DE3725344A1 - METHOD FOR PRODUCING UNSATURATED CARBONIC ACID ESTERS - Google Patents
METHOD FOR PRODUCING UNSATURATED CARBONIC ACID ESTERSInfo
- Publication number
- DE3725344A1 DE3725344A1 DE19873725344 DE3725344A DE3725344A1 DE 3725344 A1 DE3725344 A1 DE 3725344A1 DE 19873725344 DE19873725344 DE 19873725344 DE 3725344 A DE3725344 A DE 3725344A DE 3725344 A1 DE3725344 A1 DE 3725344A1
- Authority
- DE
- Germany
- Prior art keywords
- alcohol
- formula
- carboxylic acid
- marked
- unsaturated carboxylic
- 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.)
- Withdrawn
Links
- 238000004519 manufacturing process Methods 0.000 title description 7
- 150000004651 carbonic acid esters Chemical class 0.000 title 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 19
- 239000003054 catalyst Substances 0.000 claims abstract description 16
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 12
- 238000005809 transesterification reaction Methods 0.000 claims abstract description 7
- 239000002904 solvent Substances 0.000 claims abstract description 6
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000013522 chelant Substances 0.000 claims abstract description 5
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims abstract description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 4
- 239000003112 inhibitor Substances 0.000 claims abstract description 4
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 4
- XEUCQOBUZPQUMQ-UHFFFAOYSA-N Glycolone Chemical compound COC1=C(CC=C(C)C)C(=O)NC2=C1C=CC=C2OC XEUCQOBUZPQUMQ-UHFFFAOYSA-N 0.000 claims abstract description 3
- 125000005595 acetylacetonate group Chemical group 0.000 claims abstract description 3
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 3
- 125000003262 carboxylic acid ester group Chemical class [H]C([H])([*:2])OC(=O)C([H])([H])[*:1] 0.000 claims abstract 5
- 239000002738 chelating agent Substances 0.000 claims description 7
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims description 2
- -1 alkyl radical Chemical class 0.000 abstract description 8
- 125000004435 hydrogen atom Chemical group [H]* 0.000 abstract 1
- WCYWZMWISLQXQU-UHFFFAOYSA-N methyl Chemical group [CH3] WCYWZMWISLQXQU-UHFFFAOYSA-N 0.000 abstract 1
- 150000003254 radicals Chemical class 0.000 abstract 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 9
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 8
- 150000001733 carboxylic acid esters Chemical class 0.000 description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 150000001298 alcohols Chemical class 0.000 description 5
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 2
- RZVINYQDSSQUKO-UHFFFAOYSA-N 2-phenoxyethyl prop-2-enoate Chemical compound C=CC(=O)OCCOC1=CC=CC=C1 RZVINYQDSSQUKO-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 229960003505 mequinol Drugs 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229960005323 phenoxyethanol Drugs 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- 150000000211 1-dodecanols Chemical class 0.000 description 1
- RJURRZFUWSRXDY-UHFFFAOYSA-N 1-phenoxyethanol Chemical compound CC(O)OC1=CC=CC=C1.CC(O)OC1=CC=CC=C1 RJURRZFUWSRXDY-UHFFFAOYSA-N 0.000 description 1
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 description 1
- SBASXUCJHJRPEV-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethanol Chemical compound COCCOCCO SBASXUCJHJRPEV-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- JDSQBDGCMUXRBM-UHFFFAOYSA-N 2-[2-(2-butoxypropoxy)propoxy]propan-1-ol Chemical compound CCCCOC(C)COC(C)COC(C)CO JDSQBDGCMUXRBM-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- BFSVOASYOCHEOV-UHFFFAOYSA-N 2-diethylaminoethanol Chemical compound CCN(CC)CCO BFSVOASYOCHEOV-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- QCDWFXQBSFUVSP-UHFFFAOYSA-N 2-phenoxyethanol Chemical compound OCCOC1=CC=CC=C1 QCDWFXQBSFUVSP-UHFFFAOYSA-N 0.000 description 1
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 description 1
- JIGUICYYOYEXFS-UHFFFAOYSA-N 3-tert-butylbenzene-1,2-diol Chemical compound CC(C)(C)C1=CC=CC(O)=C1O JIGUICYYOYEXFS-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- CTKINSOISVBQLD-UHFFFAOYSA-N Glycidol Chemical compound OCC1CO1 CTKINSOISVBQLD-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 239000004435 Oxo alcohol Substances 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 150000001414 amino alcohols Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- SKFIUGUKJUULEM-UHFFFAOYSA-N butan-1-ol;zirconium Chemical compound [Zr].CCCCO SKFIUGUKJUULEM-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 1
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- PVFSDGKDKFSOTB-UHFFFAOYSA-K iron(3+);triacetate Chemical compound [Fe+3].CC([O-])=O.CC([O-])=O.CC([O-])=O PVFSDGKDKFSOTB-UHFFFAOYSA-K 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 1
- 229960000907 methylthioninium chloride Drugs 0.000 description 1
- HOWGUJZVBDQJKV-UHFFFAOYSA-N n-propyl-nonadecane Natural products CCCCCCCCCCCCCCCCCCCCCC HOWGUJZVBDQJKV-UHFFFAOYSA-N 0.000 description 1
- 229950000688 phenothiazine Drugs 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- JLGLQAWTXXGVEM-UHFFFAOYSA-N triethylene glycol monomethyl ether Chemical compound COCCOCCOCCO JLGLQAWTXXGVEM-UHFFFAOYSA-N 0.000 description 1
- 150000003754 zirconium Chemical class 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
- C07C69/52—Esters of acyclic unsaturated carboxylic acids having the esterified carboxyl group bound to an acyclic carbon atom
- C07C69/533—Monocarboxylic acid esters having only one carbon-to-carbon double bond
- C07C69/54—Acrylic acid esters; Methacrylic acid esters
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/03—Preparation of carboxylic acid esters by reacting an ester group with a hydroxy group
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
Description
Die Erfindung betrifft ein Verfahren zur Herstellung von ungesättigten Carbonsäureestern.The invention relates to a method for producing unsaturated carboxylic acid esters.
Die Herstellung von ungesättigten Carbonsäureestern durch katalytische Umesterung ist bekannt. Als Katalysator werden Schwefelsäure, p-Toluolsulfonsäure oder Alkoholate, wie Titan-, Natrium-, Magnesium- oder Zirkoniumalkoholate, verwendet. Diese Katalysatoren haben jedoch verschiedene Nachteile: Mit einem Katalysator, wie Schwefelsäure, ist die Reaktionsgeschwindigkeit langsam. Katalysatoren, wie Alkalimetallalkoholate, führen zur Bildung von Nebenprodukten. Titan- oder Zirkoniumalkoholate verlieren während ihrer Verwendung unter dem Einfluß von insbesondere Wasser ihre katalytische Aktivität.The production of unsaturated carboxylic acid esters by Catalytic transesterification is known. As a catalyst Sulfuric acid, p-toluenesulfonic acid or alcoholates, such as titanium, Sodium, magnesium or zirconium alcoholates used. These However, catalysts have several disadvantages: with one Catalyst, like sulfuric acid, is the rate of the reaction slowly. Catalysts, such as alkali metal alcoholates, lead to Formation of by-products. Titanium or zirconium alcoholates lose during their use under the influence of in particular Water its catalytic activity.
Aufgabe der Erfindung war es daher, ein Verfahren zur Herstellung von ungesättigten Carbonsäureestern anzugeben, das die beschriebenen Nachteile nicht aufweist. The object of the invention was therefore to provide a process for the production of unsaturated carboxylic acid esters, which the does not have the disadvantages described.
Die Aufgabe wird anspruchsgemäß gelöst durch ein Verfahren zur Herstellung von ungesättigten Carbonsäureestern, das gekennzeichnet ist durch Umsetzung eines ungesättigten Carbonsäureesters der FormelAccording to the claim, the task is solved by a method for the production of unsaturated carboxylic acid esters is by reacting an unsaturated carboxylic acid ester of the formula
H₂C=C(R)-C(O)-OR′,H₂C = C (R) -C (O) -OR ′,
in derin the
RH oder Methyl und R′geradkettiges oder verzweigtes C1-3-Alkyl bedeuten,Are RH or methyl and R′ straight-chain or branched C 1-3 alkyl,
mit einem Alkohol der Formelwith an alcohol of the formula
R′′OH,RAW,
in derin the
R′′Alkyl mit einer Anzahl an Kohlenstoffatomen von 2 bis 30, jedoch über der von R′, ist,R′′alkyl having a number of carbon atoms from 2 to 30, however above that of R ′,
in Gegenwart mindestens eines Polymerisationsinhibitors, gegebenenfalls mindestens eines Lösungsmittels, und mindestens eines vierwertigen Zirkoniumchelats als Umesterungskatalysator mit folgenden Eigenschaften:in the presence of at least one polymerization inhibitor, if appropriate at least one solvent, and at least of a tetravalent zirconium chelate as a transesterification catalyst with the following characteristics:
- ZrO₂-Gehalt (Masse-%)24 bis 30,
- Viskosität bei 20°C (mPa · s)400-12 000,
- Brechungsindex bei 20°C1,45-1,52,
- mindestens ein Chelatbildner ist ein (Poly)glykolether,
- ein oder zwei Chelatbildner sind Acetylacetonatgruppen und
- die anderen Chelatbildner sind Alkoxygruppen.- ZrO₂ content (mass -%) 24 to 30, - viscosity at 20 ° C (mPa · s) 400-12 000, - refractive index at 20 ° C1.45-1.52, - at least one chelating agent is a (poly ) glycol ether,
- One or two chelating agents are acetylacetonate groups and
- The other chelating agents are alkoxy groups.
Die im erfindungsgemäßen Verfahren verwendeten Katalysatoren werden hergestellt durch Umsetzung eines Zirkoniumtetraalkoxyderivats, wie Tetrapropyl- oder Tetrabutoxyzirkonium, mit einem (Poly)glykolether in einem Molverhältnis von 1 bis 3 und Acetylaceton in einem Molverhältnis von Zirkoniumtetraalkoxyderivat zu Acetylaceton von 1 bis 2 in Gegenwart eines organischen Lösungsmittels, wie einem Alkohol, in dem der Alkoxyrest gleich oder verschieden zu den Chelatbildnern des Zirkoniumderivats ist. Die Reaktionstemperatur beträgt dabei von 30 bis 90°C und liegt unterhalb der Siedetemperatur des Lösungsmittels. Das so hergestellte Zirkoniumchelat wird am Ende der Reaktion durch Destillation gewonnen.The catalysts used in the process according to the invention are produced by reacting a zirconium tetraalkoxy derivative, such as tetrapropyl or tetrabutoxy zirconium, with a (poly) glycol ether in a molar ratio of 1 to 3 and acetylacetone in a molar ratio of zirconium tetraalkoxy derivative to acetylacetone from 1 to 2 in the presence of an organic Solvent, such as an alcohol, in which the alkoxy radical is the same or is different from the chelating agents of the zirconium derivative. The reaction temperature is from 30 to 90 ° C and is below the boiling point of the solvent. The so made Zirconium chelate is obtained at the end of the reaction by distillation won.
Zur Herstellung des Katalysators geeignete (Poly)glykolether sind (Poly)glykol-monoether, wie Ethylenglykol-monomethylether, Diethylenglykol-monomethylether, Triethylenglykol-monomethylether, (Poly)ethylenglykol-monoethylether, Ethylenglykolmonobutylether oder (Poly)propylenglykol-ether.(Poly) glycol ethers suitable for the preparation of the catalyst are (poly) glycol monoethers, such as ethylene glycol monomethyl ether, Diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, (Poly) ethylene glycol monoethyl ether, ethylene glycol monobutyl ether or (poly) propylene glycol ether.
Als organische Lösungsmittel können zur Herstellung des Katalysators beispielsweise Ethanol, Propanol oder n-Butanol verwendet werden.As organic solvents can be used to produce the Catalyst used for example ethanol, propanol or n-butanol will.
Ungesättigte Carbonsäureester der FormelUnsaturated carboxylic acid esters of the formula
H₂C=C(R)-C(O)-OR′,H₂C = C (R) -C (O) -OR ′,
die im erfindungsgemäßen Verfahren eingesetzt werden können, sind beispielsweise Methylacrylat, Ethylacrylat, Propylacrylat, und die entsprechenden Methacrylate.which can be used in the process according to the invention, are for example methyl acrylate, ethyl acrylate, propyl acrylate, and the corresponding methacrylates.
Im erfindungsgemäßen Verfahren geeignete Alkohole der Formel R′′OH sind beispielsweise Ethanol, n- und Isopropanol, n-, Iso- und sek.-Butanol, Cyclohexanol, Glycidol, 1,3-Butandiol, Allylalkohol, Trimethylolpropan, 2-Ethylhexanol, Fettalkohole, Laurylalkohole, Stearylalkohole, Behenalkohole (Dokosanalkohole), Oxoalkohole, funktionelle Alkohole, wie Phenoxyethylalkohole, (Poly)glykole, wie Ethylenglykol, und Aminoalkohole, wie Diethylaminoethanol.Alcohols of the formula which are suitable in the process according to the invention R''OH are, for example, ethanol, n- and isopropanol, n-, Iso- and sec-butanol, cyclohexanol, glycidol, 1,3-butanediol, Allyl alcohol, trimethylol propane, 2-ethylhexanol, fatty alcohols, Lauryl alcohols, stearyl alcohols, behen alcohols (docosane alcohols), Oxo alcohols, functional alcohols, such as phenoxyethyl alcohols, (Poly) glycols, such as ethylene glycol, and amino alcohols, such as diethylaminoethanol.
Im erfindungsgemäßen Verfahren wird der Katalysator im allgemeinen in einer Menge von 0,1 bis 5 Masse-% und vorzugsweise von 0,4 bis 0,7 Masse-%, bezogen auf den Alkohol R′′OH, eingesetzt. In the process according to the invention, the catalyst is in the generally in an amount of 0.1 to 5 mass% and preferably from 0.4 to 0.7% by mass, based on the alcohol R′′OH, used.
Bei der erfindungsgemäßen Umesterungsreaktion beträgt die Temperatur von 80 bis 150°C und vorzugsweise von 110 bis 125°C. Das erfindungsgemäße Verfahren kann auch unter vermindertem Druck durchgeführt werden.In the transesterification reaction according to the invention, the Temperature from 80 to 150 ° C and preferably from 110 to 125 ° C. The inventive method can also under reduced Pressure.
Im erfindungsgemäßen Verfahren wird der ungesättigte Carbonsäureester der FormelIn the process according to the invention, the unsaturated carboxylic acid ester of the formula
H₂C=C(R)-C(O)-OR′H₂C = C (R) -C (O) -OR ′
in einem Molverhältnis zum Alkohol R′′OH von 1 bis 5 und vorzugsweise von 1,5 bis 2 eingesetzt, so daß der leichte Alkohol R′OH in Form eines azeotropen Gemisches von leichtem ungesättigten Carbonsäureesterin a molar ratio to the alcohol R''OH from 1 to 5 and preferably from 1.5 to 2 used so that the light alcohol R'OH in the form of a azeotropic mixture of lightly unsaturated carboxylic acid ester
H₂C=C(R)-C(O)-OR′H₂C = C (R) -C (O) -OR ′
und leichtem Alkohol R′OH entfernt wird.and light alcohol R'OH removed becomes.
Im erfindungsgemäßen Verfahren wird vorzugsweise ein Lösungsmittel verwendet, das mit dem im Verlauf der Umesterung gebildeten Alkohol R′OH ein azeotropes Gemisch bildet, das während der Reaktion entfernt wird. Das Lösungsmittel muß auch gegenüber der im erfindungsgemäßen Verfahren verwendeten Reaktionsteilnehmer inert sein. Geeignet sind Hexan, Cyclohexan, Benzol oder Toluol. Zweckmäßigerweise kann auch der ungesättigte Ester der FormelA solvent is preferably used in the process according to the invention used that with that in the course of the transesterification formed alcohol R'OH forms an azeotropic mixture which during the reaction is removed. The solvent must also compared to the reactants used in the process according to the invention be inert. Hexane, cyclohexane, Benzene or toluene. The unsaturated one can expediently also Esters of formula
H₂C=C(R)-C(O)-OR′H₂C = C (R) -C (O) -OR ′
selbst verwendet werden.be used yourself.
Geeignete Polymerisationsinhibitoren sind Hydrochinonmonomethylether, Hydrochinon, Phenothiazin, t-Butylbrenzcatechin, Methylenblau, Kupferacetat oder Eisenacetat in einem Massenverhältnis von 550 ppm, bezogen auf die eingesetzten Verbindungen.Suitable polymerization inhibitors are hydroquinone monomethyl ether, Hydroquinone, phenothiazine, t-butyl catechol, Methylene blue, copper acetate or iron acetate in a mass ratio of 550 ppm, based on the compounds used.
Im erfindungsgemäßen Verfahren werden hohe Ausbeuten, die oft über 98% liegen, erreicht. Die Reaktionszeit beträgt von 4 h bis 6 h 30.In the process according to the invention, high yields are obtained often over 98%. The response time is from 4 h to 6 h 30.
Die Erfindung wird durch die Beispiele erläutert. Die Prozentangaben beziehen sich auf die Masse.The invention is illustrated by the examples. The Percentages relate to the mass.
In einen Dreihalskolben, der mit einer Lufteinblasvorrichtung, einem Thermometer, einem Rührer und einer Destillationskolonne ausgerüstet ist, werden folgende Verbindungen eingebracht:In a three-necked flask equipped with an air injection device, a thermometer, a stirrer and a distillation column the following connections are made:
- Ehtylacrylat250 g
- Laurylalkohol, d. h. Alkoholschnitt mit folgenden linearen Alkoholen:
- C₈-Alkohol12,35%
- C₁₀-Alkohol14,55%
- C₁₂-Alkohol26%
- C₁₄-Alkohol21,85%
- C₁₆-Alkohol13,8%
- C₁₈-Alkohol7,7%
- C₂₀-Alkohol< 0,3%
- Hydrochinon-methylether0,219 g- Ethyl acrylate 250 g - Lauryl alcohol, ie alcohol cut with the following linear alcohols:
- C₈ alcohol12.35% - C₁₀ alcohol14.55% - C₁₂ alcohol26% - C₁₄ alcohol21.85% - C₁₆ alcohol13.8% - C₁₈ alcohol7.7% - C₂₀ alcohol <0.3% - Hydroquinone methyl ether 0.219 g
Das Reaktionsgemisch wird unter einem Druck von 0,5 bar (385 mmHg) zum Sieden erhitzt, um die Reaktionsteilnehmer zu trocknen, dabei wird das azeotrope Gemisch Ethylacrylat/Wasser abdestilliert.The reaction mixture is under a pressure of 0.5 bar (385 mmHg) heated to boiling to reactants dry, the azeotropic mixture is ethyl acrylate / water distilled off.
Dem Reaktionsgemisch werden dann 0,75 g eines Zirkoniumkatalysators mit folgenden Eigenschaften zugegeben:The reaction mixture is then 0.75 g of a zirconium catalyst with the following properties added:
- ZrO₂-Gehalt (Masse-%)24-25,2 - Volumen bei 20°C (g/ml)1,232-1,242 - Viskosität bei 20°C (mPa · s)400-600 - Brechungsindex1,498-1,502- ZrO₂ content (mass -%) 24-25.2 - Volume at 20 ° C (g / ml) 1.232-1.242 - Viscosity at 20 ° C (mPas) 400-600 - Refractive index1.498-1.502
Dieser Katalysator liegt in Form einer gelb-braunen Flüssigkeit vor, die bis zu 1,5% in Wasser und in Alkoholen, Estern, Ketonen und Kohlenwasserstoffen vollständig löslich ist. This catalyst is in the form of a yellow-brown Liquid before that is up to 1.5% in water and in alcohols, Fully soluble esters, ketones and hydrocarbons is.
Der Druck wird auf 0,9 bar (665 mmHg) eingestellt, die Temperatur im Reaktor wird so eingestellt, daß sie unter 120°C bleibt. Die Reaktion dauert 3 Stunden. Während dieser Zeit werden 79,2 g eines azeotropen Gemisches aus 44,62% Ethylacrylat und 54,7% Ethanol abdestilliert. Am Ende der Reaktion wird das überschüssige Ethylacrylat bei einem Druck von 0,04 bis 0,05 bar (30-40 mmHg) und einer Temperatur von 66 bis 115°C destilliert.The pressure is set to 0.9 bar (665 mmHg) Temperature in the reactor is set so that it is below 120 ° C. remains. The reaction takes 3 hours. During this time 79.2 g of an azeotropic mixture of 44.62% ethyl acrylate and distilled 54.7% ethanol. At the end of the reaction the excess ethyl acrylate is at a pressure of 0.04 to 0.05 bar (30-40 mmHg) and a temperature of 66 to Distilled at 115 ° C.
Es werden 110,6 g eines Produkts aus 1,08% Ethanol und 98,68% Ethylacrylat gewonnen. Beim darauffolgenden Destillieren des Laurylacrylats werden 244,5 g erhalten, was eine Reaktionsausbeute von 98,7% bedeutet.There are 110.6 g of a product from 1.08% ethanol and 98.68% ethyl acrylate. The following distillation 244.5 g of laury acrylate are obtained, which is a Reaction yield of 98.7% means.
In den Kolben des Beispiels 1 werden folgende Verbindungen eingebracht:The following compounds are used in the flask of Example 1 brought in:
- Ethylacrylat250 g - Phenoxyethylalkohol (mit einer Reinheit entsprechend 91,4 Masse-%)138 g - Hydrochinon-methylether0,114 g- ethyl acrylate 250 g - Phenoxyethyl alcohol (with a purity corresponding to 91.4% by mass) 138 g - hydroquinone methyl ether 0.114 g
Das Reaktionsgemisch wird bei einem Druck von 0,4 bar (300 mmHg) zum Sieden erhitzt, um die Reaktionsteilnehmer zu trocknen. Dann werden 0,99 g des in Beispiel 1 verwendeten Zirkoniumkatalysators zugegeben. Der Druck wird zuerst auf 0,9 bar (683 mmHg), dann so eingestellt, daß die Temperatur im Reaktionsgefäß unter 115°C bleibt. Während der Reaktion, die 6 h 30 dauert, werden 112,3 g eines azeotropen Gemisches von 61,49% Ethylacrylat und 37,63% Ethanol abdestilliert.The reaction mixture is at a pressure of 0.4 bar (300 mmHg) heated to boiling to allow the reactants to dry. Then 0.99 g of that used in Example 1 Zirconium catalyst added. The pressure first drops to 0.9 bar (683 mmHg), then set so that the temperature in the The reaction vessel remains below 115 ° C. During the reaction that Lasts 6 h 30, 112.3 g of an azeotropic mixture of 61.49% ethyl acrylate and 37.63% ethanol distilled off.
Bei einem Druck von 0,04 bis 0,05 bar (30-40 mmHg) wird das überschüssige Ethylacrylat gewonnen. Die Temperatur beträgt 70 bis 115°C. Dann werden 117 g eines Produkts aus 99,03% Ethylacrylat und 0,79% erhalten. Schließlich werden 192,6 g Phenoxyethylacrylat destilliert mit einer chromatographischen Zusammensetzung (in %):At a pressure of 0.04 to 0.05 bar (30-40 mmHg) the excess ethyl acrylate won. The temperature is 70 to 115 ° C. Then 117 g of a product from 99.03% Get ethyl acrylate and 0.79%. Finally be 192.6 g of phenoxyethyl acrylate distilled using a chromatographic Composition (in%):
- Ethanol0,05 - Ehtylacrylat0,2 - Phenoxyethanol0,1 - Phenoxyethanolacrylat91,5 - Verunreinigungen3,66.- ethanol 0.05 - ethyl acrylate 0.2 - phenoxyethanol 0.1 Phenoxyethanol acrylate 91.5 - Impurities 3.66.
Die Ausbeute beträgt 94%.The yield is 94%.
Claims (7)
- ein oder zwei Chelatbildner sind Acetylacetonatgruppen und
- die anderen Chelatbildner sind Alkoxygruppen.1. A process for the preparation of unsaturated carboxylic acid esters, characterized by reacting an unsaturated carboxylic acid ester of the formula H₂C = C (R) -C (O) -OR ', in which RH or methyl and R' is straight-chain or branched C 1-3 alkyl, with an alcohol of the formula R''OH, in whichR''alkyl having a number of carbon atoms from 2 to 30, but above that of R ', in the presence of at least one polymerization inhibitor, optionally at least one solvent, and at least one tetravalent zirconium chelate as Transesterification catalyst with the following properties: - ZrO₂ content (mass -%) 24-30, - viscosity at 20 ° C (mPa · s) 400-12,000, - refractive index at 20 ° C1,45-1,52, - at least one Chelating agent is a (poly) glycol ether,
- One or two chelating agents are acetylacetonate groups and
- The other chelating agents are alkoxy groups.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR8611091A FR2602229B1 (en) | 1986-07-31 | 1986-07-31 | PROCESS FOR THE PREPARATION OF UNSATURATED CARBOXYLIC ACID ESTERS |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE3725344A1 true DE3725344A1 (en) | 1988-02-11 |
Family
ID=9337909
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DE19873725344 Withdrawn DE3725344A1 (en) | 1986-07-31 | 1987-07-30 | METHOD FOR PRODUCING UNSATURATED CARBONIC ACID ESTERS |
Country Status (6)
| Country | Link |
|---|---|
| JP (1) | JPS6335543A (en) |
| DE (1) | DE3725344A1 (en) |
| FR (1) | FR2602229B1 (en) |
| GB (1) | GB2194944B (en) |
| IT (1) | IT1211673B (en) |
| NL (1) | NL8701639A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0736523A3 (en) * | 1995-03-07 | 1997-01-29 | Atochem North America Elf | Zirconium compounds of sulfonic acids |
| WO2002044243A1 (en) * | 2000-12-01 | 2002-06-06 | Bayer Aktiengesellschaft | Titanium/zirconium catalysts and use thereof for production of esters or polyesters |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2747675B1 (en) * | 1996-04-19 | 1998-05-22 | Atochem Elf Sa | PROCESS FOR THE PREPARATION OF (METH) ACRYLATES |
| FR2747596B1 (en) * | 1996-04-19 | 1998-06-05 | Atochem Elf Sa | PROCESS FOR THE REGENERATION OF ZIRCONIUM CATALYSTS AND PROCESS FOR THE PREPARATION OF (METH) ACRYLATES INCORPORATING SUCH A REGENERATION OF THE CATALYST |
| DE69714373T2 (en) * | 1996-10-17 | 2003-02-13 | Rohm And Haas Co., Philadelphia | Process for the production of monomers |
| FR2772375B1 (en) * | 1997-12-15 | 2000-01-14 | Atochem Elf Sa | PROCESS FOR PACKAGING LONG CHAIN ALKYL ACRYLATES |
| DE19830279A1 (en) * | 1998-07-07 | 2000-01-13 | Henkel Kgaa | Hardener for epoxy resins |
| DE19940622C1 (en) * | 1999-08-27 | 2001-05-17 | Roehm Gmbh | Process for the preparation of di (meth) acrylic acid esters |
| FR2815631B1 (en) * | 2000-10-25 | 2003-12-19 | Atofina | PROCESS FOR THE MANUFACTURE OF METHYLCYCLOHEXYL (METH) ACRYLATES |
| DE102007031468A1 (en) * | 2007-07-05 | 2009-01-08 | Evonik Röhm Gmbh | Process for the preparation of allyl methacrylate |
| FR2924114A1 (en) * | 2007-11-27 | 2009-05-29 | Arkema France | PROCESS FOR THE SYNTHESIS OF ALCOXYPOLYALKYLENE GLYCOLS (METH) ACRYLATES BY TRANSESTERIFICATION |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2956071A (en) * | 1957-05-24 | 1960-10-11 | Kendall & Co | Organo-metallic zirconium compounds and method of making the same |
| GB1573071A (en) * | 1977-02-10 | 1980-08-13 | Mitsubishi Rayon Co | Process for producing unsaturated carbocylic acid esters |
-
1986
- 1986-07-31 FR FR8611091A patent/FR2602229B1/en not_active Expired
-
1987
- 1987-07-13 NL NL8701639A patent/NL8701639A/en not_active Application Discontinuation
- 1987-07-24 IT IT8748221A patent/IT1211673B/en active
- 1987-07-24 GB GB8717640A patent/GB2194944B/en not_active Expired - Fee Related
- 1987-07-27 JP JP62187473A patent/JPS6335543A/en active Pending
- 1987-07-30 DE DE19873725344 patent/DE3725344A1/en not_active Withdrawn
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0736523A3 (en) * | 1995-03-07 | 1997-01-29 | Atochem North America Elf | Zirconium compounds of sulfonic acids |
| WO2002044243A1 (en) * | 2000-12-01 | 2002-06-06 | Bayer Aktiengesellschaft | Titanium/zirconium catalysts and use thereof for production of esters or polyesters |
| KR100799032B1 (en) * | 2000-12-01 | 2008-01-28 | 바이엘 악티엔게젤샤프트 | Titanium/Zirconium Catalysts and Use Thereof for Production of Esters or Polyesters |
Also Published As
| Publication number | Publication date |
|---|---|
| IT1211673B (en) | 1989-11-03 |
| NL8701639A (en) | 1988-02-16 |
| GB2194944B (en) | 1990-10-31 |
| FR2602229B1 (en) | 1988-09-09 |
| GB8717640D0 (en) | 1987-09-03 |
| IT8748221A0 (en) | 1987-07-24 |
| FR2602229A1 (en) | 1988-02-05 |
| GB2194944A (en) | 1988-03-23 |
| JPS6335543A (en) | 1988-02-16 |
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