GB2194944A - Preparation of unsaturated carboxylic acid esters - Google Patents
Preparation of unsaturated carboxylic acid esters Download PDFInfo
- Publication number
- GB2194944A GB2194944A GB08717640A GB8717640A GB2194944A GB 2194944 A GB2194944 A GB 2194944A GB 08717640 A GB08717640 A GB 08717640A GB 8717640 A GB8717640 A GB 8717640A GB 2194944 A GB2194944 A GB 2194944A
- Authority
- GB
- United Kingdom
- Prior art keywords
- alcohol
- process according
- carboxylic acid
- unsaturated carboxylic
- zirconium
- 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.)
- Granted
Links
- 150000001733 carboxylic acid esters Chemical class 0.000 title description 8
- 238000002360 preparation method Methods 0.000 title description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 31
- 238000000034 method Methods 0.000 claims description 17
- 239000003054 catalyst Substances 0.000 claims description 16
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 12
- 229910052726 zirconium Inorganic materials 0.000 claims description 12
- -1 alkyl radical Chemical class 0.000 claims description 11
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 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
- 239000003112 inhibitor Substances 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 238000006116 polymerization reaction Methods 0.000 claims description 3
- 125000005595 acetylacetonate group Chemical group 0.000 claims description 2
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- WCYWZMWISLQXQU-UHFFFAOYSA-N methyl Chemical group [CH3] WCYWZMWISLQXQU-UHFFFAOYSA-N 0.000 claims description 2
- 150000003254 radicals Chemical class 0.000 claims description 2
- 125000003262 carboxylic acid ester group Chemical class [H]C([H])([*:2])OC(=O)C([H])([H])[*:1] 0.000 claims 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 1
- 229910052739 hydrogen Inorganic materials 0.000 claims 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 10
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 10
- 150000001298 alcohols Chemical class 0.000 description 6
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 5
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-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
- 150000002148 esters Chemical class 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
- 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
- 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
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-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
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 2
- 238000004821 distillation Methods 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
- 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
- 239000000047 product Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 239000001117 sulphuric acid Substances 0.000 description 2
- 235000011149 sulphuric acid Nutrition 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 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
- 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
- RZVINYQDSSQUKO-UHFFFAOYSA-N 2-phenoxyethyl prop-2-enoate Chemical compound C=CC(=O)OCCOC1=CC=CC=C1 RZVINYQDSSQUKO-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
- 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
- 239000002253 acid Substances 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
- 238000007664 blowing Methods 0.000 description 1
- SKFIUGUKJUULEM-UHFFFAOYSA-N butan-1-ol;zirconium Chemical compound [Zr].CCCCO SKFIUGUKJUULEM-UHFFFAOYSA-N 0.000 description 1
- 235000019437 butane-1,3-diol Nutrition 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000007795 chemical reaction product 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
- 230000007547 defect Effects 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- BTFJIXJJCSYFAL-UHFFFAOYSA-N icosan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCCCO BTFJIXJJCSYFAL-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 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
- 238000010907 mechanical stirring Methods 0.000 description 1
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 1
- 229960000907 methylthioninium chloride Drugs 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229950000688 phenothiazine Drugs 0.000 description 1
- 229960005323 phenoxyethanol Drugs 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- XPGAWFIWCWKDDL-UHFFFAOYSA-N propan-1-olate;zirconium(4+) Chemical compound [Zr+4].CCC[O-].CCC[O-].CCC[O-].CCC[O-] XPGAWFIWCWKDDL-UHFFFAOYSA-N 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
- 238000010517 secondary reaction Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 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
- JLGLQAWTXXGVEM-UHFFFAOYSA-N triethylene glycol monomethyl ether Chemical compound COCCOCCOCCO JLGLQAWTXXGVEM-UHFFFAOYSA-N 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 1 GB2194944A 1
SPECIFICATION
Process for the preparation of esters of unsaturated carboxylic acids The present invention relates to a process for preparing unsaturated carboxylic acid esters.
It is known to prepare unsaturated carboxylic acid esters by a catalytic transesterification reaction.
As a catalyst, it is known to use sulphuric acid, para-toluenesulphonic acid or alcoholates such as titanium, sodium, magnesium or zirconium alcoholates. However, these catalysts possess many disadvantages. Thus, the reaction kinetics are slow with a catalyst such as sulphuric acid.10 Catalysts such as alkali metal alcoholates. lead to the formation of secondary reaction products.
Titanium or zirconium alcoholates have the defect of gradually losing their catalytic activity during use, especially under the influence of water.
The subject of the present invention is a process for preparing unsaturated carboxylic acid esters which does not have the disadvantages of the known processes.
More precisely, the process according to the invention is characterized in that an unsaturated carboxylic acid ester of formula:
H2GC(R)-C(O)-OR' in which:
R is an hydrogen atom or a methyl radical, R' is a linear or branched alkyl radical having 1 to 3 carbon atoms, is reacted with an alcohol of formula:
in which:
W' is an alkyl radical possessing a number of carbon atoms between 2 and 30 and greater 25 than the abovementioned radical R', in the presence of at least one polymerization inhibitor, optionally at least one solvent and at least one transesterification catalyst which is a tetravalent chelate of zirconium corresponding to the following characteristics:
Zr02 content (in % by weight): from 24 to 30, viscosity at 20% (in mPa.s) 400-12,000, refractive index at WC 1.45-1.52, and in that the tetravalent chelate of zirconium is such that:
at least one chelating group is a (poly)glycol ether one or chelating groups are acetylacetonate groups, the other chelating groups for attaining the valency IV of zirconium are alkoxy groups.
The catalysts suitable for the process according to the invention are prepared by reacting a tetraalkoxy derivative (1) of zirconium, such as tetrapropyl zirconate or tetrabutoxyzirconium, with 40 (poly)glycol ether in a mole ratio with respect to the derivative (1) of between 1 and 3, and with acetylacetone in a mole ratio with respect to the derivative (1) of between 1 and 2, and in the presence of an organic solvent which is an alcohol derivative in which the alkoxy radical may be different from or identical to the chelating groups of the derivative (1), the reaction temperature being of the order of 30 to 90'C and less than the boiling point of the alcohol derivative. The zirconium chelate thereby prepared is collected at the end of the reaction by distillation.
Among (poly)gylcol ethers suitable for the preparation of the catalyst, there may be mentioned (poly)gylcol mono-ethers such as ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, (poly)ethylene glycol monoethyl ether, ethylene glycol monobutyl ether or alternatively (poly)propylene glycol ethers.
Among organic solvents suitable for the preparation of the catalyst, ethanol, propanol and nbutanol may be mentioned.
Among unsaturated carboxylic acid esters H2C=C(R)-C(O)-OR' which are usable in the process according to the invention, methyl acrylate, ethyl acrylate, propyl acrylate and the corresponding methacrylates may be mentioned.
Among alcohols R"OH which are usable in the process according to the invention, there may be mentioned ethanol, n- and isopropanol, n-, isoand sec-butanol, cyclohexanol, glycidol, 1,3butanediol, allyl alcohol, trimethylolpropane, 2-ethylhexanol, fatty acids, lauryl alcohols, stearyl alcohols, behenyl alcohols, oxo alcohols, functional alcohols such as phenoxyethyl alcohols, (poly)-glycols such as ethylene glycol and amino alcohols such as diethylaminoethanol.
In the process according to the invention, from 0.1 to 5% by weight of catalyst with respect to the alcohol R"OH, and preferably from 0.4 to 0. 7% by weight, is generally used.
The temperature used during the transesterification reaction according to the invention is between 80 and 150'C, and preferably between 110 and 125"C, The process according to the invention can also be performed under reduced pressure.
i 1,1 2 GB2194944A 2 In the process according to the invention, a mole ratio of unsaturated carboyxlic acid ester H,C=C(R)-C(O)-OR' to the alcohol R"OH of between 1 and 5, and preferably between 1.5 and 2, is used, so as to remove the fight alcohol R'OH formed in the form of a light unsaturated carboxylic acid ester H2CC(R)-C(O)-OR'/iight alcohol R'OH azeotrope.
In the process according to the invention, a solvent is preferably used which forms, with the alcohol R'OH formed during the transesterification reaction, an azeotrope which is removed during the reaction. The solvent must also be inert towards the reagents used in the invention. Among the solvents suitable for the invention, hexane, cyclohexane, benzene and toluene may be mentioned. Advantageously, it is possible to use the light unsaturated carboxylic acid ester, H2C=C(R)-C(O)-OR', itself.
Among polymerization inhibitors which are suitable for the invention, there may be mentioned hydroquinone monomethyl ether, hydroquinone, phenothiazine, tert-butylcatechol, methylene blue, copper acetate and iron acetate, in a ratio of 500 ppm by mass with respect to the reagents involved.
The process according to the invention is advantageous. In effect, it makes it possible to 15 achieve high yields which are most frequently above 98%.
The reaction times are between 4 h and 6 h 30 min.
The examples given below for guidance and without implied limitation of the present invention will enable the invention to be better understood. In these examples, the percentages are % by weight.
EXAMPLE 1: Preparation of lauryl acrylate In a three-necked reactor equipped with a device for blowing air in, a thermometer and a mechanical stirring system, and surmounted by a distillation column, the following charge is introduced:
Ethyl acrylate: 250 g Lauryl alcohol: 188 g this is an alcohol cut composed of the following 30 linear alcohols:
C, alcohol: 12.35% C, alcohol: 14.55% C, alcohol: 26% C, alcohol: 21.85% 35 C, alcohol: 13.8% C, alcohol: 7.7% C20 alcohol: <0.3% Hydroquinone methyl ether: 0.2199.
40 The reaction mixture is brought to boiling under a pressure of 385 mmHg in order to dry the reagents by distilling off the ethyl acrylate/water azeotrope.
0.75 g of a zirconium catalyst is then added, its characteristics being as follows:
ZrO, content: 24-25.2% by weight 45 Density (at WC in g/mi): 1.232-1.242 Viscosity (in mPa.s): 400-600 (at 20OC) Refractive index: 1.498-1.502 50 This catalyst takes the form of a brownish yellow liquid. It is soluble up to 1.5% in water and completely soluble in alcohols, esters, ketones and hydrocarbons.
The pressure is set at 665 mmHg and the temperature in the reactor is adjusted so as to remain below 120C. The reaction lasts 3 hours. During this reaction, 79.2 g of an azeotrope composed of ethyl acrylate and ethanol, 44.62% and 54.7% respectively, are drawn. At the end 55 of the reaction, the excess ethyl acrylate is distilled off under a pressure of 30-40 mmHg, at a temperature varying between 66 and 115'C.
110.6 g of product composed of 1.08% of ethanol and 98.68% of ethyl acrylate are col lected. The lauryl acrylate is then distilled. 244.5 g of it are collected, The yield of the reaction is 98.7%.
EXAMPLE 2: Preparation of phenoxyethyl acryulate In an apparatus similar to that used in Example 1, the following charge is introduced:
3 GB2194944A 3 Ethyl acrylate: 250 g Phenoxyethyl alcohol: 138 g (of purity equal to 91.4% by weight) Hydroquinone methyl ether: 0.1149 The reaction mixture is brought to boiling under a pressure of 300 mmHg in order to dry the reagents.
0.99 g of catalyst, which is the zirconium catalyst used in Example 1, is then added. The pressure is set at 683 mmHg and then adjusted so that the temperature in the reactor remains below 115'C. During the reaction, which last 6 h 30 min, the ethyl acrylate/ethanol azeotrope, representing 112.3 g in all and 61.49% and 37.63% respectively, is drawn off.
The excess ethyl acrylate is then collected under a pressure of 30 to 40 mmHg. The temperature then varies from 70 to 1150C. 117 g of product consisting of 99.03% of ethyl acrylate and 0.79% of ethanol are thereby collected. The phenoxyethyl acrylate is then distilled. 192.6 g of it are collected. Its chromatographic composition is as follows (in %):
Ethanol Ethyl acrylate Phenoxyethanol 0.05 0.2 0.1 Phenoxyethanol acrylate 91.5 Impurities 3.66 The reaction yield is 94%.
Claims (7)
1 Zr02 content (in % by weight): from 24 to 30, viscosity at 20C (in mPa.s) 400-12,000, refractive index at 2TC 1.45-1.52, J 45 and in that the tetravalent chelate of zirconium is such that:
at least one of these chelating groups is a (poly)-glycol ether, one or two of these chelating groups are acetyl acetonate groups, the other chelating groups for attaining the valency IV of zirconium are alkoxy groups.
2. Process according to Claim 1, characterized in that from 0.1 to 0.5% by weight of catalyst is used with respect to the alcohol W0H.
3. Process according to Claim 2, characterized in that from 0.4 to 0.7% by weight of 50 catalyst is used with respect to the alcohol W0H.
4. Process according to any one of Claims 1 to 3, characterized in that a temperature of between 80 and 15TC is established.
5. Process according to Claim 4, characterized in that a temperature of between 110 and 12WC is established.
6. Process according to any one of Claims 1 to 5, characterized in that a mole ratio of unsaturated carboxylic acid ester H2C=C(R)-C(Cl)-OR' to the alcohol R"OH of between 0 and 5 is used.
7. Process according to Claim 6, characterized in that a mole ratio of unsaturated carboxylic acid ester H2C=C(R)C(Cl)-OR' to the alcohol R"OH of between 1.5 and 2 is used.
Published 1988 at The Patent Office, State House, 66/71 High Holborn, London WC 1 R 4TP. Further copies may be obtained from The Patent Office, Sales Branch, St Mary Cray, Orpington, Kent BR5 3RD. Printed by Burgess & Son (Abingdon) Ltd. Con. 1/87.
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 (3)
| Publication Number | Publication Date |
|---|---|
| GB8717640D0 GB8717640D0 (en) | 1987-09-03 |
| GB2194944A true GB2194944A (en) | 1988-03-23 |
| GB2194944B GB2194944B (en) | 1990-10-31 |
Family
ID=9337909
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB8717640A Expired - Fee Related GB2194944B (en) | 1986-07-31 | 1987-07-24 | Preparation of unsaturated carboxylic 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 (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6395806B1 (en) * | 1998-07-07 | 2002-05-28 | Cognis Deutschland Gmbh | Hardeners for epoxy resins, processes for producing the same and methods of using the same |
| US6639099B1 (en) * | 1999-08-27 | 2003-10-28 | Roehm Gmbh & Co. Kg | Process for synthesis of Di(meth)acrylic acid esters |
| KR101539122B1 (en) * | 2007-07-05 | 2015-07-23 | 에보니크 룀 게엠베하 | Method for synthesizing allyl methacrylate |
Families Citing this family (8)
| 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 |
| EP0837049B1 (en) * | 1996-10-17 | 2002-07-31 | Rohm And Haas Company | A process for preparing monomers |
| FR2772375B1 (en) * | 1997-12-15 | 2000-01-14 | Atochem Elf Sa | PROCESS FOR PACKAGING LONG CHAIN ALKYL ACRYLATES |
| 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 |
| 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 GB GB8717640A patent/GB2194944B/en not_active Expired - Fee Related
- 1987-07-24 IT IT8748221A patent/IT1211673B/en active
- 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 |
|---|---|---|---|---|
| US6395806B1 (en) * | 1998-07-07 | 2002-05-28 | Cognis Deutschland Gmbh | Hardeners for epoxy resins, processes for producing the same and methods of using the same |
| US6639099B1 (en) * | 1999-08-27 | 2003-10-28 | Roehm Gmbh & Co. Kg | Process for synthesis of Di(meth)acrylic acid esters |
| KR101539122B1 (en) * | 2007-07-05 | 2015-07-23 | 에보니크 룀 게엠베하 | Method for synthesizing allyl methacrylate |
Also Published As
| Publication number | Publication date |
|---|---|
| GB8717640D0 (en) | 1987-09-03 |
| IT8748221A0 (en) | 1987-07-24 |
| DE3725344A1 (en) | 1988-02-11 |
| FR2602229B1 (en) | 1988-09-09 |
| IT1211673B (en) | 1989-11-03 |
| GB2194944B (en) | 1990-10-31 |
| NL8701639A (en) | 1988-02-16 |
| JPS6335543A (en) | 1988-02-16 |
| FR2602229A1 (en) | 1988-02-05 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PCNP | Patent ceased through non-payment of renewal fee |
Effective date: 19940724 |