EP1343748A1 - Method for producing higher (meth)acrylic acid esters - Google Patents
Method for producing higher (meth)acrylic acid estersInfo
- Publication number
- EP1343748A1 EP1343748A1 EP01994797A EP01994797A EP1343748A1 EP 1343748 A1 EP1343748 A1 EP 1343748A1 EP 01994797 A EP01994797 A EP 01994797A EP 01994797 A EP01994797 A EP 01994797A EP 1343748 A1 EP1343748 A1 EP 1343748A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- meth
- reactor
- acrylic acid
- evaporator
- reflux
- 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- Withdrawn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
Definitions
- the invention relates to a process for the preparation of higher (meth) acrylic acid esters by esterification of the (meth) acrylic acid (acrylic acid, methacrylic 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 Ulimann's Encyclopedia of Industrial Chemistry, Vol. AI, 162-169, VCH 1985.
- the formation of the ester from (meth) As is well 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 have to be separated off.
- 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.
- Stirred reactors with double-wall heating are frequently used as the reactor.
- the disadvantage here is that the stirrers are susceptible to repair and polymer deposits easily on them.
- the reactor size is limited because the specific wall area available for heat transfer decreases with increasing reactor size.
- circulation evaporators are often used as reactors for the production of (meth) acrylic acid esters.
- problems mentioned do not occur here, it is necessary to add very efficient polymerization inhibitors, for example copper salts, during the esterification.
- the copper salts must be removed from the (meth) acrylic acid esters by washing them out with water.
- the wash water must be disposed of, ie it either pollutes the wastewater or the copper salts have to be removed from the wash water, for example with the aid of ion exchangers, electrolysis cells, etc.
- the present invention is therefore based on the object of providing a process for the preparation of higher (meth) acrylic esters, which is carried out in a reactor with an external circulation evaporator and in which the polymer formation is suppressed.
- the present invention therefore relates to a process for the preparation of higher (meth) acrylic esters by esterification of the (meth) acrylic acid with a higher alkanol in the presence of at least one acid catalyst, at least one polymerization inhibitor and an organic solvent which forms an azeotrope with water, while heating in a reactor having a distillation unit comprising a column and a condenser to the boiling point of the reaction mixture, the contents of the reactor being circulated and heated to the boiling point via an external evaporator, and the azeotrope being distilled off, the contained in the azeotrope organic solvent forms the reflux and at least part of the solvent reflux is passed into the circuit between the reactor and the evaporator.
- the operating mode of the reactor and evaporator used according to the invention is a recirculating evaporation.
- the evaporator is thus referred to below as a circulation evaporator.
- the esterification takes place in one or more reactors connected in series with an external circulation evaporator.
- a forced circulation evaporator using a pump can be used in the circuit.
- preference is given to using a self-circulation evaporator (natural circulation evaporator) in which the
- Circulation flow is accomplished without mechanical aids.
- Suitable circulation evaporators are known to the person skilled in the art and are described, for example, in R. Billet, Verdampfertechnik, HTB-Verlag, bibliographisches Institut Mannheim, 1965, 53.
- Examples of circulation evaporators are shell-and-tube heat exchangers, plate heat exchangers, etc.
- the starting materials are added to the reactor.
- the reaction mixture is heated to boiling with the aid of the circulation evaporator and the water formed during the esterification is distilled off as an azeotrope with the organic solvent. This is done via a placed on the reactor Distillation unit comprising a distillation column and a condenser.
- Distillation columns of conventional design are used which have internals which separate them, for example bell, sieve or dual-flow trays or random or directed packings.
- a distillation column with a random packing (bed of 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 and being collected in a separation container.
- the water phase is at least partially discharged or can be used for further processing to obtain the (meth) acrylic acid contained therein.
- the organic phase represents the reflux and this is at least partially passed into the circuit between the reactor and the circulation evaporator.
- the return line is preferably fed into the line leading from the reactor to the circulation evaporator and forming the inlet to the circulation evaporator, or alternatively into the circulation evaporator in the region of the inlet.
- the reaction mixture is returned to the reactor.
- Part of the organic phase can be passed as reflux into the top of the distillation column (generally about 20 to 60% of the organic phase).
- the process according to the invention is suitable for the preparation of esters of (meth) acrylic acid with higher alkanols.
- esters of (meth) acrylic acid with higher alkanols are preferably useful for the preparation of higher (meth) acrylic esters which have a molecular weight of> 200 or have a boiling point at normal pressure of> 200 ° C., in particular> 250 ° C.
- Such esters in general can no longer be purified by distillation.
- Monoalcohols and polyalcohols can be used as alkanols.
- the following alcohols are preferably used: C 8 -C 2 o-monoalcohols, such as 2-ethylhexyl, 2-propylheptyl, lauryl or stearyl alcohol;
- cyclopentanols and cyclohexanols such as tert-butylcyclohexanol
- C 2 -C 2 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 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.
- Typical inhibitors such as hydroquinone, hydroquinone monomethyl ether, 2, 6-di-tert are used as polymerization inhibitors.
- 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.
- Solvent 5 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 10 160 ° C., preferably 80 to 130 ° C.
- the reaction 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.
- reaction mixture is expediently subjected to extraction with water and / or an aqueous alkali or alkaline earth metal solution.
- 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 fed to further purification, as described, for example, in Ullmann's Encyclopedia of Industrial Chemistry, vol. AI, 168-169, VCH 1985.
- 25 traction can be removed with water.
- the crude ester can then be steam stripped to remove residual solvent.
- the process according to the invention has the advantage that it can be carried out with simple reaction vessels without moving parts.
- the process also offers flexibility in terms of reactor size.
- the process proceeds gently and with reduced polymer formation.
- the use of copper salts as inhibitors is therefore not necessary, so that they do not have to be extracted with water in order to be able to use the (meth) acrylic acid ester for further use. Sales will also improve.
- the process according to the invention can also be used for the production of esters of other ⁇ , ⁇ -ethylenically unsaturated carboxylic acids, such as crotonic acid, itaconic acid, maleic acid, fumaric acid or citraconic acid, with alkanols and in particular the abovementioned alkanols.
- esters of other ⁇ , ⁇ -ethylenically unsaturated carboxylic acids such as crotonic acid, itaconic acid, maleic acid, fumaric acid or citraconic acid
- FIG. 1 shows schematically an apparatus for performing the method and the process flow.
- a container without moving parts is used as reactor 1.
- the starting materials (meth) acrylic acid, alkanol, catalyst, organic solvent and polymerization inhibitor are introduced into the reactor 1 via lines 2 to 6.
- the reaction mixture 17 is circulated and heated via line 15 via the circulation evaporator 7, which is designed in the form of a tube bundle evaporator.
- the solvent used or the azeotrope from the water formed during the esterification and the solvent is separated off via the distillation column 8.
- the vapors are condensed in the condenser 9 and collected in the separation container 10.
- the condensate breaks down into a lower aqueous layer 11 and an upper organic layer 12, which essentially consists of the organic solvent used.
- the aqueous layer 11 is at least partially discharged from the process and can be subjected to a further workup in order to obtain the (meth) acrylic acid contained in the aqueous layer.
- the upper organic layer is fed via line 13 into line 15 between the reactor and circulation evaporator 7. If desired, fresh solvent is supplied via line 18. If necessary, part of the upper organic layer 12 is fed via line 14 to the distillation column 8 as reflux. When the esterification is complete, the reaction product obtained is removed from reactor 1 via line 16 and fed to further workup.
- Example 1 was repeated.
- the air dosage in the natural circulation evaporator was increased to 30 1 / h.
- the cyclohexane reflux was metered into the reactor via the top of the distillation column.
- the reactor contents were polymerized after an esterification time of 80 minutes.
- Example 1 and comparative example 1 show that the process according to the invention prevents the polymerization when operating without copper salts.
- Example 2 The same device as in Example 1 was used. 2920 g of dipropylene glycol, 3.2 g of methoxyphenol, 6.4 g of 50% phosphinic acid, 311 g of 65% p-toluenesulfonic acid and 1730 g of cyclohexane were initially charged.
- the natural circulation evaporator was a shell-and-tube heat exchanger heated with thermal oil.
- the tube bundle heat exchanger consisted of three tubes, each tube had a length of 700 mm and a diameter of 9 mm.
- the flow temperature of the heat transfer oil was 150 ° C, the oil circulation was controlled manually. In addition, air was led into the natural circulation evaporator, the air volume was 2 l / h.
- the distillation column had a diameter of 50 mm, a length of 700 mm and was filled with 8 mm glass rings. After the mixture in the evaporator was circulated, 3240 g of acrylic acid were added. The cyclohexane reflux was divided, 800 g / h were metered into the natural circulation evaporator from below, the remaining amount was pumped as reflux to the distillation column and regulated via the internal reactor temperature. The minimum reflux from the distillation column was 1600 g / h. The reaction temperature was raised to 5 ° C within 120 minutes. The experiment was terminated after an esterification period of 510 minutes. A total of 933 g of aqueous phase were removed and 7000 g of crude ester were obtained. The circled aqueous phase contained 8.9% acrylic acid. The raw ester contained 6.2% acrylic acid. The amount of water removed was 94% of theory.
- Example 2 was repeated. In addition, 11.6 g of 18% copper sulfate solution were presented. No cyclohexane was metered into the natural circulation evaporator.
- the experiment was terminated after an esterification period of 510 minutes. A total of 822 g of aqueous phase was removed and 6990 g of crude ester were obtained. The circled aqueous phase contained 7.4% acrylic acid. The crude ester contained 7.9% acrylic acid. The amount of water removed was equivalent to 82% of theory.
- Example 2 and comparative example 2 show that the process according to the invention improves the conversion.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
Claims
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE10063175A DE10063175A1 (en) | 2000-12-18 | 2000-12-18 | Process for the preparation of higher (meth) acrylic acid esters |
DE10063175 | 2000-12-18 | ||
PCT/EP2001/014902 WO2002050014A1 (en) | 2000-12-18 | 2001-12-17 | Method for producing higher (meth)acrylic acid esters |
Publications (1)
Publication Number | Publication Date |
---|---|
EP1343748A1 true EP1343748A1 (en) | 2003-09-17 |
Family
ID=7667712
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP01994797A Withdrawn EP1343748A1 (en) | 2000-12-18 | 2001-12-17 | Method for producing higher (meth)acrylic acid esters |
Country Status (4)
Country | Link |
---|---|
US (1) | US6818791B2 (en) |
EP (1) | EP1343748A1 (en) |
DE (1) | DE10063175A1 (en) |
WO (1) | WO2002050014A1 (en) |
Families Citing this family (16)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE10127938A1 (en) * | 2001-06-08 | 2002-07-25 | Basf Ag | Production of basic dialkylaminoethyl(meth)acrylates, useful for production of (co)polymers for paints, dispersion or adhesives comprises esterification of (meth)acrylic acid alkyl esters. |
DE10127939A1 (en) * | 2001-06-08 | 2002-05-29 | Basf Ag | Production of (meth)acrylate esters, e.g. dialkylaminoethyl (meth)acrylates, by catalytic transesterification involves four-stage distillation |
DE10225943A1 (en) | 2002-06-11 | 2004-01-08 | Basf Ag | Process for the preparation of esters of polyalcohols |
DE10259673A1 (en) * | 2002-12-18 | 2004-07-01 | Basf Ag | Process for the preparation of radiation-curable urethane (meth) acrylates |
DE10331450A1 (en) * | 2003-07-10 | 2005-01-27 | Basf Ag | (Meth) acrylic esters of monoalkoxylated polyols and their preparation |
CZ20032346A3 (en) | 2003-09-01 | 2005-04-13 | Spolek Pro Chemickou A Hutní Výrobu,A.S. | Process for preparing dichloropropanols from glycerin |
DE10354652A1 (en) | 2003-11-22 | 2005-07-07 | Clariant Gmbh | Process for the esterification of alcohols with olefinically unsaturated carboxylic acids |
US7910781B2 (en) * | 2004-07-21 | 2011-03-22 | Dow Global Technologies Llc | Process for the conversion of a crude glycerol, crude mixtures of naturally derived multihydroxylated aliphatic hydrocarbons or esters thereof to a chlorohydrin |
US7906690B2 (en) * | 2004-07-21 | 2011-03-15 | Dow Global Technologies Inc. | Batch, semi-continuous or continuous hydrochlorination of glycerin with reduced volatile chlorinated hydrocarbon by-products and chloracetone levels |
US7930651B2 (en) | 2007-01-18 | 2011-04-19 | Research In Motion Limited | Agenda display in an electronic device |
DE102007056926A1 (en) * | 2007-11-23 | 2009-05-28 | Evonik Röhm Gmbh | Process and installation for the purification of unsaturated compounds |
CA2715712A1 (en) * | 2008-02-27 | 2009-09-03 | Uwe Meisenburg | Process for preparing (meth)acrylates of c10-alcohol mixtures |
DE102009047228A1 (en) * | 2009-11-27 | 2011-06-01 | Basf Se | Process for the preparation of (meth) acrylates of C17-alcohol mixtures |
CN102691131A (en) * | 2012-06-19 | 2012-09-26 | 福建经纬新纤科技实业有限公司 | Manufacturing equipment system of flame-retardant polyester fiber |
US20160090348A1 (en) | 2014-09-30 | 2016-03-31 | Basf Se | Preparation of c8-c24 alkyl (meth)acrylates |
WO2016071052A1 (en) | 2014-11-05 | 2016-05-12 | Basf Se | Method for producing c8-c22-alkyl(meth)acrylates |
Family Cites Families (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE1067806B (en) | 1954-09-09 | 1959-10-29 | Roehm & Haas Gmbh | Process for the continuous production of esters of acrylic and methacrylic acids with higher molecular weight alcohols |
US2917538A (en) | 1957-12-19 | 1959-12-15 | Dow Chemical Co | Process for the production of acrylic acid esters |
NL299869A (en) * | 1963-10-29 | |||
DE2527005A1 (en) | 1975-06-18 | 1977-01-13 | Bayer Ag | STABILIZED ACRYLIC ACID ESTERS OF HIGH VALUE ALCOHOLS AND THE PROCESS FOR THEIR PRODUCTION |
NL186910C (en) | 1977-09-05 | 1991-04-02 | Ucb Sa | Radiation-curable acrylic polyesters, process for their preparation and radiation-curable mixtures. |
DE2913218A1 (en) | 1979-04-03 | 1980-10-23 | Bayer Ag | Prepn. of (meth)acrylic acid ester(s) - by esterification of (meth)acrylic acid with poly:hydric alcohol(s) in presence of phosphite ester and a phenol |
DE3843938A1 (en) * | 1988-12-24 | 1990-06-28 | Henkel Kgaa | METHOD FOR IMPROVED PRODUCTION OF (METH) ACRYLIC ACIDES OF PRESCRIBED ALCOHOLS (II) |
JP3346822B2 (en) | 1993-03-31 | 2002-11-18 | 三菱化学株式会社 | Method for producing acrylate or methacrylate |
DE19604253A1 (en) | 1996-02-06 | 1997-08-07 | Basf Ag | Process for the continuous production of alkyl esters of (meth) acrylic acid |
US5763644A (en) | 1996-04-08 | 1998-06-09 | Aristech Chemical Corporation | Method for transesterification |
-
2000
- 2000-12-18 DE DE10063175A patent/DE10063175A1/en not_active Withdrawn
-
2001
- 2001-12-17 EP EP01994797A patent/EP1343748A1/en not_active Withdrawn
- 2001-12-17 WO PCT/EP2001/014902 patent/WO2002050014A1/en active Application Filing
- 2001-12-17 US US10/450,438 patent/US6818791B2/en not_active Expired - Fee Related
Non-Patent Citations (1)
Title |
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See references of WO0250014A1 * |
Also Published As
Publication number | Publication date |
---|---|
WO2002050014A1 (en) | 2002-06-27 |
US20040024241A1 (en) | 2004-02-05 |
US6818791B2 (en) | 2004-11-16 |
DE10063175A1 (en) | 2002-06-20 |
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