSN=C12 DRLGIZIAMHIQHL-UHFFFAOYSA-N 0.000 description 1
- PDQRQJVPEFGVRK-UHFFFAOYSA-N 2,1,3-benzothiadiazole Chemical compound C1=CC=CC2=NSN=C21 PDQRQJVPEFGVRK-UHFFFAOYSA-N 0.000 description 1
- IWQKAMJGVIHECB-UHFFFAOYSA-N 4-nitro-2,1,3-benzothiadiazole Chemical compound [O-][N+](=O)C1=CC=CC2=NSN=C12 IWQKAMJGVIHECB-UHFFFAOYSA-N 0.000 description 1
- QQCMLCGOLBUDJF-UHFFFAOYSA-N 5,6-dimethyl-2,1,3-benzothiadiazole Chemical compound C1=C(C)C(C)=CC2=NSN=C21 QQCMLCGOLBUDJF-UHFFFAOYSA-N 0.000 description 1
- XDQJAYFCPRWDOL-UHFFFAOYSA-N 5-methyl-2,1,3-benzothiadiazole Chemical compound C1=C(C)C=CC2=NSN=C21 XDQJAYFCPRWDOL-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- LOMVENUNSWAXEN-UHFFFAOYSA-N Methyl oxalate Chemical compound COC(=O)C(=O)OC LOMVENUNSWAXEN-UHFFFAOYSA-N 0.000 description 1
- 239000004902 Softening Agent Substances 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 229910052728 basic metal Inorganic materials 0.000 description 1
- 150000003818 basic metals Chemical class 0.000 description 1
- 150000004054 benzoquinones Chemical class 0.000 description 1
- 230000031709 bromination Effects 0.000 description 1
- 238000005893 bromination reaction Methods 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- IVSWQMIJNRQCHM-UHFFFAOYSA-N carbonyl dichloride;diphenyl carbonate Chemical compound ClC(Cl)=O.C=1C=CC=CC=1OC(=O)OC1=CC=CC=C1 IVSWQMIJNRQCHM-UHFFFAOYSA-N 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000003749 cleanliness Effects 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 150000001868 cobalt Chemical class 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000000994 depressogenic effect Effects 0.000 description 1
- DWNAQMUDCDVSLT-UHFFFAOYSA-N diphenyl phthalate Chemical compound C=1C=CC=C(C(=O)OC=2C=CC=CC=2)C=1C(=O)OC1=CC=CC=C1 DWNAQMUDCDVSLT-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000007172 homogeneous catalysis Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- INIOZDBICVTGEO-UHFFFAOYSA-L palladium(ii) bromide Chemical compound Br[Pd]Br INIOZDBICVTGEO-UHFFFAOYSA-L 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 230000003244 pro-oxidative effect Effects 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 231100000004 severe toxicity Toxicity 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- NESLWCLHZZISNB-UHFFFAOYSA-M sodium phenolate Chemical compound [Na+].[O-]C1=CC=CC=C1 NESLWCLHZZISNB-UHFFFAOYSA-M 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a preparation method of diaryl carbonate, which is used for synthesizing diaryl carbonate by oxidative carbonylation of phenols, carbon monoxide and oxygen, in particular to a method for synthesizing diphenyl carbonate by phenol.
Description
Technical field
The present invention relates to a kind of preparation method of diaryl carbonate, it carries out oxidation carbonylation and carbonate synthesis diaryl ester, particularly by phenol synthesis diphenyl carbonate by phenols and carbon monoxide and oxygen.
Background technology
Diphenyl carbonate (Diphenyl Carbonate, DPC) be little, the free of contamination organism of a kind of toxicity, and be important engineering plastics intermediate, can be used for the synthesis of much important medicine, agricultural chemicals, other organic compound and macromolecular material, as monoisocyanates, vulcabond, polycarbonate, poly-to carbonyl benzoic acid ester, poly-aryl carbonates etc., can also as the softening agent of polymeric amide and polyester and solvent etc.
The method of current diphenyl carbonate synthesis mainly contains three kinds, i.e. phosgenation, ester-interchange method and phenol oxidation carbonylation method.Phosgenation is method the earliest, is also the main method of producing diphenyl carbonate in the past, but because of complex process, raw material phosgene severe toxicity, serious environment pollution, is eliminated gradually.Ester-interchange method uses methylcarbonate (United States Patent (USP) the 4th, 410, No. 464) or dimethyl oxalate (No. 08-325207th, Japanese Patent) replace phosgene and phenol to carry out transesterification reaction Formed diphenyl phthalate, for the main flow of current non-phosgene diphenyl carbonate synthesis technique, but because methylcarbonate price is more expensive, limit the development of this technique.Phenol oxidation carbonylation method is shown below, directly utilize carbon monoxide, oxygen and phenol one-step synthesis diphenyl carbonate, adjoint by product only has water, thus there is the advantages such as reaction process is simple, raw material cheap, cleanliness without any pollution, be a kind of operational path of very attractive, there is good DEVELOPMENT PROSPECT and researching value.
Unusual company of the U.S. is at United States Patent (USP) the 4th, 096, disclose in No. 168 in diaryl carbonate technique and include phenol, carbon monoxide, alkali (base) and oxidation state and be greater than the group VIIIB metallic compound of 0 as catalyzer, wherein alkali is to have the amine of steric barrier (sterically hindered).United States Patent (USP) the 4th, also disclosing this reactive system in 096, No. 169 can carry out under without any the existence of solvent, and using reactant phenols simultaneously as reactant and solvent; Also the alkali disclosed in catalysis system can be organic or inorganic alkali in addition, as the amine etc. of the ammonium of basic metal or alkaline earth metal and oxyhydroxide thereof, level Four and squama, one-level to three grade.The group VIIIB metal that above-mentioned catalysis system is greater than 0 because of oxidation state carries out along with reaction and after being reduced into zeroth order, again cannot be oxidized back previous oxidation valence mumber, makes the stopping of reaction.
United States Patent (USP) the 4th, 349, No. 485 diaryl carbonate techniques disclosed are except comprising phenol, carbon monoxide, alkali and group VIIIB metal, also comprise oxidant air and redox promotor four tooth base manganese (four tooth manganese, tetradentate manganese, manganese tetradentate), and use molecular sieve and Tetrabutyl amonium bromide respectively as water-removal agent and consisting of phase-transferring agent, after reacting 80 hours, its phenol conversion is about 50%, but initial reaction stage (1 ~ 3 hour) phenol conversion is then lower than 5%.
United States Patent (USP) the 5th, 132, No. 477 then use the homogeneous catalysis system of palladium/Cobaltous diacetate/Tetrabutyl amonium bromide and add benzoquinones, promote diphenyl carbonate productive rate by (top pressure reaches 2050psi) in a high voltage state.United States Patent (USP) the 5th, 284, No. 964 find under organic promoter three pyridine exists, using palladium as Primary Catalysts, 2-salicylic aldehyde-3,3 '-two amido-N-methyl dipropylamine cobalt (CoSMDPT) is as inorganic cocatalysts, tetraalkyl brometo de amonio or the six alkyl bromination guanidinesalts source as bromide, under high pressure, (top pressure reaches 1600psi) introduces carbon monoxide and the oxygen of fixing composition, and the productive rate of diphenyl carbonate can be made to reach 45%.For obtaining the still acceptable speed of reaction of commercialization and selection rate, carbon monoxide and the oxygen that under high pressure must introduce definite composition react to carry out this, but under the situation that improves constantly of reaction stagnation pressure, greatly increase business-like facility investment expense.
European patent the 350th, No. 700, using cobalt salt as inorganic cocatalysts, are added quinone or Resorcinol as Electron-Transfer Catalyst.But remove Electron-Transfer Catalyst in this process to need to spend sizable expense.2 OH bases that Resorcinol provides also can make phenol form the by product of carbonates, and the cost removing this by product is large, and Electron-Transfer Catalyst cannot regenerate and reuses, and the generation of by product makes selection rate decline, economical load increase.
United States Patent (USP) the 5th, using palladium bromide/Tetrabutyl amonium bromide/manganese acetylacetonate/sodium phenylate as catalysis system in 498, No. 742, because its catalyzer needs first to activate with a large amount of carbon monoxide, does not meet economic benefit yet.
And the development of supported catalyst such as Takagi et a1. (J.Mol.Catal.A:Chem.129 (1998) L1) is dominant catalyst with 5%Pd/C, PbO is pro-oxidant, can obtain the diphenyl carbonate productive rate of 9.55%.Song et al. (J.Mol.Catal.A:Chem.154 (2000) 243) more loaded Pd catalyzer 5%Pd/C, Pd/Al in addition
2o
3, Pd/SiO
2with the catalytic activity of Pd/MgO, find that activity carbon carrier is better than other carrier.Due to the carrying out of water meeting inhibited reaction, and Al
2o
3, SiO
2make it have wetting ability with oxide carriers such as MgO because there being carbonyl to exist on the surface, activity carbon carrier then has a hydrophobicity, and therefore activity carbon carrier helps reaction on the contrary.But both reaction pressures above are up to 80 ~ 90Kg/cm
2and reaction efficiency is not high.
Summary of the invention
Because the problems referred to above, main purpose of the present invention is to provide a kind of preparation method under compared with low reaction pressure with the diaryl carbonate of high reaction conversion ratio.
Another object of the present invention is to provide a kind of preparation method with the diaryl carbonate of high reaction preference.
Another object of the present invention is to provide a kind of preparation method with the diaryl carbonate of high reaction convertibility.
Another object of the present invention is to provide a kind of preparation method that can improve the diaryl carbonate of productive rate.
For reaching above-mentioned and other object, according to the preparation method of diaryl carbonate provided by the present invention, in use group VIIIB metal halide catalyst collocation at least one or the catalysis system that forms as organic promoter of multiple nitrogen-containing heterocycle compound, phenolic compound, carbon monoxide and oxygen is made to carry out oxidation carbonylation and generate diaryl carbonate, thus can improve transformation efficiency and the selectivity of catalyzed reaction, and improve W-response productive rate.
Especially, the present invention to arrange in pairs or groups the catalysis system of one or more nitrogen-containing heterocycle compounds as organic promoter by using halogenation palladium catalyst, the oxidation carbonylation of catalysis of phenol and diphenyl carbonate synthesis.
The feature of the preparation method of diaryl carbonate of the present invention is comprise following ingredients in the medium of its oxidation carbonylation: (1) metal halide catalyst, (2) phenolic compound, (3) alkali, (4) inorganic cocatalysts, (5) halogenation quarternary ammonium salt, (6) carbon monoxide, (7) oxygen, (8) organic promoter.Wherein, this phenolic compound is especially phenol; This metal halide catalyst can be halogenation palladium, such as Palladous chloride; And this organic promoter can be the nitrogen-containing heterocycle compound that one or more are expressed from the next:
In above formula, R
1-R
4be hydrogen separately, straight or branched C
1-12alkyl, C
3-12cycloalkyl, C
3-12aralkyl, C
3-12aryl, C
3-12alkaryl, halogen, nitro, cyano group, amido, containing the C of oxygen, sulphur, nitrogen or carboxyl
1-10alkyl, C
1-10aralkyl, C
1-10cycloalkyl, C
1-10aryl or C
1-10alkaryl, or the salt containing oxygen, sulphur, nitrogen or carboxyl.
Especially, this organic promoter is 2, 1, 3-diazosulfide class nitrogen-containing heterocycle compound, and this 2, 1, the example of 3-diazosulfide class organic promoter comprises, but to be non-ly confined to, 2, 1, 3-diazosulfide (2, 1, 3-benzothiadiazole), 4-nitro-2, 1, 3-diazosulfide (4-nitro-2, 1, 3-benzothiadiazole), 4-amido-2, 1, 3-diazosulfide (4-amino-2, 1, 3-benzothiadiazole), 5-methyl-2, 1, 3-diazosulfide (5-methyl-2, 1, 3-benzothiadiazole) with 5, 6-dimethyl-2, 1, 3-diazosulfide (5, 6-dimethyl-2, 1, 3-benzothiadiazole).
According to a specific embodiment of the present invention, catalysis system is by metal halide, particularly halogenation palladium (such as Palladous chloride), one or more nitrogen-containing heterocycle compounds of arranging in pairs or groups formed as organic promoter, carry out oxidation carbonylation and diphenyl carbonate synthesis by phenol in 1L high-pressure reactor.The temperature range that this reaction is carried out is 60 ~ 120 DEG C, is preferably 70 ~ 90 DEG C, and pressure range is 5 ~ 80kg/cm
2, be preferably 6 ~ 12kg/cm
2, the mol ratio of the promotor that collocation is added and catalyzer is 10: 1 to 1: 10, is preferably 5: 1 to 1: 5, and the metal concentration scope of catalyzer is 100 ~ 8000ppm, is preferably 200 ~ 2000ppm.
Further illustrate feature of the present invention and effect below by way of particular specific embodiment, but it is not for limiting the scope of the invention.
Embodiment
Transformation efficiency, selection rate and productive rate described in specification sheets of the present invention 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)
By phenol 231.72 grams (2.4 moles), manganese acetylacetonate 0.35 gram (0.00139 mole), Tetrabutylammonium bromide 3.87 grams (0.012 mole), 0.35 gram, sodium hydroxide (0.00878 mole), be placed in the stainless steel high-pressure reactor of 1L with agitator containing the palladium chloride catalyst of palladium amount 265ppm, air in reactor is replaced with carbon monoxide and oxygen mixed gas, then start agitator, build and be depressed into 10kg/cm
2and reactive system is warming up to 80 DEG C, between the reaction period, the volume ratio of oxygen/carbon monoxide is 5/95, and reactor all maintains pressure 10kg/cm
2, sample after reaction carries out 60 minutes, sample is with gas chromatograph analysis.Afterwards, the experimental result together with other embodiment is listed in following table.
(embodiment 1-5)
Repeat the step of comparative example, but add different organic promoters, and the mol ratio making organic promoter and catalyzer is 1: 1, result is as shown in table 1, shows the arrange in pairs or groups productive rate of different promotors of palladium chloride catalyst and all has raising in various degree.
The different organic promoter of table 1 increasing the benefit to diphenyl carbonate productive rate
(embodiment 6-7)
Repeat the step of comparative example, adding organic promoter is 2,1,3-diazosulfide, and react under different reaction pressures, result is as shown in table 2, be presented at after adding organic promoter of the present invention, at various pressures, still can maintain the productive rate higher than original system.
The impact that table 2 pressure generates diphenyl carbonate
| Reaction pressure (kg/cm 2) | Transformation efficiency (%) | Selection rate (%) | Productive rate (%) | |
| Comparative example | 10 | 5.9 | 98.9 | 5.8 |
| Embodiment 1 | 10 | 9.1 | 100 | 9.1 |
| Embodiment 6 | 8 | 8.9 | 97.4 | 8.6 |
| Embodiment 7 | 12 | 9.5 | 99.7 | 9.4 |
(embodiment 8-9)
Repeat the step of comparative example, adding organic promoter is 2,1,3-diazosulfide, and react under different temperature of reaction, result is as shown in table 3, be presented at after adding organic promoter of the present invention, at different temperature, still can maintain the productive rate higher than original system.
Table 3 temperature is on the impact of diphenyl carbonate generation
| Temperature of reaction (DEG C) | Transformation efficiency (%) | Selection rate (%) | Productive rate (%) | |
| Comparative example | 80 | 5.9 | 98.9 | 5.8 |
| Embodiment 1 | 80 | 9.1 | 100 | 9.1 |
| Embodiment 8 | 70 | 8.6 | 99.8 | 8.6 |
| Embodiment 9 | 90 | 6.8 | 99.4 | 6.7 |
(embodiment 10-11)
Repeat the step of comparative example, add organic promoter 2,1,3-diazosulfide, the mol ratio coordinating organic promoter and catalyzer is 1: 1 ~ 5: 1, result is as shown in table 4, under being presented at the mol ratio of different organic promoter and catalyzer, still can obtain the diphenyl carbonate productive rate higher than comparative example.
The impact that the mol ratio of table 4 organic promoter and palladium generates diphenyl carbonate
| Organic promoter/palladium | Transformation efficiency (%) | Selection rate (%) | Productive rate (%) | |
| Comparative example | Without organic promoter | 5.9 | 98.9 | 5.8 |
| Embodiment 1 | 1/1 | 9.1 | 100 | 9.1 |
| Embodiment 10 | 1/2 | 6.4 | 100 | 6.4 |
| Embodiment 11 | 5/1 | 6.7 | 100 | 6.7 |
Claims (9)
1. the preparation method of a diaryl carbonate, in the catalysis system that its organic promoter of arranging in pairs or groups one or more nitrogen-containing heterocycle compounds at use metal halide catalyst forms, oxidation carbonylation is carried out and carbonate synthesis diaryl ester by phenol and carbon monoxide and oxygen, wherein, described organic promoter is for being selected from by 2, 1, 3-diazosulfide, 4-nitro-2, 1, 3-diazosulfide, 4-amido-2, 1, 3-diazosulfide, 5-methyl-2, 1, 3-diazosulfide and 5, 6-dimethyl-2, 1, in the group of 3-diazosulfide composition 2, 1, 3-diazosulfide compounds, and described metal halide catalyst is Palladous chloride.
2. preparation method according to claim 1, wherein, the scope of the mol ratio of described organic promoter and described metal halide catalyst is 10:1 to 1:10.
3. preparation method according to claim 2, wherein, the scope of the mol ratio of described organic promoter and described metal halide catalyst is 5:1 to 1:5.
4. preparation method according to claim 1, wherein, the metal concentration in described metal halide catalyst is 100 ~ 8000ppm.
5. preparation method according to claim 4, wherein, the metal concentration in described metal halide catalyst is 200 ~ 2000ppm.
6. preparation method according to claim 1, wherein, reacts and carries out under the temperature range of 60 ~ 120 DEG C.
7. preparation method according to claim 6, wherein, reacts and carries out under the temperature range of 70 ~ 90 DEG C.
8. preparation method according to claim 1, wherein, reacts at 5 ~ 80kg/cm
2pressure range under carry out.
9. preparation method according to claim 8, wherein, reacts at 6 ~ 12kg/cm
2pressure range under carry out.
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| TW99146247A TWI427061B (en) | 2010-12-28 | 2010-12-28 | Preparation of Diaryl Carbonate |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1227218A (en) * | 1998-02-03 | 1999-09-01 | 通用电气公司 | Method for preparing diaryl carbonates with improved selectivity |
| 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 |
| CN101234965A (en) * | 2007-01-30 | 2008-08-06 | 中国石油化学工业开发股份有限公司 | Method for producing dialkyl carbonate |
| CN102140065A (en) * | 2010-01-29 | 2011-08-03 | 中国石油化学工业开发股份有限公司 | Preparation method of diaryl carbonate |
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| CN1194261A (en) * | 1997-03-24 | 1998-09-30 | 通用电气公司 | Method for preparing diaryl ester carbonate using beta diketone |
| DE10141622A1 (en) * | 2001-08-24 | 2003-03-06 | Bayer Ag | Process for the preparation of diaryl carbonates |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1227218A (en) * | 1998-02-03 | 1999-09-01 | 通用电气公司 | Method for preparing diaryl carbonates with improved selectivity |
| 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 |
| CN101234965A (en) * | 2007-01-30 | 2008-08-06 | 中国石油化学工业开发股份有限公司 | Method for producing dialkyl carbonate |
| CN102140065A (en) * | 2010-01-29 | 2011-08-03 | 中国石油化学工业开发股份有限公司 | Preparation method of diaryl carbonate |
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| TWI427061B (en) | 2014-02-21 |
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