EP1345887A1 - Verfahren zur herstellung von (meth)acrylsäureestern - Google Patents
Verfahren zur herstellung von (meth)acrylsäureesternInfo
- Publication number
- EP1345887A1 EP1345887A1 EP01984858A EP01984858A EP1345887A1 EP 1345887 A1 EP1345887 A1 EP 1345887A1 EP 01984858 A EP01984858 A EP 01984858A EP 01984858 A EP01984858 A EP 01984858A EP 1345887 A1 EP1345887 A1 EP 1345887A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- meth
- copper
- acrylic acid
- column
- alkanol
- 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- Withdrawn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
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/48—Separation; Purification; Stabilisation; Use of additives
- C07C67/62—Use of additives, e.g. for stabilisation
Definitions
- the invention relates to a process for the preparation of (meth) acrylic acid esters by esterification of the (meth) acrylic acid with an alkanol.
- (Meth) acrylic acid esters are valuable starting compounds for the production of polymers and copolymers, which are used, for example, as paints, dispersions or adhesives.
- the preparation of (meth) acrylic acid esters by acid-catalyzed esterification of (meth) acrylic acid with alkanols is generally known, see for example Ull ann's Encyclopedia of Industrial Chemistry, Vol. AI, 162-169, VCH 1985.
- the formation of the ester from (meth ) As is known, acrylic acid and alkanol are based on an equilibrium reaction. In order to achieve economic sales, a feedstock is generally used in excess and / or the esterification water formed is removed from the equilibrium.
- an organic solvent is usually added which is immiscible with water or which forms an azeotrope with water.
- Aliphatic, cycloaliphatic and / or aromatic hydrocarbons are often used as solvents, such as pentanes, hexanes, heptanes, cyclohexane or toluene, see for example DE 20 50 678 A, DE 29 13 218 A, US 4,053,504 A, US 2,917,538 A and EP 618 187 A.
- a major problem in the esterification of (meth) acrylic acid is the high tendency of the (meth) acrylic compounds to polymerize due to their reactive double bonds. This is particularly true when the (meth) acrylic compounds are exposed to higher temperatures, see for example WO 97/37962.
- the (meth) acrylic compounds are exposed to temperatures which can easily trigger undesired polymerization and lead to polymer formation. This results in contamination of the equipment, clogging of lines and pumps and the occupation of column trays and heat exchanger surfaces (fouling). Cleaning the equipment is a complex, expensive and environmentally harmful process, see DE 10 67 806 A. In addition, the yield and the availability of the systems is greatly reduced.
- Polymerization inhibitors are therefore usually added for stabilization, i.e. Compounds that are able to largely suppress the radical polymerization.
- the polymerization inhibitors must be separated off, for example by distillation of the (meth) acrylic compounds.
- inhibitors can be used which can be separated in another way, for example by extraction, filtration or adsorption, or which do not interfere with further processing.
- DE 28 38 691 A describes the use of Cu (I) oxide as an inhibitor, the Cu (I) oxide being removed by extraction.
- WO 90/07487 describes the use of hydroquinone with the addition of activated carbon to the esterification mixture.
- the activated carbon which is filtered off after the esterification, is added during the esterification in order to avoid discoloration of the ester due to the hydroquinone.
- DE 29 13 218 A discloses the use of phosphites, such as triethyl phosphite, as a polymerization inhibitor.
- the esterification of (meth) acrylic acid generally takes place in a reactor on which a distillation column with a condenser is placed, which serves to remove the water from the reactor in the form of the azeotrope with the solvent.
- a disadvantage of the known processes is that, despite the use of polymerization inhibitors, polymer is formed very quickly in the distillation column attached to the reactor. This significantly shortens the runtime of the esterification apparatus and requires complex and environmentally harmful cleaning work, for example cooking with an aqueous alkali solution.
- the present invention is therefore based on the object of providing a process for the preparation of (meth) acrylic esters, in particular higher (meth) acrylic esters, in which the polymer formation in the distillation column attached to the reactor is suppressed.
- the present invention therefore relates to a process for the preparation of (meth) acrylic acid esters by esterification of the (meth) acrylic acid with an alkanol in the presence of an acidic catalyst, a polymerization inhibitor and an organic solvent which forms an azeotrope with water with heating in a reactor Distillation unit, which comprises a column and a condenser, to the boiling point of the reaction mixture, the azeotrope being distilled off, the organic solvent being returned to the column as reflux and at least part of the column reflux being brought into contact with copper or copper-containing materials.
- Distillation unit which comprises a column and a condenser, to the boiling point of the reaction mixture, the azeotrope being distilled off, the organic solvent being returned to the column as reflux and at least part of the column reflux being brought into contact with copper or copper-containing materials.
- the esterification is carried out in the usual way. It takes place in one or more reactors connected in series, the mixing of the reaction mixture taking place in a customary manner, for example by stirring, pumping over or self-circulation.
- the heat can be supplied via wall heating and / or external or internal heat exchangers, for example tubular or plate heat exchangers. Suitable reactors, such as stirred tanks, etc. are known to the person skilled in the art.
- the starting materials are added to the reactor and mixed.
- the reaction mixture is heated to the boil and the water formed during the esterification is distilled off as an azeotrope with the organic solvent. This takes place via a distillation unit placed on the reactor, which comprises a distillation column and a condenser. Distillation columns of conventional design are used, the internally separating internals, for example bell, sieve or
- a distillation column with a random packing is preferably used.
- the packing can be of conventional shape, such as Raschig, Intos or Pall rings, Barrel or Intalox saddles, Top-Pak etc., see also Ullmann's Encyclopedia of Industrial Chemistry, Vol. B3, 4-71 to 4- 84, VCH 1988.
- the condensers are also of a known type, for example they can be tube or plate heat exchangers. They are preferably operated with water or brine.
- the azeotrope of the water formed and the organic solvent is separated off via the distillation column and then condensed in the condenser, the condensate breaking down into a water phase and an organic phase.
- the water phase is at least partially discharged or can be used for tion of the (meth) acrylic acid contained therein for further processing.
- the organic phase is at least partially applied as reflux to the internals of the column or to the column bed.
- At least part of the column return is brought into contact with copper (copper metal) or a copper-containing material.
- copper-containing materials are, in particular, alloys of copper with zinc, tin, aluminum or nickel.
- copper is preferably used (in the following reference is always made to copper alone by way of example).
- the return line from the condenser to the distillation column from copper or with a copper surface, e.g. by lining with copper.
- the walls of the distillation column can also be provided, in particular in the upper region, with a copper surface or with copper internals (which have no separating effect).
- the separating internals or the packs are preferably at least partially made of copper or with a copper surface. It is generally sufficient if about 1 to 30% of the internals, beds or packings have a copper surface, expediently in the upper region of the column.
- the process according to the invention is suitable for the preparation of esters of (meth) acrylic acid with all customary alkanols. However, it is preferably useful for the preparation of higher (meth) acrylic acid esters, in particular those (meth) acrylic acid esters which have a molecular weight of> 200. Such esters can no longer be purified by distillation. Monoalcohols and polyalcohols can be used as alkanols. The following alcohols are preferably used:
- o-monoalcohols such as 2-ethylhexyl, 2-propylheptyl, lauryl or stearyl alcohol;
- C 2 -C 12 diols such as ethylene glycol, 1,2- and 1,3-propylene glycol, 1,2-, 1,3- or 1,4-butylene glycol, 1,6-hexanediol, etc. and their mono- C ⁇ -C alkyl ethers;
- Polyethylene and polypropylene glycols such as diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, etc. and their mono-C ⁇ -C 4 alkyl ether;
- Triols and higher polyols such as glycerol, trimethylolpropane, pentaerythritol, etc. or the C 1 -C 4 alkyl ethers thereof with at least one free hydroxyl group;
- the equivalent ratio of alkanol: (meth) acrylic acid is generally in the range from 1: 0.7 to 2.
- P-Toluenesulfonic acid is preferably used as the acidic esterification catalyst.
- Other useful esterification catalysts are organic sulfonic acids, e.g. Methanesulfonic acid, benzenesulfonic acid or dodecylbenzenesulfonic acid, and / or sulfuric acid, which is preferred.
- the esterification catalyst is generally used in an amount of 0.1 to 10% by weight, preferably 0.5 to 5% by weight, based on (meth) acrylic acid and alkanol.
- Usual inhibitors are used as polymerization inhibitors, such as hydroquinone, hydroquinone monomethyl ether, 2,6-di-tert-butyl-4-methylphenol, 2,4-di-tert-butyl-6-methylphenol, tert-butyl catechol, p-benzoquinone , p-nitrosophenol, phenothiazine or N-oxyl compounds such as 4-hydroxy-2,2,6,6-tetramethyl-1-oxyl-piperidine or mixtures thereof.
- the inhibitors are usually used in an amount of 200 to 2000 ppm, based on (meth) acrylic acid and alkanol. If necessary, they can be used with the addition of air or oxygen-containing gas mixtures.
- Suitable organic solvents are those which form an azeotrope with water.
- Aliphatic, cycloaliphatic and / or aromatic hydrocarbons such as pentanes, hexanes, heptanes, cyclohexane or toluene, are preferably used.
- the solvent is generally used in an amount of 5 to 50% by weight, based on the reaction mixture.
- the esterification is carried out at elevated temperature.
- the reaction temperature is generally in the range from 60 to 160 ° C., preferably 80 to 130 ° C.
- the response time is generally in the range of 1 to 20 hours, preferably 2 to 10 hours.
- the pressure is not critical, you can use negative pressure, positive pressure or preferably ambient pressure.
- the reaction mixture is expediently subjected to extraction with water and / or an aqueous alkali or alkaline earth solution.
- the organic solvent is then distilled off via a distillation column.
- the (meth) acrylic acid ester remains together with the catalyst and the inhibitor as a residue and can be subjected to further purification, as described, for example, in Ullmann's Encyclopedia of Industrial Chemistry, Vol. AI, 168-169, VCH 1985.
- the acidic esterification catalyst, residual (meth) acrylic acid and optionally inhibitor can be removed by extraction with water.
- the crude ester can then be steam stripped to remove residual solvent.
- the process according to the invention has the advantage that essentially no polymer is formed in the distillation column.
- the conversion is generally in the range from 95 to 98% and the ester content is generally 90 to 99% by weight.
- the process according to the invention is also used to produce esters of other ⁇ , ⁇ -ethylenically unsaturated carboxylic acids, such as crotonic acid, itaconic acid, maleic acid, fumaric acid or citric acid, with alkanols and in particular those mentioned above Alkanols, useful.
- Example 2 The procedure was as in Example 1.
- the distillation column only contained Raschig rings made of glass (8 mm). After 5 hours, a clear formation of polymer was observed in the column.
- a mixture of 2380 parts of acrylic acid, 2660 parts of ethoylated trimethylolpropane (M 266), 2500 parts of cyclohexane, 140 parts of p-toluenesulfonic acid, 10th was in a 10 1 stirred reactor with double wall heating and attached distillation column (5 cm x 80 cm) Parts of 50% phosphinic acid and 5 parts of hydroquinone monomethyl ether heated to boiling.
- the water of reaction formed was discharged as an azeotrope with cyclohexane and condensed, the condensate disintegrating into two phases.
- the aqueous phase was separated off and the cyclohexane phase was applied to the column bed as reflux.
- the column was filled with Raschi rings, the uppermost part of the filling (approx. 1 cm) consisting of copper Raschi rings (5 mm) and the remaining part made of glass Raschi rings (8 mm). 538 parts of water were separated off within 9 hours (acrylic acid content 3.5%). Depending on the amount of water removed, the conversion was approx. 95%.
- the column was free of polymer.
- Example 3 The procedure was as in Example 3.
- the distillation column only contained Raschig rings made of glass (8 mm). After 5 hours, the esterification had to be stopped because of a liquid backlog in the column due to polymer formation.
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
Claims
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE10063176 | 2000-12-18 | ||
DE10063176A DE10063176A1 (de) | 2000-12-18 | 2000-12-18 | Verfahren zur Herstellung von (Meth)acrylsäureestern |
PCT/EP2001/014903 WO2002050015A1 (de) | 2000-12-18 | 2001-12-17 | Verfahren zur herstellung von (meth)acrylsäureestern |
Publications (1)
Publication Number | Publication Date |
---|---|
EP1345887A1 true EP1345887A1 (de) | 2003-09-24 |
Family
ID=7667713
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP01984858A Withdrawn EP1345887A1 (de) | 2000-12-18 | 2001-12-17 | Verfahren zur herstellung von (meth)acrylsäureestern |
Country Status (4)
Country | Link |
---|---|
US (1) | US20040030179A1 (de) |
EP (1) | EP1345887A1 (de) |
DE (1) | DE10063176A1 (de) |
WO (1) | WO2002050015A1 (de) |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1667953B1 (de) * | 2003-09-24 | 2008-12-10 | Dow Global Technologies Inc. | Metalloberflächen zur verhinderung der polymerisation von ethylenisch ungesättigten monomeren |
DE102009047228A1 (de) | 2009-11-27 | 2011-06-01 | Basf Se | Verfahren zur Herstellung von (Meth)acrylaten von C17-Alkoholgemischen |
US20160090348A1 (en) | 2014-09-30 | 2016-03-31 | Basf Se | Preparation of c8-c24 alkyl (meth)acrylates |
WO2016071052A1 (de) | 2014-11-05 | 2016-05-12 | Basf Se | Verfahren zur herstellung von c8-c22-alkyl(meth)acrylaten |
Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB405699A (en) * | 1932-08-12 | 1934-02-12 | John William Croom Crawford | Improvements in or relating to the manufacture of esters of methacrylic acid |
US2917538A (en) * | 1957-12-19 | 1959-12-15 | Dow Chemical Co | Process for the production of acrylic acid esters |
US3052714A (en) * | 1961-04-04 | 1962-09-04 | Du Pont | Process for the purification of liquids |
US3261686A (en) * | 1963-04-23 | 1966-07-19 | Du Pont | Photopolymerizable compositions and elements |
JP3346822B2 (ja) * | 1993-03-31 | 2002-11-18 | 三菱化学株式会社 | アクリル酸エステル又はメタクリル酸エステルの製造法 |
DE19929258A1 (de) * | 1999-06-25 | 2000-12-28 | Basf Ag | Verfahren zur Herstellung von (Meth)acrylsäureestern |
-
2000
- 2000-12-18 DE DE10063176A patent/DE10063176A1/de not_active Withdrawn
-
2001
- 2001-12-17 EP EP01984858A patent/EP1345887A1/de not_active Withdrawn
- 2001-12-17 US US10/433,614 patent/US20040030179A1/en not_active Abandoned
- 2001-12-17 WO PCT/EP2001/014903 patent/WO2002050015A1/de active Application Filing
Non-Patent Citations (1)
Title |
---|
See references of WO0250015A1 * |
Also Published As
Publication number | Publication date |
---|---|
WO2002050015A1 (de) | 2002-06-27 |
US20040030179A1 (en) | 2004-02-12 |
DE10063176A1 (de) | 2002-06-20 |
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