CN1227218A - Process for the preparation of diaryl carbonates with improved selectivity - Google Patents
Process for the preparation of diaryl carbonates with improved selectivity Download PDFInfo
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- CN1227218A CN1227218A CN99101728A CN99101728A CN1227218A CN 1227218 A CN1227218 A CN 1227218A CN 99101728 A CN99101728 A CN 99101728A CN 99101728 A CN99101728 A CN 99101728A CN 1227218 A CN1227218 A CN 1227218A
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- Prior art keywords
- polyaniline
- palladium
- bromide
- compound
- carbon monoxide
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- 238000000034 method Methods 0.000 title claims abstract description 37
- -1 diaryl carbonates Chemical class 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 6
- 229920000767 polyaniline Polymers 0.000 claims abstract description 30
- 239000000203 mixture Substances 0.000 claims abstract description 21
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical group [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052751 metal Inorganic materials 0.000 claims abstract description 15
- 239000003054 catalyst Substances 0.000 claims abstract description 13
- 150000001875 compounds Chemical class 0.000 claims abstract description 13
- 150000003839 salts Chemical class 0.000 claims abstract description 13
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 12
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims abstract description 10
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 10
- 239000001301 oxygen Substances 0.000 claims abstract description 10
- 239000011230 binding agent Substances 0.000 claims abstract description 4
- 229920000642 polymer Polymers 0.000 claims abstract description 3
- 125000001453 quaternary ammonium group Chemical group 0.000 claims abstract description 3
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 14
- 229910052763 palladium Inorganic materials 0.000 claims description 8
- 238000005810 carbonylation reaction Methods 0.000 claims description 7
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical group Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 5
- MUJIDPITZJWBSW-UHFFFAOYSA-N palladium(2+) Chemical compound [Pd+2] MUJIDPITZJWBSW-UHFFFAOYSA-N 0.000 claims description 5
- 230000002378 acidificating effect Effects 0.000 claims description 3
- 230000006315 carbonylation Effects 0.000 claims description 3
- 150000002941 palladium compounds Chemical class 0.000 claims description 3
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 2
- 229910052783 alkali metal Inorganic materials 0.000 claims description 2
- PMOIAJVKYNVHQE-UHFFFAOYSA-N phosphanium;bromide Chemical compound [PH4+].[Br-] PMOIAJVKYNVHQE-UHFFFAOYSA-N 0.000 claims description 2
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 2
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical group [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims 2
- JFJNVIPVOCESGZ-UHFFFAOYSA-N 2,3-dipyridin-2-ylpyridine Chemical compound N1=CC=CC=C1C1=CC=CN=C1C1=CC=CC=N1 JFJNVIPVOCESGZ-UHFFFAOYSA-N 0.000 claims 1
- 239000012736 aqueous medium Substances 0.000 claims 1
- SUHYKYPAFONDDV-UHFFFAOYSA-M bis(diethylamino)methylidene-diethylazanium;bromide Chemical compound [Br-].CCN(CC)C(N(CC)CC)=[N+](CC)CC SUHYKYPAFONDDV-UHFFFAOYSA-M 0.000 claims 1
- 150000001805 chlorine compounds Chemical group 0.000 claims 1
- 230000001590 oxidative effect Effects 0.000 claims 1
- LXNAVEXFUKBNMK-UHFFFAOYSA-N palladium(II) acetate Substances [Pd].CC(O)=O.CC(O)=O LXNAVEXFUKBNMK-UHFFFAOYSA-N 0.000 claims 1
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 claims 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 abstract description 6
- ROORDVPLFPIABK-UHFFFAOYSA-N diphenyl carbonate Chemical compound C=1C=CC=CC=1OC(=O)OC1=CC=CC=C1 ROORDVPLFPIABK-UHFFFAOYSA-N 0.000 abstract description 3
- 125000004185 ester group Chemical group 0.000 abstract description 2
- 150000001649 bromium compounds Chemical class 0.000 abstract 1
- 150000004820 halides Chemical group 0.000 abstract 1
- 150000002440 hydroxy compounds Chemical class 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 9
- 238000003756 stirring Methods 0.000 description 8
- 102000040350 B family Human genes 0.000 description 7
- 108091072128 B family Proteins 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000012153 distilled water Substances 0.000 description 6
- 230000003647 oxidation Effects 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 6
- 239000002002 slurry Substances 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 4
- 125000001931 aliphatic group Chemical group 0.000 description 4
- 230000031709 bromination Effects 0.000 description 4
- 238000005893 bromination reaction Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229960003280 cupric chloride Drugs 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000002808 molecular sieve Substances 0.000 description 3
- 229920000515 polycarbonate Polymers 0.000 description 3
- 239000004417 polycarbonate Substances 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical group [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 3
- 239000004160 Ammonium persulphate Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- 235000019395 ammonium persulphate Nutrition 0.000 description 2
- ZSZGLSAHRNYXPR-UHFFFAOYSA-N bis(diethylamino)methylidene-diethylazanium Chemical compound CCN(CC)C(N(CC)CC)=[N+](CC)CC ZSZGLSAHRNYXPR-UHFFFAOYSA-N 0.000 description 2
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical class [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000002932 luster Substances 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- DZLFLBLQUQXARW-UHFFFAOYSA-N tetrabutylammonium Chemical compound CCCC[N+](CCCC)(CCCC)CCCC DZLFLBLQUQXARW-UHFFFAOYSA-N 0.000 description 2
- MNAHQWDCXOHBHK-UHFFFAOYSA-N 1-phenylpropane-1,1-diol Chemical compound CCC(O)(O)C1=CC=CC=C1 MNAHQWDCXOHBHK-UHFFFAOYSA-N 0.000 description 1
- CJWNFAKWHDOUKL-UHFFFAOYSA-N 2-(2-phenylpropan-2-yl)phenol Chemical compound C=1C=CC=C(O)C=1C(C)(C)C1=CC=CC=C1 CJWNFAKWHDOUKL-UHFFFAOYSA-N 0.000 description 1
- AUFVJZSDSXXFOI-UHFFFAOYSA-N 2.2.2-cryptand Chemical compound C1COCCOCCN2CCOCCOCCN1CCOCCOCC2 AUFVJZSDSXXFOI-UHFFFAOYSA-N 0.000 description 1
- KLSLBUSXWBJMEC-UHFFFAOYSA-N 4-Propylphenol Chemical compound CCCC1=CC=C(O)C=C1 KLSLBUSXWBJMEC-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical class NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- NSOXQYCFHDMMGV-UHFFFAOYSA-N Tetrakis(2-hydroxypropyl)ethylenediamine Chemical compound CC(O)CN(CC(C)O)CCN(CC(C)O)CC(C)O NSOXQYCFHDMMGV-UHFFFAOYSA-N 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
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- MDFFNEOEWAXZRQ-UHFFFAOYSA-N aminyl Chemical compound [NH2] MDFFNEOEWAXZRQ-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 150000004700 cobalt complex Chemical class 0.000 description 1
- 229910000001 cobalt(II) carbonate Inorganic materials 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 150000001896 cresols Chemical class 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 150000002171 ethylene diamines Chemical class 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- AWJUIBRHMBBTKR-UHFFFAOYSA-N iso-quinoline Natural products C1=NC=CC2=CC=CC=C21 AWJUIBRHMBBTKR-UHFFFAOYSA-N 0.000 description 1
- 150000003956 methylamines Chemical class 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 1
- 150000003003 phosphines Chemical class 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920002959 polymer blend Polymers 0.000 description 1
- 229920006380 polyphenylene oxide Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000003222 pyridines Chemical class 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 125000004151 quinonyl group Chemical group 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- 125000002256 xylenyl group Chemical class C1(C(C=CC=C1)C)(C)* 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/96—Esters of carbonic or haloformic acids
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
诸如碳酸二苯酯之类的碳酸二芳酯的制备方法，包括：在下述催化剂组合物存在下使诸如苯酚之类的羟基化合物与氧和一氧化碳进行反应；所述催化剂组合物包含诸如钯之类的ⅧB族金属元素或其化合物，诸如季铵或六烷基鈲的溴化物之类的溴化物源和处于部分氧化与部分还原态的聚苯胺。优选聚苯胺是搀入卤化物的，且呈与含有醚基或酯基的粘结剂聚合物和形成配合物的盐的共混物的形式。Process for the preparation of diaryl carbonates such as diphenyl carbonate, comprising: reacting a hydroxy compound such as phenol with oxygen and carbon monoxide in the presence of a catalyst composition comprising, for example, palladium Group VIIIB metal elements or their compounds, bromide sources such as quaternary ammonium or hexaalkylguanidine bromides, and polyaniline in partially oxidized and partially reduced states. Preferably the polyaniline is halide doped and in a blend with a binder polymer containing ether or ester groups and a complex forming salt.
Description
Background of invention
The present invention relates to prepare the method for diaryl carbonate by carbonylation.Specifically, the present invention relates in carbonylation reaction, use the catalyst composition of simplifying.
Diaryl carbonate is by carrying out the valuable intermediate that transesterify prepares polycarbonate with the fusion bisphenol compound.This method for preparing polycarbonate than use the toxic gas phosgene as reactant, use such as the environmentally harmful chlorination aliphatic hydrocrbon of methylene dichloride and have the advantage that helps environment protection as the method for solvent.
The method that various carbonylation reactions by hydroxy aromatic compound and carbon monoxide and oxygen prepare diaryl carbonate is disclosed.In general, carbonylation reaction needs quite complicated catalyzer.Referring to, for example, United States Patent (USP) 5,231,210,5,284,964 and 5,399,734 and the common unsettled application serial no of owning together [RD-25582].Wherein said catalyst composition comprises the VIII B family metal metal of ruthenium, rhodium, palladium, osmium, iridium and platinum (that is: be selected from) or its title complex.They be used in combination such as bromide source such as bromination tetra-n-butyl ammonium and bromination Hexaethyl Guanidinium.
According to above listed patent and application, need other catalyst component.They comprise inorganic promotor, be typically, cobalt (II) salt and the title complex that can form the organic compound of title complex, the five tooth title complexs that particularly are mated, representational this class organic compound is a nitrogen-containing heterocycle compound, comprising: pyridines, bipyridyliums, terpyridyl, quinoline, iloquinoline derivative and diquinolyl class, aliphatic polyamines class such as quadrol and tetraalkyl ethylenediamines, crown ether-like, aromatics or aliphatic amidogen ether such as kryptofix 222 (cryptanes) and Schiff's base.Particularly preferred inorganic promotor is the title complex of cobalt (II) and two [3-(salicylic aldehyde amino) propyl group] methylamines in many examples.
Organic promoter also is necessary.They can comprise various terpyridyls, phenanthroline, quinoline and isoquinoline compound, comprising: 2,2 ': 6 ', 2 " terpyridyl, 4 '-methylthio group-2; 2 ': 6 ', 2 " terpyridyl and 2,2 ': 6 ', 2 " terpyridyl N-oxide compound; 1,10-phenanthroline, 2,4; 7,8-tetramethyl--1,10-phenanthroline, 4; 7-phenylbenzene-1,10-phenanthroline and 3,4; 7,8-tetramethyl--1,10-phenanthroline.General terpyridyl preferably, particularly 2,2 ': 6 ', 2 " terpyridyls.
Comprising in the presence of the catalyst composition of less composition, and particularly, it is desirable carrying out carbonylation reaction in the presence of the catalyst composition that does not need to comprise than expensive cobalt complex and terpyridyl.The present invention relates to the application of this catalyst composition.
Summary of the invention
The present invention is a kind of method for preparing diaryl carbonate, this method comprises: significant quantity concerning carbonylation at least a except comprising VIII B family's metallic element and compound thereof, do not contain other metallic elements, do not contain in the presence of the catalyst composition of terpyridyl yet, at least a hydroxy aromatic compound is contacted with oxygen and carbon monoxide, described catalystic material comprises VIII B family's metallic element or its compound, bromide source and the polyaniline that is in partial oxidation and partial reduction attitude.
Describe in detail; Preferred embodiment
Can use any hydroxy aromatic compound in the present invention.General preferred monohydroxyaromatic compound, for example phenol, cresols, xylenol and to cumyl phenol, most preferably phenol.Yet the present invention also can use dihydroxy aromatic compounds, for example; Resorcinol, Resorcinol and 2, two (4-hydroxy phenyl) propane of 2-or " dihydroxyphenyl propane ", this moment, product was a polycarbonate.
The basic reagent of other that uses in the method for the present invention is oxygen and carbon monoxide, and they and phenol reactant form needed diaryl carbonate.
Catalyst composition basal component is one of VIII B family metallic element used according to the present invention, is preferably palladium or its compound.Therefore, what be fit to is palladium black or is deposited on element palladium on the carbon, and palladium compound, the salt that forms as halogenide, nitrate, carboxylate salt, with aliphatic beta-diketon and comprise title complex such as the compounds of carbon monoxide, amine, phosphine class and alkene.Preferred organic acid the most often is C in most of examples
2～6The palladium of aliphatic carboxylic acid (II) salt and such as 2, the palladium of the beta-diketon of 4-diacetylmethane and so on (II) salt.General palladium (II) and 2 most preferably, 4-diacetylmethane palladium (II).
Catalytic material also contains bromide source.It can be quaternary ammonium or quaternary phosphonium bromide, perhaps six alkyl Guanidinium bromides.Often preferred Guanidinium salt; Comprise α, ω-two (five alkyl Guanidinium) alkane salts.Particularly preferably be the salt that contains 2～6 carbon atoms in the alkyl, particularly bromination tetra-n-butyl ammonium and bromination Hexaethyl Guanidinium.
According to the basic catalyst component of another kind of the present invention is the polyaniline of partial oxidation and partial reduction attitude.Polyaniline is well known in the art.This compound can prepare the aniline oxidation by electrochemistry or chemical process.
The typical method of preparation polyaniline is in water medium, in the presence of the acidic cpd that is fit to such as hydrofluoric acid or spirit of salt, to make the aniline oxidation with ammonium persulphate.When using spirit of salt, the pH of water medium is quite low, is generally below 1.0.This method is described in the Indian patent application of the S.Radhakrishnan that submitted in 1997 and S.Unde, and its exercise question is " being applied to the preparation method of the electrically conductive polyaniline of chemical-sensitive element ".It provides the polyaniline as partial oxidation and partial reduction material uniquely, wherein has and contains-C
6H
4The alternative quinonyl that the reduction of NH-structural unit part (about 40～60% weight) and containing is separated by trivalent nitrogen atom and the oxidized portion of phenylene.
One of the characteristic that occupies the polyaniline of critical role in the present invention is to have higher electroconductibility.But, often find that Zhi Bei polyaniline has the low electric conductivity that does not meet the requirements as stated above.
So, for the present invention, usually preferred use by slightly different method synthetic dope halid, particularly dope muriatic polyaniline composition, the step of described method comprises: the oxygenizement under low pH, with inert binder blend and coordination.In the method, aniline being dissolved in the acidic medium, generally is the spirit of salt aqueous solution, its pH scope is about 3.0～4.5, adds the oxygenant that is fit to again, generally is alkali-metal persulphate or iron(ic) chloride, general preferred as alkali persulphate, particularly Sodium Persulfate.The polyaniline that contains additive can be precipitated out from the gained reaction mixture when leaving standstill.Employing generally comprises filters and the exsiccant usual way, and it is separated.Then with itself and the binder polymer blend that contains ether or ester group; The polymkeric substance that is fit to comprises polyoxygenated alkane polyphenylene oxide and acrylate addition polymer.Resulting polymeric blends is dissolved in the suitable solvent; Mix with salt, for example cupric chloride with its formation title complex; Stirring is until obtaining the heavy-gravity slurry.This slurry can be used as catalyst component.
Following example explanation is as the polyaniline preparation of compositions method of catalyst component.
Example 1
10ml (milliliter) aniline is added drop-wise to the dense spirit of salt of 5.5g (gram) in the mixture of 150ml distilled water, the while vigorous stirring, formation pH is 4.3 transparent liquid.Slowly add the solution of 5.3g ammonium persulphate in 100ml water, stir simultaneously, allow reaction mixture at room temperature leave standstill 20 hours, so separate out a large amount of green brown precipitates.This mixture is poured into makes polyaniline precipitation in the 1000ml distilled water.
Sedimentary polyaniline is filtered, with distilled water wash several times, dry then.With its sample of 200mg (milligram) and 800mg molecular weight is about 3000 polyethylene oxide and the 20ml methanol mixed that contains the 80mg cupric chloride.This solution of vigorous stirring is until the thickness slurry that forms even color and luster and denseness.This slurry is the muriatic polyaniline of doping of needed partial reduction.
Example 2
9.3ml aniline is added drop-wise to the dense spirit of salt of 5.5g in the mixture of 150ml distilled water, the while vigorous stirring, formation pH is 3.8 transparent liquid.Slowly add the solution of 3.2g iron(ic) chloride in 20ml water, stir simultaneously, allow reaction mixture at room temperature leave standstill 24 hours, so separate out a large amount of light green precipitations.This mixture is poured into makes polyaniline precipitation in the 1000ml distilled water.
Sedimentary polyaniline is filtered, with distilled water wash several times, dry then.With its sample of 200mg (milligram) and 800mg molecular weight is about 3000 polyethylene oxide and the 20ml methanol mixed that contains the 80mg cupric chloride.This solution of vigorous stirring is until the thickness slurry that forms even color and luster and denseness.This slurry is the muriatic polyaniline of doping of needed partial reduction.
The ratio in employed in the method for the invention VIII B family metallic element source is, is enough to for per 800～10,000, preferred 2,000～5, and 000mol (mole) hydroxy aromatic compound provides the amount of about 1 grammeatom metallic element.Concerning every grammeatom VIII B family metallic element, use about 5～150, preferred about 20～50mol bromide source usually.The scope of the weight ratio of polyaniline and VIII B family metallic element compound is generally about 0.2～5.0: 1.
Infeed gas in reaction mixture, its ratio is about 2～50% (mole) oxygen, and rest part is a carbon monoxide.Gas can add respectively or add with the form of mixture, to the total pressure scope be about 10～250 normal atmosphere.General range of reaction temperature is about 60～150 ℃.In reaction vessel, can there be siccative.It generally is molecular sieve.For reaction is carried out as quickly as possible, preferably keep reaction pressure, till hydroxy aromatic compound transforms fully according to above-mentioned United States Patent (USP) 5,399,734.
The diaryl carbonate that generates by method of the present invention can adopt traditional method to separate.Often preferably form and the adducts of pyrolysis diaryl carbonate and hydroxy aromatic compound, as at United States Patent (USP) 5,239,106 and 5,312, such described in 955.
Following example explanation the present invention.
Example 3～5
In each high-pressure reactor (50ml volume), add each batch reaction thing, palladium (II) that reactant consists of about 20g phenol, 800mg Tetrabutylammonium bromide and different amounts and the polyaniline similar to example 1, described polyaniline is 50% reduction and 50% oxidation state, and its molecular weight is about 3380.The activation 3A type molecular sieve that about 4.5g is fresh places the basket that is fixed on each reactor head.
With the reactor sealing, with carbon monoxide cleaning twice,, be heated to 100 ℃, simultaneously vigorous stirring with 66.3 normal atmosphere carbon monoxide and 5.1 normal atmosphere oxygen superchargings.Fall the monitoring reaction process by record still internal pressure, and with gas make-up pressure, its condition is a carbon monoxide to the ratio of oxygen is necessary 2: 1.When reaction is finished,, and analyze the cooling of the material in the reactor.It the results are shown in the following table." phenol conversion " is the ratio that is converted into the phenol of product, and " selectivity " (for diphenyl carbonate) is to be the percent value of the diphenyl carbonate that is generated of benchmark in the total reaction product.
| Example 345 | |
| Phenol, g palladium (II), the mg polyaniline, the mg molecular sieve, the g reaction times, hour phenol conversion, the % selectivity, % | ?20.845????21.09????19.63 ?22????????22???????44 ?50????????9????????10 ?4.56??????4.0??????4.0 ?9?????????8????????8 ?25????????13.6?????47.2 ?40????????52???????6.0 |
Claims (17)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| IN175/CAL/98 | 1998-02-03 | ||
| IN175CA1998 | 1998-02-03 |
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| Publication Number | Publication Date |
|---|---|
| CN1227218A true CN1227218A (en) | 1999-09-01 |
| CN1161320C CN1161320C (en) | 2004-08-11 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB991017285A Expired - Fee Related CN1161320C (en) | 1998-02-03 | 1999-02-01 | Process for the preparation of diaryl carbonates with improved selectivity |
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| Country | Link |
|---|---|
| JP (1) | JPH11279114A (en) |
| KR (1) | KR19990072367A (en) |
| CN (1) | CN1161320C (en) |
| AR (1) | AR016018A1 (en) |
| BR (1) | BR9900615A (en) |
| ZA (1) | ZA99367B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102557949A (en) * | 2010-12-28 | 2012-07-11 | 中国石油化学工业开发股份有限公司 | Process for producing diaryl carbonate |
| US12006299B2 (en) | 2019-09-05 | 2024-06-11 | Shell Usa, Inc. | Process and system for the production of ethylene carbonate and/or ethylene glycol |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2466123C2 (en) * | 2007-08-14 | 2012-11-10 | Шелл Интернэшнл Рисерч Маатсхаппий Б.В. | Method of producing alkylene glycol |
-
1999
- 1999-01-18 AR ARP990100182A patent/AR016018A1/en unknown
- 1999-01-19 ZA ZA9900367A patent/ZA99367B/en unknown
- 1999-01-27 JP JP11017856A patent/JPH11279114A/en active Pending
- 1999-02-01 CN CNB991017285A patent/CN1161320C/en not_active Expired - Fee Related
- 1999-02-02 BR BR9900615-4A patent/BR9900615A/en not_active IP Right Cessation
- 1999-02-02 KR KR1019990003345A patent/KR19990072367A/en not_active Application Discontinuation
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102557949A (en) * | 2010-12-28 | 2012-07-11 | 中国石油化学工业开发股份有限公司 | Process for producing diaryl carbonate |
| CN102557949B (en) * | 2010-12-28 | 2014-12-31 | 中国石油化学工业开发股份有限公司 | Process for producing diaryl carbonate |
| US12006299B2 (en) | 2019-09-05 | 2024-06-11 | Shell Usa, Inc. | Process and system for the production of ethylene carbonate and/or ethylene glycol |
Also Published As
| Publication number | Publication date |
|---|---|
| ZA99367B (en) | 1999-07-19 |
| JPH11279114A (en) | 1999-10-12 |
| AR016018A1 (en) | 2001-05-30 |
| BR9900615A (en) | 2000-04-11 |
| CN1161320C (en) | 2004-08-11 |
| KR19990072367A (en) | 1999-09-27 |
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