EP0000880B1 - Procédé pour préparer des carbonates aromatiques - Google Patents

Procédé pour préparer des carbonates aromatiques Download PDF

Info

Publication number
EP0000880B1
EP0000880B1 EP78100571A EP78100571A EP0000880B1 EP 0000880 B1 EP0000880 B1 EP 0000880B1 EP 78100571 A EP78100571 A EP 78100571A EP 78100571 A EP78100571 A EP 78100571A EP 0000880 B1 EP0000880 B1 EP 0000880B1
Authority
EP
European Patent Office
Prior art keywords
methanol
dimethyl carbonate
transesterification
azeotrope
acid esters
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired
Application number
EP78100571A
Other languages
German (de)
English (en)
Other versions
EP0000880A1 (fr
Inventor
Heinrich Dr. Krimm
Hans-Josef Dr. Buysch
Hans Dr. Rudolph
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Bayer AG
Original Assignee
Bayer AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Bayer AG filed Critical Bayer AG
Publication of EP0000880A1 publication Critical patent/EP0000880A1/fr
Application granted granted Critical
Publication of EP0000880B1 publication Critical patent/EP0000880B1/fr
Expired legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C68/00—Preparation of esters of carbonic or haloformic acids
    • C07C68/06—Preparation of esters of carbonic or haloformic acids from organic carbonates

Definitions

  • the invention relates to a process for the preparation of aromatic carbonic acid esters from dimethyl carbonate and phenols by transesterification.
  • transesterification of aliphatic carbonic acid esters with phenols in the presence of strong bases or of alkali compounds is known according to DBP 971 790, 1 020 184, 1 026 958 and 1 031 512.
  • Transesterification processes catalyzed in this way have the disadvantage of not being very selective, since considerable amounts of carbon dioxide are released in a side reaction.
  • DE-OS 2 528 412 describes a corresponding transesterification process for the preparation of aromatic carbonic acid esters in the presence of Lewis acids, i.e. Transition metal halides, or the corresponding acyloxy, alkoxy or aryloxy compounds described as catalysts.
  • Lewis acids i.e. Transition metal halides
  • acyloxy, alkoxy or aryloxy compounds described as catalysts.
  • a complex cleaning and separation operation must be carried out to obtain pure dimethyl carbonate (USP 3803201, DBP 2450856 and DE-OS 2 607 003), since in the known production processes of dimethyl carbonate (USP 2 642 858 and DE -OS 2 615 665) an approximately 30% by weight azeotrope with methanol is obtained.
  • dimethyl carbonate is thus transesterified with phenols to give the corresponding aromatic carbonates, transesterification catalysts being present.
  • Example 9 is carried out in the presence of n-hexane and an azeotrope of hexane, dimethyl carbonate and methyl alcohol is distilled off from the mixture of dimethyl carbonate, phenol, hexane and methyl alcohol. The consequence of this is that hexane and dimethyl carbonate have to be supplied continuously. In other words, with the methyl alcohol to be removed from the reaction, hexane and dimethyl carbonate are also separated, which is actually undesirable.
  • the task was therefore to find a transesterification process which allows the use of this azeotrope or another mixture of dimethyl carbonate and methanol.
  • concentration of dimethyl carbonate in methanol is in the range from 95 to 10% by weight.
  • the technically important 30% by weight azeotrope is preferred.
  • the invention therefore relates to a process for the preparation of aromatic carbonic acid esters by transesterification of dimethyl carbonate with phenols with the elimination of methanol in the presence of transesterification catalysts, which is characterized in that mixtures of dimethyl carbonate / methanol and methanol-immiscible azeotrope formers for methanol are used for the transesterification.
  • Azeotropic agents suitable according to the invention are preferably saturated aliphatic hydrocarbons with C 5 C 8 and with boiling points of 40-130 ° C, such as pentane, hexane, heptane, octane and isooctane, and also technical gasoline fractions which predominantly contain the hydrocarbons mentioned, such as petroleum ether, ligroin and Light petrol, as well as mixtures of the hydrocarbons mentioned.
  • the azeotroping agents are expediently used at least in an amount which is sufficient to distill over both the mixture introduced with the dimethyl carbonate / methano) mixture and the methanol formed during the transesterification.
  • the amount of azeotroping agent to be added can be found in the known tables (e.g. in Handbook of Chemistry and Physics, 51st Edit. (1970), the Rubber Comp., Cleveland / Ohio) with the information about the respective azeotrope compositions or can be determined by simple preliminary tests. An excess of azeotrope does not harm, it can only be kept as low as possible in the interest of an economic energy balance.
  • the process according to the invention succeeds in separating the azeotrope formed from the methanol formed during the transesterification reaction and one of the hydrocarbons mentioned, although these hydrocarbons are also known to form azeotropic-boiling mixtures with dimethyl carbonate.
  • the process of the invention achieves practically the same yields as in the known process without the dimethyl carbonate used having to be isolated before the transesterification reaction.
  • Suitable phenols are preferably compounds of the general formula (I) in which X is hydrogen, an alkyl radical with C, -C 3 , a halogen atom, preferably chlorine, or a nitro group and n is 1 or 2, phenol, o, m, p-cresol, o, m, p are particularly preferred -Chlorphenol, o, m, p-ethylphenol, o, m, p-propylphenol, o, m, p-nitrophenol, 2e-dimethylphenol, 2,4-dimethylphenol or 3,4-dimethylphenol used.
  • X is hydrogen, an alkyl radical with C, -C 3 , a halogen atom, preferably chlorine, or a nitro group and n is 1 or 2
  • phenol, o, m, p-cresol, o, m, p are particularly preferred -Chlorphenol, o, m, p-ethylphenol
  • bisphenols such as dihydroxydiarylalkanes with C 1 -C 4 in the alkyl radical, such as bisphenol A, can also be used.
  • the known transesterification catalysts can be used as catalysts. These are preferably alkali compounds such as lithium, sodium, potassium hydroxides, alcoholates, phenolates, carboxylates and carbonates. Preferably also be organotin compounds such as trimethyltin acetate, Triäthylzinnbenzoat, tributyltin acetate, triphenyltin acetate, dibutyltin acetate, dibutyltin dilaurate, dioctyltin dilaurate, Dibutylzinnadipinat, Methoxytributylzinn, Methoxytriphenylzinn, Phenoxytriäthylzinn, Dimethyldibutylzinn, Dimethylzinnglykolat, Diäthoxydibutylzinn, Diphenoxydibutylzinn, Dimethoxydiphenylzinn, Triäthylzinnhydroxid, triphenyltin hydroxide, Hexa
  • the catalysts are used in concentrations of about 0.001-20% by weight, based on the total reaction amount.
  • the weight ratio of dimethyl carbonate: phenol can vary within wide limits and can be between about 1:99 and 99: 1, preferably 1: 9 and 9: 1. It depends on this ratio whether arylphenyl carbonate or diaryl carbonate predominates in the final product.
  • the methylaryl carbonate formed in addition to diaryl carbonate can be separated off without difficulty by distillation and either reacted with fresh phenol or, after the diaryl carbonate has been separated off, recycled for further reaction.
  • the reaction temperatures are preferably in the range from 50 to 250 ° C., particularly preferably from 100 to 200 ° C. It is advantageous to work at a pressure of 1 Torr to 20 Atms., Preferably 1-5 Atms.
  • the preferred procedure is to bring the transesterification mixture to the desired reaction temperature in a longer column, to separate the methanol to the extent that it is released in the reaction mixture together with the azeotrope, if appropriate with the aid of an inert gas stream, and to dimethyl carbonate with the azeotrope in the Measurements of how poor the reaction material on both substances are to be fed to the lower part of the column.

Claims (4)

1. Procédé de production d'esters aromatiques d'acide carbonique par transestérification de carbonate de diméthyle avec des phénols, avec élimination de méthanol, en présence de catalyseurs de transestérification, caractérisé en ce qu'on utilise pour la transestérification des mélanges de carbonate de diméthyle et méthanol et d'agents formant un azéotrope pour le méthanol, qui ne sont pas miscibles au méthanol, et on chasse le mélange de méthanol et d'agent formant un azéotrope par distillation pendant la réaction.
2. Procédé selon la revendication 1, caractérisé en ce qu'on utilise comme agents formant un azéotrope des hydrocarbures aliphatiques saturés en Cs à Ca ou des fractions techniques d'essence qui contiennent principalement les hydrocarbures mentionnés.
3. Procédé suivant les revendications 1 et 2, caractérisé en ce que la concentration du carbonate de diméthyle dans le méthanol se situe dans la plage de 10 à 95% en poids.
4. Procédé suivant les revendications 1 à 3, caractérisé en ce que la transestérification est conduite à des températures de 50 à 250°C.
EP78100571A 1977-08-10 1978-08-02 Procédé pour préparer des carbonates aromatiques Expired EP0000880B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE2736063 1977-08-10
DE19772736063 DE2736063A1 (de) 1977-08-10 1977-08-10 Verfahren zur herstellung aromatischer kohlensaeureester

Publications (2)

Publication Number Publication Date
EP0000880A1 EP0000880A1 (fr) 1979-03-07
EP0000880B1 true EP0000880B1 (fr) 1981-01-14

Family

ID=6016077

Family Applications (1)

Application Number Title Priority Date Filing Date
EP78100571A Expired EP0000880B1 (fr) 1977-08-10 1978-08-02 Procédé pour préparer des carbonates aromatiques

Country Status (5)

Country Link
US (1) US4252737A (fr)
EP (1) EP0000880B1 (fr)
JP (1) JPS5448732A (fr)
DE (2) DE2736063A1 (fr)
IT (1) IT7850655A0 (fr)

Families Citing this family (38)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5625138A (en) * 1979-08-09 1981-03-10 Nisso Yuka Kogyo Kk Preparation of aromatic carbonate
US4431838A (en) * 1981-02-09 1984-02-14 National Distillers And Chemical Corporation Extractive distillation of alcohol-ester mixtures and transesterification
US4533504A (en) * 1982-01-08 1985-08-06 General Electric Company Process for the preparation of diaryl carbonates
US4410464A (en) * 1982-03-15 1983-10-18 General Electric Company Diaryl carbonate process
DE3324917A1 (de) * 1983-07-09 1985-01-17 Basf Ag, 6700 Ludwigshafen Verfahren zur herstellung von ss-n-aziridino-probionsaeureestern
US4661609A (en) * 1986-07-31 1987-04-28 Texaco Inc. Process for cosynthesis of ethylene glycol and dimethyl carbonate
EP0461274B1 (fr) * 1989-12-28 1994-06-15 Asahi Kasei Kogyo Kabushiki Kaisha Procede de production en continu de carbonate aromatique
US5241098A (en) * 1990-11-16 1993-08-31 Hoechst Celanese Corporation Method for preparing a salt of 4-hydroxystyrene and for preparing 4-tertiary-butoxycarbonyloxystyrene therefrom
DE4036594A1 (de) * 1990-11-16 1992-05-21 Bayer Ag Verfahren zur herstellung von aromatischen kohlensaeurediestern
DE4141954A1 (de) * 1991-12-19 1993-06-24 Bayer Ag Verfahren zum spalten von polycarbonaten
US6093842A (en) * 1998-09-25 2000-07-25 General Electric Company Process for continuous production of carbonate esters
US7919644B2 (en) 2004-06-17 2011-04-05 Asahi Kasei Chemicals Corporation Process for producing an aromatic carbonate
US20070260095A1 (en) * 2004-06-25 2007-11-08 Shinsuke Fukuoka Process for the Industrial Production of Aromatic Carbonate
BRPI0512524A (pt) * 2004-06-25 2008-03-11 Asahi Kasei Chemicals Corp processo para a produção de um carbonato aromático, processo para a produção industrial do mesmo, carbonato aromático, e, coluna de destilação contìnua de múltiplos estágios
JP4224510B2 (ja) 2004-07-13 2009-02-18 旭化成ケミカルズ株式会社 芳香族カーボネート類の工業的製造法
CN100543006C (zh) * 2004-07-14 2009-09-23 旭化成化学株式会社 芳香族碳酸酯类的工业制备方法
US7812189B2 (en) 2004-08-25 2010-10-12 Asahi Kasei Chemicals Corporation Industrial process for production of high-purity diphenyl carbonate
US20070260083A1 (en) * 2004-09-02 2007-11-08 Shinsuke Fukuoka Industrial Process for Production of High-Purity Diphenyl Carbonate
WO2006025478A1 (fr) * 2004-09-03 2006-03-09 Asahi Kasei Chemicals Corporation Procédé de fabrication de carbonate de diaryle de grande pureté à échelle commerciale
BRPI0514888B1 (pt) 2004-09-17 2015-06-09 Asahi Kasei Chemicals Corp Processo industrial para a separação de um álcool subproduzido em um caso de produção em massa contínua de um carbonato aromático em uma escala industrial
KR100871306B1 (ko) * 2004-09-21 2008-12-01 아사히 가세이 케미칼즈 가부시키가이샤 부생 알코올류를 공업적으로 분리하는 방법
EA010579B1 (ru) * 2004-09-27 2008-10-30 Асахи Касеи Кемикалз Корпорейшн Промышленный способ получения ароматического карбоната
EA010425B1 (ru) 2004-10-14 2008-08-29 Асахи Касеи Кемикалз Корпорейшн Способ получения диарилкарбоната высокой чистоты
TWI321561B (en) * 2004-12-21 2010-03-11 Asahi Kasei Chemicals Corp Method for producing aromatic carbonate
JP4195717B2 (ja) 2004-12-24 2008-12-10 旭化成ケミカルズ株式会社 芳香族カーボネートの製造方法
JP5030788B2 (ja) * 2005-11-30 2012-09-19 旭化成ケミカルズ株式会社 高品質芳香族ポリカーボネートの工業的製造方法
WO2007069463A1 (fr) * 2005-12-12 2007-06-21 Asahi Kasei Chemicals Corporation Procede de production industrielle de polycarbonate aromatique de haute qualite
KR20080069697A (ko) * 2005-12-19 2008-07-28 아사히 가세이 케미칼즈 가부시키가이샤 고순도 디페닐카르보네이트를 공업적 규모로 제조하는 방법
EP1995233A3 (fr) 2007-05-25 2010-06-02 Bayer MaterialScience AG Procédé de fabrication de carbonates de diaryle ou d'arylalkyle à partir de carbonates de dialkyle
DE102007044033A1 (de) 2007-09-14 2009-03-19 Bayer Materialscience Ag Verfahren zur Herstellung von Diaryl- oder Alkylarylcarbonaten aus Dialkylcarbonaten
DE102007055266A1 (de) 2007-11-20 2009-05-28 Bayer Materialscience Ag Verfahren zur Reinigung von Diarylcarbonaten
DE102008029514A1 (de) 2008-06-21 2009-12-24 Bayer Materialscience Ag Verfahren zur Herstellung von Diarylcarbonaten aus Dialkylcarbonaten
DE102009016853A1 (de) 2009-04-08 2010-10-14 Bayer Materialscience Ag Verfahren zur Herstellung von Diaryl- oder Alkylarylcarbonaten aus Dialkylcarbonaten
DE102009053370A1 (de) 2009-11-14 2011-05-19 Bayer Materialscience Ag Verfahren zur Reinigung von Dialkylcarbonaten
DE102010042937A1 (de) 2010-10-08 2012-04-12 Bayer Materialscience Aktiengesellschaft Verfahren zur Herstellung von Diarylcarbonaten aus Dialkylcarbonaten
EP2650278A1 (fr) 2012-04-11 2013-10-16 Bayer MaterialScience AG Procédé de fabrication de diarylcarbonates à partir de dialkylcarbonates
EP2711353B1 (fr) 2012-09-20 2018-10-31 SABIC Global Technologies B.V. Procédé pour la fabrication en continu de carbonate d'alkyle aryle et de carbonate de diaryle par recompression de vapeur
WO2014095776A1 (fr) 2012-12-18 2014-06-26 Bayer Materialscience Ag Procédé de production de diarylcarbonate

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2406561A (en) * 1943-12-27 1946-08-27 Nasa Azeotropic distillation of methanol from admixture with acrylic esters
US3011954A (en) * 1958-10-13 1961-12-05 Borden Co Separation of methanol and methyl acetate
CH400107A (de) * 1961-10-11 1965-10-15 Lonza Ag Verfahren zur Gewinnung von Methanol durch Verseifung von Methylacetat
FR1490688A (fr) * 1966-06-22 1967-08-04 Melle Usines Sa Procédé pour séparer les constituants de mélanges azéotropiques de méthanol et d'ester aliphatique inférieur
AR204957A1 (es) * 1974-06-25 1976-03-19 Snam Progetti Procedimiento para la preparacion de carbonatos aromatico
IT1025961B (it) * 1974-11-25 1978-08-30 Snam Progetti Processo per la preparazione di carbonati aromatici

Also Published As

Publication number Publication date
JPS5448732A (en) 1979-04-17
EP0000880A1 (fr) 1979-03-07
DE2736063A1 (de) 1979-02-22
IT7850655A0 (it) 1978-08-08
DE2860326D1 (en) 1981-03-12
US4252737A (en) 1981-02-24

Similar Documents

Publication Publication Date Title
EP0000880B1 (fr) Procédé pour préparer des carbonates aromatiques
EP0000879B1 (fr) Procédé pour préparer des carbonates aromatiques
EP0001082B1 (fr) Procédé de préparation de dialkylcarbonates
EP0001083B1 (fr) Procédé de préparation de dialkylcarbonates
DE2528412B2 (de) Verfahren zur Herstellung von aromatischen Carbonaten
DE2552907A1 (de) Verfahren zur herstellung von aromatischen carbonaten
DE3308921A1 (de) Verfahren zur herstellung von diarylcarbonaten
EP0039452B1 (fr) Procédé de préparation de polycarbonates aromatiques
EP0444293B1 (fr) Procédé de préparation de diesters d'acide carbonique contenant au moins un groupement ester aromatique
DE1595446B2 (de) Verfahren zur Herstellung von Carbonatreste enthaltenden Dihydroxyverbindungen
EP0547479B1 (fr) Procédé de dissociation de polycarbonates
DE10063296A1 (de) Verfahren zur Herstellung von Kohlensäurediarylester
EP0751118B1 (fr) Procédé de préparation de mélanges comprenant des diphénylméthanes-diisocyanates et des polyphénylméthylène-polyisocyanates ayant une mesure colorémétrique à base d'iode réduite et à basse teneur en chlore
EP0000894B1 (fr) Procédé de séparation du carbonate de diméthyle à partir de l'azéotrope avec le méthanol
DE60216117T2 (de) Verfahren zur herstellung von hexafluoraceton und dessen hydrat
EP0454742A1 (fr) Procede pour la fabrication d'alcools de guerbet
EP0057825B1 (fr) Procédé de préparation de carbonates aliphatiques cycliques
DE2538310B2 (de) Verfahren zur Herstellung von O.O-Dialkylthionophosphorsäurechloriden
DE2749754A1 (de) Verfahren zur herstellung von kohlensaeureestern
DE2645770C3 (de) Verfahren zur Herstellung von o-Kresol durch Transmethylierung von kernmethylierten Phenolen
DE2612075A1 (de) Verfahren zur methylierung von o-cresol in fluessiger phase
DE1197469B (de) Verfahren zur Herstellung von mehrkernigen Polyphenolen
DE19751150C1 (de) Verfahren zur kontinuierlichen Herstellung von Fettsäurepolyolestern
AT340900B (de) Verfahren zur herstellung von aromatischen carbonaten
DE19816497A1 (de) Verfahren zur Herstellung von Dibenzylcarbonaten

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed
AK Designated contracting states

Designated state(s): DE FR GB NL

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Designated state(s): DE FR GB NL

REF Corresponds to:

Ref document number: 2860326

Country of ref document: DE

Date of ref document: 19810312

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 19820819

Year of fee payment: 5

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NL

Payment date: 19820831

Year of fee payment: 5

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 19820930

Year of fee payment: 5

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Effective date: 19840301

GBPC Gb: european patent ceased through non-payment of renewal fee
NLV4 Nl: lapsed or anulled due to non-payment of the annual fee
PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Effective date: 19840501

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19840502

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Effective date: 19881117

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT