CN102557949A - Process for producing diaryl carbonate - Google Patents
Process for producing diaryl carbonate Download PDFInfo
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- CN102557949A CN102557949A CN2011101132517A CN201110113251A CN102557949A CN 102557949 A CN102557949 A CN 102557949A CN 2011101132517 A CN2011101132517 A CN 2011101132517A CN 201110113251 A CN201110113251 A CN 201110113251A CN 102557949 A CN102557949 A CN 102557949A
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- diazosulfide
- metal halide
- organic promoter
- halide catalyst
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- -1 diaryl carbonate Chemical compound 0.000 title claims abstract description 20
- 238000000034 method Methods 0.000 title abstract description 11
- 230000008569 process Effects 0.000 title description 2
- 238000002360 preparation method Methods 0.000 claims abstract description 20
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000001301 oxygen Substances 0.000 claims abstract description 14
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 14
- 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
- 150000002989 phenols Chemical class 0.000 claims abstract description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 26
- 239000003054 catalyst Substances 0.000 claims description 17
- 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
- 238000006555 catalytic reaction Methods 0.000 claims description 9
- 229910052763 palladium Inorganic materials 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 230000015572 biosynthetic process Effects 0.000 claims description 8
- 230000006315 carbonylation Effects 0.000 claims description 8
- 238000005810 carbonylation reaction Methods 0.000 claims description 8
- 238000003786 synthesis reaction Methods 0.000 claims description 8
- 230000026030 halogenation Effects 0.000 claims description 5
- 238000005658 halogenation reaction Methods 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 4
- 239000005864 Sulphur Substances 0.000 claims description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 125000003368 amide group Chemical group 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- IBGCXOFOCKCBNQ-UHFFFAOYSA-N nitro cyanate Chemical compound [O-][N+](=O)OC#N IBGCXOFOCKCBNQ-UHFFFAOYSA-N 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 abstract description 20
- 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
- 230000002194 synthesizing effect Effects 0.000 abstract 2
- 238000005832 oxidative carbonylation reaction Methods 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 22
- 230000000052 comparative effect Effects 0.000 description 9
- 230000009466 transformation Effects 0.000 description 7
- 239000003513 alkali Substances 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 239000002585 base Substances 0.000 description 5
- 239000006227 byproduct Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 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
- 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
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 208000012839 conversion disease Diseases 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
- 239000002994 raw material Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- FNQJDLTXOVEEFB-UHFFFAOYSA-N 1,2,3-benzothiadiazole Chemical compound C1=CC=C2SN=NC2=C1 FNQJDLTXOVEEFB-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
- 230000004913 activation Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 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
- 150000001408 amides Chemical class 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 238000004458 analytical method Methods 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
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 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
- 230000000994 depressogenic effect Effects 0.000 description 1
- LONDRPCAODOVLM-UHFFFAOYSA-N diphenyl carbonate;phenol Chemical compound OC1=CC=CC=C1.C=1C=CC=CC=1OC(=O)OC1=CC=CC=C1 LONDRPCAODOVLM-UHFFFAOYSA-N 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000007172 homogeneous catalysis Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002808 molecular sieve Substances 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
- 150000003222 pyridines Chemical class 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 238000010405 reoxidation reaction Methods 0.000 description 1
- 238000005070 sampling Methods 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
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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 the carbonate synthesis diaryl ester by phenols and carbon monoxide and oxygen, particularly by the phenol diphenyl carbonate synthesis.
Background technology
Diphenyl carbonate (Diphenyl Carbonate; DPC) be little, the free of contamination organism of a kind of toxicity; And be important engineering plastics midbody; Can be used for the synthetic of many important medicine, agricultural chemicals, other organic cpds and macromolecular material, like monoisocyanates, vulcabond, polycarbonate, gather the carbonyl benzoic acid ester, gather aryl carbonates etc., can also be as the softening agent of polymeric amide and polyester and solvent etc.
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 a method the earliest, also is 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 (USP the 4th; 410; No. 464) or dimethyl oxalate (Japanese Patent 08-325207 number) replace phosgene and phenol to carry out transesterification reaction generation diphenyl carbonate; Be the main flow of present non-phosgene diphenyl carbonate synthesis technology, but, limit the development of this technology because the methylcarbonate price is more expensive.The phenol oxidation carbonylation method is shown below; Directly utilize carbon monoxide, oxygen and phenol one-step synthesis diphenyl carbonate; The by product of following has only water; Thereby have advantages such as reaction process is simple, raw material cheap, cleanliness without any pollution, and be a kind of operational path of very attractive, have good DEVELOPMENT PROSPECT and researching value.
The unusual company of the U.S. is at USP the 4th; 096; Disclose in No. 168 include in the diaryl carbonate technology phenol, carbon monoxide, alkali (base) and oxidation state greater than 0 VIIIB family metallic compound as catalyzer, wherein alkali is main with the amine with steric barrier (sterically hindered).USP the 4th, 096, also disclose in No. 169 this reactive system can have no solvent in the presence of carry out, and with the reactant phenols simultaneously as reactant and solvent; The alkali that also discloses in addition in the catalysis system can be organic or inorganic alkali, like amine of the ammonium of basic metal or alkaline earth metal and oxyhydroxide thereof, level Four and squama, one-level to three grade 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.
USP the 4th; 349; The diaryl carbonate technology that discloses for No. 485 also comprises oxygenant air and redox promotor four tooth base manganese (four tooth manganese, tetradentate manganese, manganese tetradentate) except that comprising phenol, carbon monoxide, alkali and VIIIB family metal; And use molecular sieve and Tetrabutyl amonium bromide respectively as water-removal additive and consisting of phase-transferring agent; After reaction 80 hours, its phenol conversion is about 50%, but initial reaction stage (1～3 hour) phenol conversion then is lower than 5%.
USP the 5th, 132 then uses the homogeneous catalysis system of palladium/Cobaltous diacetate/Tetrabutyl amonium bromide and adds benzoquinones for No. 477, through under high pressure conditions (top pressure reaches 2050psi) promote the diphenyl carbonate productive rate.USP the 5th; 284; Find that as Primary Catalysts, 2-salicylic aldehyde-3,3 '-two amidos-N-methyl dipropylamine cobalt (CoSMDPT) is as inorganic promotor, tetraalkyl brometo de amonio or the six alkyl bromination guanidinesalts source as bromide with palladium in the presence of organic promoter three pyridines for No. 964; (top pressure reaches 1600psi) introduced fixing carbon monoxide and the oxygen of forming under high pressure, can make the productive rate of diphenyl carbonate reach 45%.For obtaining commercialization still acceptable response speed and selection rate, carbon monoxide and the oxygen that must under high pressure introduce definite composition carry out this reaction, but under the situation that the reaction stagnation pressure improves constantly, increase business-like facility investment expense greatly.
No. the 350th, 700, European patent as inorganic promotor, adds quinone or Resorcinol as Electron-Transfer Catalyst with cobalt salt.But in this technology, remove Electron-Transfer Catalyst and need spend sizable expense.2 OH bases that Resorcinol provides also can make phenol form the by product of carbonates, and the cost that removes this by product is big, and Electron-Transfer Catalyst repeateds use of can't regenerating, and production of by-products makes selection rate descend, the economical load increase.
USP the 5th, 498, in No. 742 with palladium bromide/Tetrabutyl amonium bromide/manganese acetylacetonate/sodium phenylate as catalysis system, because of its catalyzer needs earlier also not meet economic benefit with a large amount of carbon monoxide activation.
And the development of supported catalyst such as Takagi et a1. (J.Mol.Catal.A:Chem.129 (1998) L1) are main catalyzer with 5%Pd/C, and PbO is a pro-oxidant, can get 9.55% diphenyl carbonate productive rate.The more loaded Pd catalyzer 5%Pd/C of Song et al. (J.Mol.Catal.A:Chem.154 (2000) 243), Pd/Al in addition
2O
3, Pd/SiO
2With the catalytic activity of Pd/MgO, find that activity carbon carrier is superior to other carrier.Because the carrying out of water meeting inhibited reaction, and Al
2O
3, SiO
2Then have hydrophobicity with oxide carrier such as MgO because of having carbonyl to exist to make its possess hydrophilic property, activity carbon carrier on the surface, so activity carbon carrier helps reaction on the contrary.But above both reaction pressures 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 provides a kind of preparation method who has the diaryl carbonate of high reaction conversion ratio under than low reaction pressure.
Another object of the present invention provides a kind of preparation method with diaryl carbonate of high reaction preference.
A purpose more of the present invention provides a kind of preparation method with diaryl carbonate of high reaction conversion property.
Another purpose of the present invention provides a kind of preparation method that can improve the diaryl carbonate of productive rate.
For reaching above-mentioned and other purpose; Preparing method according to diaryl carbonate provided by the present invention; Be in the catalysis system that uses VIIIB family at least a or multiple nitrogen-containing heterocycle compound of metal halide catalyst collocation to form as organic promoter; Make phenolic cpd, carbon monoxide and oxygen carry out oxidation carbonylation and generate diaryl carbonate, thereby can improve the transformation efficiency and the selectivity of catalyzed reaction, and improve the W-response productive rate.
Especially, the present invention is through using the catalysis system of one or more nitrogen-containing heterocycle compounds of halogenation palladium catalyst collocation as organic promoter, the oxidation carbonylation of catalysis of phenol and diphenyl carbonate synthesis.
Being characterized as of the preparation method of diaryl carbonate of the present invention comprises following ingredients in the medium of its oxidation carbonylation: (1) metal halide catalyst, (2) phenolic cpd, (3) alkali, (4) inorganic promotor, (5) halogenation quarternary ammonium salt, (6) carbon monoxide, (7) oxygen, (8) organic promoter.Wherein, this phenolic cpd especially is a phenol; 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
4The hydrogen of respectively doing for oneself, straight or branched C
1-12Alkyl, C
3-12Naphthenic base, C
3-12Aralkyl, C
3-12Aryl, C
3-12Alkaryl, halogen, nitro, cyanic acid, amido contains the C of oxygen, sulphur, nitrogen or carboxyl
1-10Alkyl, C
1-10Aralkyl, C
1-10Naphthenic base, C
1-10Aryl or C
1-10Alkaryl, or contain the salt of oxygen, sulphur, nitrogen or carboxyl.
Especially, this organic promoter is 2,1,3-diazosulfide class nitrogen-containing heterocycle compound, and this 2,1, the instance of 3-diazosulfide class organic promoter comprises; But non-being confined to, 2,1, the 3-diazosulfide (2,1,3-benzothiadiazole), 4-nitro-2; 1, and the 3-diazosulfide (4-nitro-2,1,3-benzothiadiazole), 4-amido-2,1,3-diazosulfide (4-amino-2; 1,3-benzothiadiazole), 5-methyl-2,1, the 3-diazosulfide (5-methyl-2,1,3-benzothiadiazole) with 5; 6-dimethyl--2,1, and the 3-diazosulfide (5,6-dimethyl-2,1,3-benzothiadiazole).
According to a specific embodiment of the present invention; Catalysis system is by metal halide; Halogenation palladium (for example Palladous chloride) particularly; One or more nitrogen-containing heterocycle compounds of arranging in pairs or groups are formed as organic promoter, in the 1L high-pressure reactor, carry out oxidation carbonylation and diphenyl carbonate synthesis by phenol.The TR that this reaction is carried out is 60～120 ℃, is preferably 70～90 ℃ that 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 be 10: 1 to 1: 10, be preferably 5: 1 to 1: 5, the metal concentration scope of catalyzer is 100～8000ppm, be preferably 200～2000ppm.
Below further specify characteristics of the present invention and effect through particular specific embodiment, but it is not to be used to limit scope of the present 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 gram (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), the palladium chloride catalyst that contains palladium amount 265ppm are placed the stainless steel high-pressure reactor with the 1L of whisking appliance; Air in the reactor drum is with carbon monoxide and oxygen mixed gas displacement; Then start whisking appliance, 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 drum all maintains pressure 10kg/cm
2, sampling after reaction is carried out 60 minutes, sample is with the gas chromatograph analysis.Afterwards, will list in following each table together with the experimental result of other embodiment.
(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 that the result is as shown in table 1, show that the arrange in pairs or groups productive rate of different promotors of palladium chloride catalyst all has raising in various degree.
The different organic promoters of table 1 increasing the benefit to the diphenyl carbonate productive rate
(embodiment 6-7)
Repeat the step of comparative example, adding organic promoter is 2,1; The 3-diazosulfide, and under different reaction pressures, react, the result is as shown in table 2; After being presented at interpolation organic promoter of the present invention, under different pressure, still can keep the productive rate higher than original system.
The influence 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; The 3-diazosulfide, and under different temperature of reaction, react, the result is as shown in table 3; After being presented at interpolation organic promoter of the present invention, under different temperature, still can keep the productive rate higher than original system.
Table 3 temperature is to the influence of diphenyl carbonate generation
| Temperature of reaction (℃) | 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, the 3-diazosulfide; Cooperating the mol ratio of organic promoter and catalyzer is 1: 1～5: 1; The result is as shown in table 4, is presented under the mol ratio of different organic promoters and catalyzer, still can obtain the diphenyl carbonate productive rate higher than comparative example.
The influence 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 | No 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 (12)
1. the preparation method of a diaryl carbonate; It carries out oxidation carbonylation and the carbonate synthesis diaryl ester by phenols and carbon monoxide and oxygen in the catalysis system that the organic promoter that uses one or more nitrogen-containing heterocycle compounds of metal halide catalyst collocation is formed.
2. preparation method according to claim 1, wherein, said metal halide catalyst is the halogenation palladium.
3. preparation method according to claim 1 and 2, wherein, said organic promoter is one or more nitrogen-containing heterocycle compounds that is expressed from the next:
In following formula, R
1～R
4The hydrogen of respectively doing for oneself, straight or branched C
1-12Alkyl, C
3-12Naphthenic base, C
3-12Aralkyl, C
3-12Aryl, C
3-12Alkaryl, halogen, nitro, cyanic acid, amido contains the C of oxygen, sulphur, nitrogen or carboxyl
1-10Alkyl, C
1-10Aralkyl, C
1-10Naphthenic base, C
1-10Aryl or C
1-10Alkaryl, or contain the salt of oxygen, sulphur, nitrogen or carboxyl.
4. preparation method according to claim 3, wherein, said 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; 1,2,1 in the group that the 3-diazosulfide is formed, 3-diazosulfide compounds.
5. preparation method according to claim 1, wherein, the scope of the mol ratio of said organic promoter and said metal halide catalyst is 10: 1 to 1: 10.
6. preparation method according to claim 5, wherein, the scope of the mol ratio of said organic promoter and said metal halide catalyst is 5: 1 to 1: 5.
7. preparation method according to claim 1, wherein, the metal concentration in the said metal halide catalyst is 100～8000ppm.
8. preparation method according to claim 7, wherein, the metal concentration in the said metal halide catalyst is 200～2000ppm.
9. preparation method according to claim 1 wherein, is reflected under 60～120 ℃ the TR and carries out.
10. preparation method according to claim 9 wherein, is reflected under 70～90 ℃ the TR and carries out.
11. preparation method according to claim 1 wherein, is reflected at 5～80kg/cm
2Pressure range under carry out.
12. preparation method according to claim 11 wherein, is reflected 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 |
| TW099146247 | 2010-12-28 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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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 |
|---|---|---|---|---|
| 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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| CN102557949B (en) | 2014-12-31 |
| TW201226389A (en) | 2012-07-01 |
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