NL8701639A - METHOD FOR PREPARING ESTERS OF UNSATURATED CARBONIC ACIDS. - Google Patents
METHOD FOR PREPARING ESTERS OF UNSATURATED CARBONIC ACIDS. Download PDFInfo
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- NL8701639A NL8701639A NL8701639A NL8701639A NL8701639A NL 8701639 A NL8701639 A NL 8701639A NL 8701639 A NL8701639 A NL 8701639A NL 8701639 A NL8701639 A NL 8701639A NL 8701639 A NL8701639 A NL 8701639A
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- Prior art keywords
- alcohol
- process according
- unsaturated carboxylic
- carboxylic acid
- ester
- Prior art date
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- 238000000034 method Methods 0.000 title claims description 22
- 150000004653 carbonic acids Chemical class 0.000 title 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 27
- 239000003054 catalyst Substances 0.000 claims description 16
- 150000002148 esters Chemical class 0.000 claims description 14
- -1 alkyl radical Chemical class 0.000 claims description 11
- 229910052726 zirconium Inorganic materials 0.000 claims description 10
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 8
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 8
- 238000002360 preparation method Methods 0.000 claims description 8
- 239000002738 chelating agent Substances 0.000 claims description 7
- 150000001735 carboxylic acids Chemical class 0.000 claims description 5
- 239000013522 chelant Substances 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- 238000005809 transesterification reaction Methods 0.000 claims description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 238000006116 polymerization reaction Methods 0.000 claims description 3
- 125000005595 acetylacetonate group Chemical group 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 239000003112 inhibitor Substances 0.000 claims description 2
- WCYWZMWISLQXQU-UHFFFAOYSA-N methyl Chemical compound [CH3] WCYWZMWISLQXQU-UHFFFAOYSA-N 0.000 claims description 2
- 150000003254 radicals Chemical class 0.000 claims description 2
- 125000003158 alcohol group Chemical group 0.000 claims 2
- 150000001875 compounds Chemical class 0.000 claims 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 11
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 10
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 8
- 150000001298 alcohols Chemical class 0.000 description 8
- 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
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 239000000376 reactant Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 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
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-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
- 238000004821 distillation Methods 0.000 description 2
- 150000002334 glycols Chemical class 0.000 description 2
- NWVVVBRKAWDGAB-UHFFFAOYSA-N hydroquinone methyl ether Natural products COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 description 2
- 229960003505 mequinol Drugs 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 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
- 239000011541 reaction mixture Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- CNHDIAIOKMXOLK-UHFFFAOYSA-N toluquinol Chemical compound CC1=CC(O)=CC=C1O CNHDIAIOKMXOLK-UHFFFAOYSA-N 0.000 description 2
- JWZZKOKVBUJMES-UHFFFAOYSA-N (+-)-Isoprenaline Chemical compound CC(C)NCC(O)C1=CC=C(O)C(O)=C1 JWZZKOKVBUJMES-UHFFFAOYSA-N 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
- 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
- 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
- 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
- GOKIPOOTKLLKDI-UHFFFAOYSA-N acetic acid;iron Chemical compound [Fe].CC(O)=O.CC(O)=O.CC(O)=O GOKIPOOTKLLKDI-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
- 238000010533 azeotropic distillation Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 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
- BCNCKJAYWXWHDQ-UHFFFAOYSA-N ethanol;ethyl prop-2-enoate Chemical compound CCO.CCOC(=O)C=C BCNCKJAYWXWHDQ-UHFFFAOYSA-N 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 230000005484 gravity Effects 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
- 230000002401 inhibitory effect Effects 0.000 description 1
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Substances CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 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
- 239000000463 material Substances 0.000 description 1
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 1
- 229960000907 methylthioninium chloride Drugs 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
- 230000035484 reaction time Effects 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 150000003755 zirconium compounds 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)
Description
* -1- 26601/Vk/tj* -1- 26601 / Vk / tj
Korte aanduiding: Werkwijze voor de bereiding van esters van onverzadigde carbonzuren.Short designation: Process for the preparation of esters of unsaturated carboxylic acids.
De uitvinding heeft betrekking op een werkwijze voor de bereiding 5 van esters van onverzadigde carbonzuren.The invention relates to a process for the preparation of esters of unsaturated carboxylic acids.
Het is bekend de esters van onverzadigde carbonzuren te bereiden door een katalytische transveresteringsreaktie.It is known to prepare the esters of unsaturated carboxylic acids by a catalytic transesterification reaction.
Als katalysator is het bekend zwavelzuur, paratolueensulfonzuur of alkoholaten te gebruiken zoals titaanalkoholaat in de vorm van de na-10 trium-, magnesium- of zirconiumverbinding. Die katalysatoren hebben echter een aantal nadelen. Zo is de reaktiekinetiek langzaam met een katalysator zoals zwavelzuur. De katalysatoren zoals de alkalimetaalalkoholaten leiden tot de vorming van reaktie-bijprodukten. De titaan- of zirconiumalko-holaten hebben het nadeel dat ze beetje bij beetje de katalytische akti-15 viteiten verliezen tijdens het gebruik hiervan onder invloed van met name water.As a catalyst it is known to use sulfuric acid, paratoluene sulfonic acid or alcoholates such as titanium alcoholate in the form of the sodium, magnesium or zirconium compound. However, those catalysts have a number of drawbacks. For example, the reaction kinetics are slow with a catalyst such as sulfuric acid. The catalysts such as the alkali metal alcoholates lead to the formation of reaction by-products. The titanium or zirconium alcoholates have the drawback that they gradually lose the catalytic activities during their use under the influence of, in particular, water.
De onderhavige uitvinding heeft als doel een werkwijze te verkrijgen voor de bereiding van esters van onverzadigde carbonzuren, welke werkwijze de nadelen niet heeft van de bekende werkwijzen.The object of the present invention is to obtain a process for the preparation of esters of unsaturated carboxylic acids, which process does not have the disadvantages of the known processes.
20 Met name wordt de werkwijze volgens de uitvinding hierdoor geken merkt dat men een ester van een onverzadigd carbonzuur met formule: H2C=C(R)-C(0)-0R' waarin: - R een waterstofatoom is of een methylradicaal, 25 - R' een lineair of vertakt alkylradicaal is met 1 tot 3 koolstof- atomen, in reaktie brengt met een alkohol met formule R"0H waarbij: - R" een alkylradicaal is met een aantal koolstofatomen tussen 2 en 30 en meer dan het eerder vermelde radicaal Rf, 30 in aanwezigheid van ten minste een de polymerisatie remmende stof, eventueel met ten minste een oplosmiddel en ten minste een transveresterings-katalysator hetgeen een vierwaardig chelaat van zirconium is, dat voldoet aan de volgende karakteristieken: - gehalte aan ZrOjCin gew. %) : 24 tot 30 35 - viscositeit bij 20 °C (uitgedrukt in mPa.s): 400-12.000 - brekingsindex bij 20 °c : 1,45-1,52, 87 0 1 S 39In particular, the process according to the invention is characterized in that an ester of an unsaturated carboxylic acid of formula: H2C = C (R) -C (0) -0R 'in which: - R is a hydrogen atom or a methyl radical, - R 'is a linear or branched alkyl radical of 1 to 3 carbon atoms, reacting with an alcohol of formula R "0H wherein: - R" is an alkyl radical with a number of carbon atoms between 2 and 30 and more than the previously mentioned radical Rf. 30 in the presence of at least one polymerization-inhibiting substance, optionally with at least one solvent and at least one transesterification catalyst which is a tetravalent chelate of zirconium having the following characteristics: - content of ZrOjCin wt. %): 24 to 30 35 - viscosity at 20 ° C (expressed in mPa.s): 400-12,000 - refractive index at 20 ° c: 1.45-1.52, 87 0 1 S 39
If -2- 26601/Vk/tj en waarbij het chelaat van vierwaardig zirconium zodanig is dat: - ten minste een chelaatvormend middeL een ether is van (poly)-glycol, - een of twee chelaatvormende middelen acetylacetonaatgroepen 5 zijn, - de andere chelaatvormende middelen voor het bereiken van de vier-waardige valentie van zirconium alkoxygroepen zijn.If -2-26601 / Vk / tj and wherein the chelate of tetravalent zirconium is such that: - at least one chelating agent is an ether of (poly) glycol, - one or two chelating agents are acetylacetonate groups 5, - the other chelating agents means for achieving the tetravalent valence of zirconium alkoxy groups.
De voor de werkwijze volgens de uitvinding geschikte katalysatoren worden bereid door een tetraalkoxyzirconiumderivaat (I), zoals tetra-10 propylzirconaat of tetrabutoxyzirconium te doen reageren met (poly)glycol-ether in een molaire verhouding ten opzichte van derivaat (I) tussen 1 en 3, met acetylaceton in een molaire verhouding ten opzichte van derivaat (I) tussen 1 en 2 en in aanwezigheid van een organisch oplosmiddel hetgeen een alkoholderivaat is waarin de alkoxyradicaal gelijk of verschillend kan zijn 15 met de chelaatvormende middelen van derivaat (I) waarbij de reaktietempe-ratuur is gelegen tussen 30 en 90 °C en lager dan het kookpunt van de al-koholderivaat. Het aldus bereide zirconiumchelaat wordt op het einde van de reaktie verzameld door destillatie.The catalysts suitable for the process according to the invention are prepared by reacting a tetraalkoxyzirconium derivative (I), such as tetra-10-propyl zirconate or tetrabutoxyzirconium, with (poly) glycol ether in a molar ratio to derivative (I) between 1 and 3. , with acetylacetone in a molar ratio to derivative (I) between 1 and 2 and in the presence of an organic solvent which is an alcohol derivative in which the alkoxy radical may be the same or different with the chelating agents of derivative (I) with the reaction temperature temperature is between 30 and 90 ° C and below the boiling point of the alcohol derivative. The zirconium chelate thus prepared is collected by distillation at the end of the reaction.
Van de (poly)glycolethers die geschikt zijn voor de bereiding van 20 de katalysator kan men de monoethers van (poly)glycolen vermelden zoals monomethylether van ethyleenglycol, monomethylether van diethyleenglycol, monomethylether van triethyleenglycol, monoethylether van (poly)ethyleen-glycol, monobutylether van ethyleenglycol of verder de (poly)propyleen-glycolethers.Of the (poly) glycol ethers suitable for the preparation of the catalyst, one can mention the monoethers of (poly) glycols such as monomethyl ether of ethylene glycol, monomethyl ether of diethylene glycol, monomethyl ether of triethylene glycol, monoethyl ether of (poly) ethylene glycol, monobutyl ether of ethylene glycol or further the (poly) propylene glycol ethers.
25 Als organische oplosmiddelen geschikt voor de bereiding van de katalysator kan men ethanol, propanol en n-butanol noemen.Ethanol, propanol and n-butanol can be mentioned as organic solvents suitable for the preparation of the catalyst.
Van de esters van het onverzadigde carbonzuur H2C=C(R)-C(0)-0R', toepasbaar volgens de werkwijze van de uitvinding kan worden genoemd me-thylacrylaat, ethylacrylaat, propylacrylaat en de hiermee overeenkomende 30 methacrylaten.The esters of the unsaturated carboxylic acid H 2 C = C (R) -C (0) -O R 'usable according to the process of the invention may be mentioned methyl acrylate, ethyl acrylate, propyl acrylate and the corresponding methacrylates.
Van de alkoholen R"0H, geschikt volgens de werkwijze van de uitvinding, kan men ethanol, n- en isopropanol, n-, iso- en sec-butanol, cy-clohexanol, glycidol, butaandiol-1,3, allylalkohol, trimethylolpropaan, 2-ethylhexanol, alkoholen van vetten, taurylalkoholen, stearylalkoholen, 35 behinealkoholen, oxoalkoholen, funktionele alkoholen zoals fenoxyethy'l- alkoholen, (poly)glycolen zoals ethyleenglycol en de aminoalkoholen zoals diethylaminoethanol noemen.The alcohols R "0H suitable according to the process of the invention may be ethanol, n- and isopropanol, n-, iso and sec-butanol, cyclohexanol, glycidol, butanediol-1,3, allyl alcohol, trimethylol propane, 2-ethylhexanol, fatty alcohols, tauryl alcohols, stearyl alcohols, behine alcohols, oxo alcohols, functional alcohols such as phenoxyethyl alcohols, (poly) glycols such as ethylene glycol and the amino alcohols such as diethylaminoethanol.
87016398701639
Jr -3- 26601/Vk/tjJr -3- 26601 / Vk / tj
Bij de werkwijze voLgens de uitvinding gebruikt men in het algemeen 0,1 tot 5 gewichtsdelen katalysator ten opzichte van de alkohol R"0H en bij voorkeur 0,4 tot 0,7 gew. %.The process of the invention generally uses from 0.1 to 5 parts by weight of the catalyst relative to the R 10 OH alcohol, and preferably from 0.4 to 0.7% by weight.
De temperatuur die is toegepast bij de transveresteringsreaktie 5 volgens de uitvinding ligt tussen 80 en 150 °C en bij voorkeur tussen 110 en 125 °C.The temperature used in the transesterification reaction 5 according to the invention is between 80 and 150 ° C and preferably between 110 and 125 ° C.
De werkwijze volgens de uitvinding kan ook worden uitgevoerd onder verlaagde druk.The method according to the invention can also be carried out under reduced pressure.
Bij de werkwijze volgens de uitvinding maakt men gebruik van een 10 molaire verhouding van de ester van het onverzadigde carbonzuur H^C=CCR)-C(0)-0R' ten opzichte van de alkohol R"0H gelegen tussen 1 en 5 en bij voorkeur tussen 1,5 en 2 waarbij de lage alkohol R’OH, gevormd als een azeotroop met de lage ester van het onverzadigde carbonzuur ^C^CRj-ClOj-OR' -lage alkohol R'OH, wordt verwijderd.The process according to the invention makes use of a 10 molar ratio of the ester of the unsaturated carboxylic acid H 2 C = CCR) -C (0) -0R 'to the alcohol R "0H between 1 and 5 and at preferably between 1.5 and 2, wherein the lower alcohol R'OH, formed as an azeotrope with the low ester of the unsaturated carboxylic acid (C 1 -C 18 -C 18 Cl-OR '-low alcohol R 10 OH), is removed.
15 Men gebruikt bij voorkeur bij de werkwijze volgens de uitvinding een oplosmiddel dat met de alkohol R'OH, gevormd tijdens de transveresteringsreaktie, een azeotroop vormt die men tijdens de reaktie verwijdert.Preferably, a solvent is used in the process according to the invention which forms an azeotrope with the alcohol R'OH formed during the transesterification reaction, which is removed during the reaction.
Het oplosmiddel moet eveneens inert zijn ten aanzien van de toegepaste reaktieve stoffen volgens de uitvinding. Als oplosmiddelen die geschikt 20 zijn volgens de uitvinding kunnen hexaan, cyclohexaan, benzeen en tolueen worden genoemd. Bij voorkeur maakt men gebruik van de lage ester van het onverzadigde carbonzuur zelf te weten H2C=CCR)-C(0)-0R'.The solvent must also be inert to the reactants used according to the invention. As the solvents suitable according to the invention, hexane, cyclohexane, benzene and toluene can be mentioned. Preferably use is made of the low ester of the unsaturated carboxylic acid itself, namely H 2 C = CCR) -C (0) -OR '.
Als middel om de polymerisatie te remmen volgens de uitvinding kan men monomethylhydrochinonether,hydrochinon, fenothiazine, tertiobutyl-25 catechol, methyleen-blauw, koperacetaat, ijzeracetaat noemen in een gewichtsverhouding van 500 dpm ten opzichte van de toegepaste reaktieve stoffen.Monomethylhydroquinone ether, hydroquinone, phenothiazine, tertiobutyl-catechol, methylene blue, copper acetate, iron acetate in a weight ratio of 500 ppm to the reactants used may be mentioned as an inhibitor of the polymerization according to the invention.
De werkwijze volgens de uitvinding kan met voordeel worden toegepast omdat men een verhoogd rendement kan bereiken,dat meestal ligt bo-30 ven 98%.The method according to the invention can be used advantageously because it is possible to achieve an increased efficiency, which is usually above 98%.
De reaktietijd is gelegen tussen 4 en 6,5 uren.The reaction time is between 4 and 6.5 hours.
De uitvinding wordt nader toegelicht aan de hand van de volgende voorbeelden waarin de vermelde percentages berekend zijn op het gewicht.The invention is further illustrated by the following examples in which the percentages stated are based on weight.
Voorbeeld IExample I
35 De bereiding van laurylacrylaat.35 The preparation of lauryl acrylate.
In een driehatskolf voorzien van een luchttoevoerbuis, een thermometer, een mechanische roerder en voorzien van een destillatiekoLom brengt men de volgende stoffen: 8701639 y * -4- 26601 /Vk/tj - ethylacrylaat: 250 g - laurylalkohol: 188 g hetgeen een hoeveelheid alkoholen is,samengesteld uit de volgende 5 lineaire alkoholen: - Cg-alkohol : 12,35% - C^g-alkohol : 14,55% - C^-alkohol : 26% - C..-alkohol : 21,85% 14 10 - C16-alkohol : 13,8% - C^g-alkohol : 7,7% - Cgg-alkohol : < 0,3% - hydrochinonmethylether: 0,219 g.The following substances are introduced into a three-hat flask equipped with an air supply tube, a thermometer, a mechanical stirrer and equipped with a distillation column: 8701639 y * -4-26601 / Vk / tj - ethyl acrylate: 250 g - lauryl alcohol: 188 g, which is an amount of alcohols is composed of the following 5 linear alcohols: - C 2 alcohol: 12.35% - C 2 alcohol: 14.55% - C 2 alcohol: 26% - C ... alcohol: 21.85% 14 10 - C16 alcohol: 13.8% - C18 g alcohol: 7.7% - C18 alcohol: <0.3% - hydroquinone methyl ether: 0.219 g.
Het reaktiemengsel wordt tot koken gebracht onder een druk van 15 385 mm Hg teneinde de reaktieve stoffen te drogen door azeotrope destilla tie van ethylacrylaat-water.The reaction mixture is brought to a boil under a pressure of 15 385 mm Hg to dry the reactants by azeotropic distillation of ethyl acrylate water.
Vervolgens voegt men 0,75 g toe van een zirconiumkatalysator met de volgende eigenschappen: - gehalte aan ZrO^: 24-25,2 gew. % 20 - soortelijk gewicht (bij 20 °C in g/ml): 1,232-1,242 - viscositeit (in mPa.s): 400-600 (bij 20 °C) - brekingsindex: 1,498-1,502.Then 0.75 g of a zirconium catalyst with the following properties are added: - content of ZrO 2: 24-25.2 wt. % 20 - specific gravity (at 20 ° C in g / ml): 1.232-1.242 - viscosity (in mPa.s): 400-600 (at 20 ° C) - refractive index: 1.498-1.502.
Deze katalysator is aanwezig in de vorm van een geel-bruine vloei-25 stof. Hij is oplosbaar tot 1,5% in water en volledig oplosbaar in de alkoholen, de esters, de ketonen en de koolwaterstoffen.This catalyst is in the form of a yellow-brown liquid. It is soluble up to 1.5% in water and completely soluble in the alcohols, esters, ketones and hydrocarbons.
De druk wordt ingesteld op 665mmHg en de temperatuur in de reak-tor wordt zodanig geregeld dat deze lager blijft dan 120 °C. De reaktie duurt 3 uren. Tijdens deze reaktie onttrekt men 79,2 g azeotrope samen-30 stelling van ethylacrylaat en ethanol in respectieve hoeveelheden van 44,62% en 54,7%. Op het einde van de reaktie destilleert men ethylacrylaat in overmaat onder een druk van 30-40 mm Hg tot een temperatuur die varieert tussen 66 em 115 °C.The pressure is set at 665mmHg and the temperature in the reactor is controlled to remain below 120 ° C. The reaction lasts 3 hours. During this reaction, 79.2 g of azeotropic composition of ethyl acrylate and ethanol are extracted in amounts of 44.62% and 54.7%, respectively. At the end of the reaction, ethyl acrylate is distilled in excess under a pressure of 30-40 mm Hg to a temperature ranging between 66 and 115 ° C.
Men verzamelt 110,6 g van het produkt samengesteld uit 1,08% 35 ethanol en 98,68% ethylacrylaat. Daarna destilleert men laurylacrylaat. men verzamelt 244,5 g.110.6 g of the product composed of 1.08% ethanol and 98.68% ethyl acrylate are collected. Lauryl acrylate is then distilled. 244.5 g are collected.
Het rendement van de reaktie is 98,7%.The yield of the reaction is 98.7%.
8701630 ï -5- 26601/Vk/tj8701630 ï -5- 26601 / Vk / tj
Voorbeeld IIExample II
De bereiding van fenoxyethylacrylaat.The preparation of phenoxyethyl acrylate.
In een apparaat vergelijkbaar met dat toegepast in voorbeeld I brengt men de volgende stoffen: 5 ~ ethylacrylaat 250 g - fenoxyethylalkohol 138 g (zuiverheid gelijk aan 91,4 gew. %) - hydrochinonmethylether: 0,114 gThe following materials are added to an apparatus similar to that used in Example 1: ethyl acrylate 250 g - phenoxyethyl alcohol 138 g (purity equal to 91.4% by weight) - hydroquinone methyl ether: 0.114 g
Het reaktiemengsel wordt tot koken gebracht onder een druk van 10 300mm Hg teneinde de reaktieve stoffen te drogen.The reaction mixture is brought to a boil under a pressure of 300mmHg to dry the reactants.
Men voegt vervolgens 0,99 g katalysator toe hetgeen de zirconium-katalysator is zoals gebruikt in voorbeeld I. De druk wordt ingesteld op 683mm Hg, daarna zodanig geregeld dat de temperatuur in de reaktor blijft beneden 115 °C. Tijdens de reakite die 6,5 uren duurt, onttrekt men azeo-15 troop ethylacrylaat-ethanol,hetgeen overeenkomt met 112,3 g, respectievelijk 61,49% en 37,63%.0.99 g of catalyst, which is the zirconium catalyst as used in Example 1, is then added. The pressure is adjusted to 683 mm Hg, then adjusted so that the temperature in the reactor remains below 115 ° C. During the reaction, which lasts for 6.5 hours, azeotropic ethyl acrylate ethanol is extracted, which corresponds to 112.3 g, 61.49% and 37.63%, respectively.
Men verzamelt vervolgens ethylacrylaat in overmaat onder een druk van 30-40 mm Hg.De temperatuur varieert dan van 70 tot 115 °C. Zodoende verzamelt men 117 g van het produkt bestaande 99,03% ethylacrylaat en 0,79% 20 ethanol. Vervolgens destilleert men fenoxyethylacrylaat af. Men verzamelt 192,6 g. De chromatografische samenstelling hiervan is als volgt (uitgedrukt in %): -ethanol : 0,05 - ethylacrylaat : 0,2 25 - fenoxyethanol : 0,1 - fenoxyethanolacrylaat : 91,5 - onzuiverheden : 3,66Ethyl acrylate is then collected in excess under a pressure of 30-40 mm Hg and the temperature ranges from 70 to 115 ° C. Thus, 117 g of the product consisting of 99.03% ethyl acrylate and 0.79% ethanol are collected. Phenoxyethyl acrylate is then distilled off. 192.6 g are collected. The chromatographic composition thereof is as follows (expressed in%): -ethanol: 0.05 - ethyl acrylate: 0.2 - phenoxyethanol: 0.1 - phenoxyethanol acrylate: 91.5 - impurities: 3.66
Het rendement van de reaktie is 94%.The reaction yield is 94%.
8 7 0 1 Θ 3 98 7 0 1 Θ 3 9
Claims (7)
Applications Claiming Priority (2)
| 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 |
| FR8611091 | 1986-07-31 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| NL8701639A true NL8701639A (en) | 1988-02-16 |
Family
ID=9337909
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| NL8701639A NL8701639A (en) | 1986-07-31 | 1987-07-13 | METHOD FOR PREPARING ESTERS OF UNSATURATED CARBONIC ACIDS. |
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) |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5614650A (en) * | 1995-03-07 | 1997-03-25 | Sandler; Stanley R. | Zirconium compounds of sulfonic acids |
| 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 & Haas | 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 |
| DE10059612A1 (en) * | 2000-12-01 | 2002-06-20 | Bayer Ag | Titanium / zirconium catalysts and their use for the production of esters or polyesters |
| 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
Also Published As
| Publication number | Publication date |
|---|---|
| GB2194944A (en) | 1988-03-23 |
| FR2602229A1 (en) | 1988-02-05 |
| DE3725344A1 (en) | 1988-02-11 |
| GB2194944B (en) | 1990-10-31 |
| IT8748221A0 (en) | 1987-07-24 |
| GB8717640D0 (en) | 1987-09-03 |
| FR2602229B1 (en) | 1988-09-09 |
| JPS6335543A (en) | 1988-02-16 |
| IT1211673B (en) | 1989-11-03 |
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