EP2421908A1 - Procédés de fabrication d'esters d'acides (méth)acryliques d'alcools contenant des groupes polyalkoxy - Google Patents

Procédés de fabrication d'esters d'acides (méth)acryliques d'alcools contenant des groupes polyalkoxy

Info

Publication number
EP2421908A1
EP2421908A1 EP10715208A EP10715208A EP2421908A1 EP 2421908 A1 EP2421908 A1 EP 2421908A1 EP 10715208 A EP10715208 A EP 10715208A EP 10715208 A EP10715208 A EP 10715208A EP 2421908 A1 EP2421908 A1 EP 2421908A1
Authority
EP
European Patent Office
Prior art keywords
meth
acrylic acid
alcohol
reaction
mol
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Withdrawn
Application number
EP10715208A
Other languages
German (de)
English (en)
Inventor
Virginie Bette
Jochen Petzoldt
Hermann Bergmann
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Original Assignee
BASF SE
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Publication of EP2421908A1 publication Critical patent/EP2421908A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/32—Polymers modified by chemical after-treatment
    • C08G65/329—Polymers modified by chemical after-treatment with organic compounds
    • C08G65/331—Polymers modified by chemical after-treatment with organic compounds containing oxygen
    • C08G65/332—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing carboxyl groups, or halides, or esters thereof
    • C08G65/3322—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing carboxyl groups, or halides, or esters thereof acyclic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/02—Polyalkylene oxides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/05—Polymer mixtures characterised by other features containing polymer components which can react with one another

Definitions

  • the present invention relates to a process for the catalytic preparation of (meth) acrylic acid esters of polyalkoxy-containing alcohols and their use.
  • (meth) acrylic acid is understood to mean acrylic acid and / or methacrylic acid, acrylic acid esters and / or methacrylic acid esters being (meth) acrylic esters.
  • (meth) acrylic esters are also referred to as (meth) acrylates.
  • the preparation of (meth) acrylic acid esters is usually carried out by catalytic esterification of (meth) acrylic acid or transesterification of other (meth) acrylic acid esters with alcohols.
  • strong acids or bases are often used, so that acid- or base-sensitive (meth) acrylic acid esters can not be selectively produced by an esterification or transesterification in this way as a rule.
  • EP 0 902 017 A1 discloses (meth) acrylic acid esters of polyalkoxy-containing alcohols.
  • the reaction takes place by means of transesterification with tin-containing catalysts, magnesium alcoholates, lithium, lithium carbonate or lithium hydroxide.
  • tin-containing catalysts magnesium alcoholates, lithium, lithium carbonate or lithium hydroxide.
  • From the group of polyalkoxy-containing alcohols only Polyethoxyalkohole with a cetyl-stearyl-alkyl chain (alkyl chain de) and with a lauryl-myristyl alkyl chain (alkyl chain C14-C12) are called.
  • a dehydration is required according to this document, wherein an azeotropic mixture of acrylate and water is distilled off. Due to this, the catalyst can be added only after separation of the azeotropic mixture.
  • JP 04 066555 A1 discloses the transesterification of (meth) acrylic acid esters with C 3 -C 20 -alcohols in the presence of tetralkyl titanate as catalyst.
  • the alcohols disclosed therein have a short alkyl and a short alkoxy chain, such as methoxyethanol and ethoxyethanol.
  • EP 0 837 049 A1 discloses a process for the synthesis of ethoxylated C 10 -C 20 linear alcohols.
  • the catalysts used are Zr compounds.
  • the object of the present invention was to provide a further process by means of which (meth) acrylic acid esters of polyalkoxy-containing alcohols can be prepared.
  • the synthesis should proceed under mild conditions, resulting in products with a low color number and high purity.
  • the implementation of the method should be industrially feasible.
  • the object is achieved by a process for the preparation of (meth) acrylic acid esters (E) of polyalkoxy-containing alcohols (A) in which polyalkoxy-containing alcohols (A) of the formula (I)
  • n is an integer from 1 to 100 and
  • R is a straight-chain, saturated or unsaturated alcohol having 1 to 30 C
  • the polyalkoxy-containing alcohol used may contain a plurality of different alkylene oxide units, wherein the alkylene oxide units may be randomly distributed.
  • the polyalkoxy-containing alcohols (A) preferably contain only one group of alkylene oxide units, preferably ethylene oxide units.
  • n is in the range between 5 and 90, particularly preferably between 10 and 80 and particularly preferably between 20 and 50.
  • the substituent R is a straight-chain, saturated or unsaturated alcohol having 1 to 60 carbon atoms. These may be monoalcohols having 1 to 12 carbon atoms, such as, for example, methanol, ethanol, isopropanol, n-propanol, n-butanol, isobutanol, sec-butanol, tert-butanol, n-hexanol, n-heptanol , n-octanol, n-decanol, 2-ethylhexanol, act.
  • the substituent R is preferably straight-chain, saturated or unsaturated primary alcohols having 6 to 22 carbon atoms, known as fatty alcohols.
  • fatty alcohols are, for example, hexan-1-ol (hexyl alcohol, caproic alcohol), heptan-1-ol (heptyl alcohol, eananthalcohol), octan-1-ol (octyl alcohol, capryl alcohol), nonan-1-ol (nonyl alcohol, pelargonyl alcohol), Decan-1-ol (decyl alcohol, capric alcohol), undecan-1-ol (undecyl alcohol), undec-10-en-1-ol, dodecan-1-ol (dodecyl alcohol, lauryl alcohol), tridecan-1-ol (tridecyl alcohol ), Tetradecan-1-ol (tetradecyl alcohol, myristyl alcohol), pentadecan-1-ol (pentadecyl alcohol), hex
  • fatty alcohols having 6 to 22 carbon atoms are preferably used. Preference is given to using fatty alcohols containing 8 to 18, preferably 10 to 16, carbon atoms. These may also be any desired mixtures of fatty alcohols, for example a mixture of fatty alcohols with a C16 and C18 alkyl chain, with a C13 and Cis-alkyl chain or with a C12 and C14-alkyl chain. For mixtures of fatty alcohols, those having a C16 and Cis alkyl chain are preferred.
  • the usable in the present process comprising polyalkoxy alcohols are marketed under the brand name Lutensol ® or Pluriol® ® from BASF SE.
  • the transesterification is carried out with at least one, preferably exactly one (meth) acrylic ester (D) in the presence of at least one inorganic salt as a catalyst.
  • (Meth) acrylic acid esters (D) are those of a saturated alcohol, preferably saturated C 1 -C 10 -alkyl esters or C 3 -C 12 -cycloalkyl esters of (meth) acrylic acid, particularly preferably saturated C 1 -C 4 -alkyl esters of (meth) acrylic acid.
  • Examples of compounds (D) are (meth) acrylic acid methyl, ethyl, n-butyl, iso-butyl, tert-butyl, n-octyl and 2-ethylhexyl, 1, 2-Ethylenglycoldi and mono (meth) acrylic esters, 1,4-butanediol and mono (meth) acrylic esters, 1, 6
  • (meth) acrylic acid methyl, ethyl, n-butyl and 2-ethylhexyl esters very particular preference to methyl, ethyl and n-butyl (meth) acrylates, in particular (meth) acrylic acid methyl and ethyl ester and especially methyl (meth) acrylate.
  • inorganic salts are used as catalysts for the transesterification.
  • Preferred are those having a pKa of not more than 7.0, preferably not more than 6.0, and more preferably not more than 4.0.
  • the pK ⁇ should not be less than 1, 0, preferably not less than 1.5, and more preferably not less than 1.6.
  • Inorganic salts which can be used according to the invention are preferably heterogeneous inorganic salts.
  • Heterogeneous inorganic salts in the context of this document according to the invention are those which have a solubility in the reaction medium at 25 0 C of not more than 1 g / L, preferably not more than 0.5 g / L and more preferably not more than 0.25 g / L.
  • the inorganic salt preferably has at least one anion selected from the group consisting of carbonate (CO 3 2 "), hydrogencarbonate (HCO 3 ), phosphate (PO 4 3 "), hydrogenphosphate (HPO 4 2 “), dihydrogenphosphate (H 2 PO 4 "), Sulfate (SO 4 2 “), sulfite (SO 3 2 ”) and carboxylate (R 1 -COO-), wherein R 1 is Ci-Cis-alkyl or optionally by one or more oxygen and / or sulfur atoms and / or one or more substituted or unsubstituted imino groups is interrupted C2-Cis-alkyl or C ⁇ -CH-aryl.
  • C 1 -C 6 -alkyl straight-chain or branched hydrocarbon radicals having up to 18 carbon atoms, preferably C 1 -C 10 -alkyl, such as methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, 1, 1-dimethylethyl, Pentyl, 2-methylbutyl, 1, 1-dimethylpropyl, 1, 2-dimethylpropyl, 2,2-dimethylpropyl, 1-ethylpropyl, hexyl, 2-methylpentyl, 3-methylpentyl, 1, 1-dimethylbutyl, 1, 2-dimethylbutyl, 1, 3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3- Dimethylbutyl, 2-ethylbutyl, 1, 1, 2-trimethylpropyl, 1, 2,2-trimethylpropyl, 1-ethyl-1-methyl
  • C6-Ci4-aryl a mono- to trinuclear aromatic ring system containing 6 to 14 carbon ring members, eg. As phenyl, naphthyl and anthracenyl, preferably a mononuclear to dinuclear, more preferably a mononuclear aromatic ring system.
  • Preferred anions are phosphate, hydrogen phosphate, sulfate, sulfite and carboxylate, phosphate is particularly preferred.
  • Phosphate is also to be understood as the condensation products, such as, for example, diphosphates, triphosphates and polyphosphates.
  • the inorganic salt preferably has at least one, more preferably exactly one cation selected from the group consisting of alkali metals, alkaline earth metals, ammonium, cerium, iron, manganese, chromium, molybdenum, cobalt, nickel or zinc.
  • alkali metals Preference is given to alkali metals and particular preference to lithium, sodium or potassium.
  • Particularly preferred inorganic salts are LJsPO 4 , K 3 PO 4 , NajiPCu, K 2 CO 3 and Na 2 CO 3 and their hydrates, most preferably K 3 PO 4.
  • K3PO4 can be used according to the invention in anhydrous form and as tri-, hepata- or nonahydrate.
  • the addition of the inorganic salt may be carried out as a solid, i. in both cases as pure substance, carried out or dissolved in a suitable solvent.
  • the salt is metered in as solids, with no further component being added to the reaction system, which has to be removed with difficulty.
  • the inorganic salt used as a catalyst is completely added at the beginning of the reaction, i. not continuously during the course of the reaction.
  • the catalyst can be added only after separation of the water from the reaction mixture.
  • it is therefore advantageous, since a staggered or continuous addition of the catalyst is often not possible due to technical problems.
  • the transesterification is generally carried out at from 30 to 140 ° C., preferably from 30 to 120 ° C., more preferably from 40 to 100 ° C., and very preferably from 60 to 95 ° C.
  • the reaction is carried out under a slight vacuum of, for example, 200 hPa to atmospheric pressure, preferably 200 be carried out to 900 hPa and more preferably 300 to 700 hPa, if the resulting in the transesterification low-boiling alcohol, optionally as an azeotrope, to be distilled off.
  • the molar ratio between (meth) acrylic acid ester (D) and polyalkoxy-containing alcohol (A) in the case of the transesterification catalyzed by an inorganic salt is generally 1-20: 1 mol / mol, preferably 1-18: 1 mol / mol, and especially preferably 1-15: 1 mol / mol.
  • the reaction time is usually 45 minutes to 18 hours, preferably 2 hours to 12 hours and more preferably 3 to 10 hours.
  • the content of inorganic salts in the reaction medium is generally in the range of about 0.01 to 10 mol%, preferably 0.1 to 8 and particularly preferably 0.3 to 6 mol% based on the sum of the polyalkoxy-containing alcohols (A).
  • oxygen-containing gases s.u.
  • the products having a color number below 500 APHA, preferably below 200 and particularly preferably below 150 are generally obtained.
  • the reaction can take place in organic solvents or mixtures thereof or without the addition of solvents.
  • the batches are generally largely anhydrous (i.e., below 10, preferably below 5, more preferably below 1, and most preferably below 0.5 percent by weight water content).
  • the approaches are largely free of primary and secondary alcohols, i. below 10, preferably below 5, more preferably below 1 and most preferably below 0.5 wt .-% alcohol content.
  • Suitable organic solvents are those known for this purpose, for example tertiary monools, such as Cs-C ⁇ alcohols, preferably tert-butanol, tert-amyl alcohol, pyridine, poly-C 1 -C 4 -alkylene glycol di-C 1 -C 4 -alkyl ethers, preferably polyethylene glycol di-C 1 -C 4 -alkyl ethers, for example 1, 2-dimethoxyethane, diethylene glycol dimethyl ether, polyethylene glycol dimethyl ether 500, C 1 -C 4 -alkylene carbonates, in particular propylene carbonate, C 3 -C 6 -alkyl acetic acid esters, in particular tert-butylacetic acid esters, THF, toluene , 1, 3-dioxolane, acetone, isobutyl methyl ketone, ethyl methyl ketone, 1, 4-dioxane, ter
  • the reaction is carried out in the (meth) acrylic acid ester (D) used as starting material.
  • the product (E) is obtained after completion of the reaction as about 10 to 80 wt .-% solution in the (meth) acrylic acid ester (D) used as starting material, in particular as 20 to 50 wt .-% solution.
  • the educts are either dissolved, suspended as solids, as a melt or in emulsion in the reaction medium before.
  • the inorganic salt is preferably used as a solid.
  • the polyalkoxy-containing alcohol (A) is preferably used as a solid or as a melt.
  • the reaction can be carried out continuously, for example in a tubular reactor or in a stirred reactor cascade, or discontinuously.
  • the inorganic salt is added completely at the beginning of the reaction, i. not continuously during the course of the reaction.
  • the reaction can be carried out in all reactors suitable for such a reaction. Such reactors are known to the person skilled in the art.
  • the reaction preferably takes place in a stirred tank reactor or a fixed bed reactor.
  • any method can be used. Special stirring devices are not required.
  • the mixing can be carried out, for example, by feeding in a gas, preferably an oxygen-containing gas (see below).
  • the reaction medium can be monophase or polyphase and the reactants are dissolved, suspended or emulsified therein.
  • the temperature is adjusted to the desired value during the reaction and, if desired, can be increased or decreased during the course of the reaction.
  • the removal of alcohols which are released in the transesterification from the (meth) acrylic acid esters (D) is carried out continuously or stepwise in a manner known per se, e.g. by vacuum, azeotropic removal, stripping, absorption, pervaporation and diffusion via membranes or extraction.
  • the stripping can be carried out, for example, by passing an oxygen-containing gas, preferably an air or air-nitrogen mixture, through the reaction mixture, optionally in addition to a distillation.
  • an oxygen-containing gas preferably an air or air-nitrogen mixture
  • Molecular sieves or zeolites pore size, for example, in the range of about 3-10 Angstroms
  • a separation by distillation or by means of suitable semipermeable membranes are preferably suitable for absorption.
  • reaction mixture obtained from the transesterification can be used without further purification or, if necessary, purified in a further step.
  • a separation from the catalyst is usually carried out by filtration, electro filtration, absorption, centrifugation or decantation or by distillation or rectification.
  • the separated catalyst can then be used for further reactions.
  • the reaction mixture may be previously diluted to achieve a handleable concentration for the separation of the catalyst.
  • the separation from the organic solvent is usually carried out by distillation, rectification or solid reaction products by filtration.
  • the optionally purified reaction mixture can be subjected to a distillation, in which the (meth) acrylic acid ester (E) of the polyalkoxy-containing alcohols is separated by distillation from unreacted (meth) acrylic acid ester (D) and optionally formed by-products.
  • the distillation units are usually rectification columns of conventional design with circulation evaporator and condenser.
  • the feed takes place in the preferred
  • the bottom temperature is here, for example, 130-160 0 C, preferably 150- 160 0 C, the head temperature preferably 140-145 0 C and the top pressure 3 - 20, preferably 3 to 5 mbar.
  • the respective (meth) acrylic acid esters (E) of the polyalkoxy-containing alcohols can be purified by distillation. What is essential here is a separation of the desired product of reactants and by-products under conditions in which the desired product is exposed to as possible no degradation reaction.
  • the distillation unit usually has from 5 to 50 theoretical plates.
  • the distillation units are of a known type and have the usual installations. In principle, all standard installations are suitable as column internals, for example trays, packings and / or fillings. Of the soils, bubble-cap trays, sieve trays, valve trays, Thormann trays and / or dual-flow trays are preferred, from the beds are those with rings, helices, calipers, Raschig, Intos or Pall rings, Barrel or Intalox saddles, top Pak etc. or braids preferred.
  • the desired product is distilled batchwise, initially low boilers are removed from the reaction mixture, usually solvent or unreacted (meth) acrylic acid esters (D). After separation of these low boilers, the distillation temperature is increased and / or reduced the vacuum and the desired product distilled off.
  • the remaining distillation residue is usually discarded.
  • the catalyst is separated off as described above, this separation preferably takes place by filtration. It may be necessary for the reaction mixture to be diluted with a suitable solvent before filtration in order to achieve a manageable concentration for the separation of the catalyst. Subsequently, the optionally present solvent is separated off by distillation and replaced by another solvent.
  • the optionally present solvent may first be removed by distillation and, if appropriate, be replaced by another solvent without the catalyst having to be separated off from the reaction mixture. This can then be separated by the aforementioned methods.
  • solvents are, for example, other (meth) acrylic esters, (meth) acrylic acid, alcohols, customary organic solvents, water and any mixtures thereof. Preference is given to using (meth) acrylic acid, particularly preferably methacrylic acid, as the new solvent.
  • the end product (E) may contain very small amounts of starting materials, in particular of the original (meth) acrylic acid ester (D).
  • the proportion of (meth) acrylic ester (D) in the (meth) acrylic ester (E) is usually less than 20 wt .-%, preferably less than 10 wt .-% and particularly preferably less than 5 wt .-%.
  • the reaction conditions in the transesterification according to the invention are mild. Due to the low temperatures and other mild conditions, the formation of byproducts in the reaction is avoided, which can otherwise be derived for example from strongly acidic or basic catalysts, or by unwanted radical polymerization of the (meth) acrylic acid ester (D) used, which otherwise only by addition Stabilizers can be prevented.
  • additional stabilizer may be added to the reaction mixture via the storage stabilizer which is present anyway in the (meth) acrylic ester (D), for example hydroquinone monomethyl ether, phenothiazine, phenols, for example 2-tert-butyl-4-methylphenol, 6 tert-butyl-2,4-dimethyl-phenol or N-oxyls such as 4-hydroxy-2,2,6,6-tetramethyl-piperidine-N-oxyl, 4-oxo-2,2,6,6 -tetramethyl- piperidine-N-oxyl or Uvinul ® 4040P from BASF SE or amines such as BPD Kerobit ® BASF SE (N, N'-di-sec-butyl-p-phenylenediamine), for example in quantities of 50 to 2000 ppm ,
  • BPD Kerobit ® BASF SE N, N'-di-sec-butyl-p-phenylenediamine
  • the transesterification is advantageously carried out in the presence of an oxygen-containing gas, preferably air or air-nitrogen mixtures.
  • the (meth) acrylic esters (E) of polyalkoxy-containing alcohols according to the invention are used, for example, as monomers or comonomers in the preparation of dispersions, for example acrylic dispersions, as reactive diluents, for example in radiation-curable coating compositions or in paints, preferably in exterior paints, and in dispersions for use in the paper sector, in the cosmetics sector, in the pharmaceutical sector, in agricultural formulations, in the textile industry and in the field of oil extraction.
  • the transesterification took place in a 750 ml mini-plan reactor with Oldershaw column and liquid distributor.
  • the reflux ratio was 25: 1 (reflux: drain), the stirring speed (armature stirrer) 300 rpm and the air inlet 1, 5 L / h.
  • the crude bottoms product (200.66 g) was then analyzed by NMR and OH number, containing 50 mol% MMA and 50 mol% polyethoxymethacrylate.
  • the crude product was diluted to a 25 wt .-% solution in MMA and filtered. This gave a clear, colorless solution (25 wt .-% in MMA, APHA color number 42) of the final product polyethoxymethacrylate.
  • the number of OH groups was determined, it was less than 1 mg KOH / g.
  • the potassium content was less than 0.001 g / 100 g.
  • the haze value in methanol (1:10) was 0.16 NTU.
  • the transesterification took place in a 750 ml mini-plan reactor with Oldershaw column and liquid distributor.
  • the reflux ratio was 25: 1 (reflux: drain), the stirring speed (armature stirrer) 300 rpm and the air inlet 1, 5 L / h.
  • the crude bottoms product (569.96 g) was then analyzed by NMR containing 20 mol% MMA and 80 mol% polyethoxymethacrylate.
  • the transesterification was carried out in a 4 L mini planter reactor with packed column with Sulzer packing made of stainless steel and liquid distributor.
  • the reflux ratio was 25: 1 (reflux: drain), the stirring speed (propeller stirrer) 300 rpm and the air inlet 1, 5 L / h.
  • the temperature in the bottom was between 87 0 C and 93 0 C, the steam temperature was between 82 0 C and 83 0 C.
  • the kinetics of the reaction was monitored by NMR and showed a complete reaction after only 4.5 h. After 7 h, the reaction was stopped and the vacuum was released. The suspension was cooled. The crude bottoms product (1714 g) was then analyzed by NMR containing 88 mol% MMA and 12 mol% polyethoxymethacrylate.
  • the transesterification was carried out in a 4 L mini planter reactor with packed column with Sulzer packing made of stainless steel and liquid distributor.
  • the reflux ratio was 25: 1 (reflux: drain), the stirring speed (propeller stirrer) 300 rpm and the air inlet 1, 5 L / h.
  • the temperature in the bottom was between 87 0 C and 93 0 C, the steam temperature was between 82 0 C and 83 0 C. After 6 h, the vacuum was reduced to 100 mbar, then to 6 mbar. The temperature in the bottom was maintained at 50 to 60 0 C. At a temperature of 60 ° C., 1045 g (12 mol) of methacrylic acid were added to the suspension.
  • the crude bottoms product (2100 g) was then analyzed by NMR (49% by weight of methacrylic acid, 2% by weight of MMA, 45% by weight of polyethoxymethacrylate, 2% by weight of polyethoxyalcohol) containing 9.4 g of residual catalyst K3PO4.
  • the transesterification was carried out in a 4 L mini planter reactor with packed column with Sulzer packing made of stainless steel and liquid distributor.
  • the reflux ratio was 25: 1 (reflux: drain), the stirring speed (propeller stirrer) 300 rpm and the air inlet 1, 5 L / h.
  • a viscous solution (1525 g, APHA color number 89) was obtained, which was subsequently analyzed by NMR.
  • the suspension contained 63 mol% MMA and 37 mol% polyethoxy methacrylate.
  • the transesterification took place in a 750 ml miniplane reactor with Oldershaw column and liquid distributor.
  • the reflux ratio was 25: 1 (reflux: drain), the stirring speed (armature stirrer) 300 rpm and the air inlet 1, 5 L / h.
  • the temperature in the bottom was between 77 0 C and 82 0 C, the steam temperature was between 46 0 C and 74 0 C. After 5.5 h, the reaction was stopped and the vacuum was released. The suspension was cooled and filtered through a pleated filter. Subsequently, excess MMA was evaporated.
  • a white solid product (486 g) was obtained, which was subsequently analyzed by NMR.
  • the product contained> 98 mol% Polyethoxymethacrylat and ⁇ 1 wt .-% Polyetho- xyalkohol.
  • the number of OH groups was determined, it was 0.3 mg KOH / g).
  • the transesterification took place in a 750 ml mini-plan reactor with Oldershaw column and liquid distributor.
  • the reflux ratio was 25: 1 (reflux: drain), the stirring speed (armature stirrer) 300 rpm and the air inlet 1, 5 L / h.
  • MMA methyl methacrylate
  • 246 g (0.25 mol) of a powdered polyethoxyalcohol (MeO- (CH 2 CH (Me) O) 9 - (CH 2 CH 2 O) I 0 -H, OH number 57, M w ca. 948) and 2.13 g (4 mol%) of potassium phosphate were initially charged and stirred. Subsequently, the mixture was gradually heated to 70 0 C and the vacuum was set (400 mbar). During the reaction was continuously removed distillate (MMA and methanol) and partially recycled (reflux ratio 25: 1). The temperature in the bottom was between 70 0 C and 77 0 C, the steam temperature was between 50 0 C and 65 0 C. After 3 h, the reaction was stopped and the vacuum was released. The suspension was cooled and filtered through pleated filters. Subsequently, excess MMA was evaporated.
  • a viscous solution (240 g) was obtained, which was subsequently analyzed by NMR. It contained 2 mol% of polyethoxyalcohol and 95 mol% of polyethoxymethacrylate.
  • the transesterification was carried out in a 4 L mini planter reactor with packed column with Sulzer packing made of stainless steel and liquid distributor.
  • the reflux ratio was 10: 1 (reflux: drain), the stirring speed (armature stirrer) 180 U / min and the air inlet 1, 5 L / h.
  • the temperature in the bottom was between 85 0 C and 89 0 C, the steam temperature was between 73 0 C and 77 0 C. After 5 h, the reaction was stopped and the vacuum was released. The suspension was cooled and filtered through a pleated filter. Finally, excess MMA was evaporated.
  • a white, waxy suspension (1165 g) was obtained, which was subsequently analyzed by NMR.
  • the suspension contained 99 mol% of the desired product.
  • the transesterification took place in a 750 ml mini-plan reactor with Oldershaw column and liquid distributor.
  • the reflux ratio was 15: 1 (reflux: drain), the stirring speed (armature stirrer) 250 rpm and the air inlet 1, 5 L / h.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

L'invention concerne des procédés de fabrication d'esters d'acides (méth)acryliques (E) d'alcools (A) contenant des groupes polyalkoxy, consistant à transestérifier des alcools (A) contenant des groupes polyalkoxy, représentés par la formule (I) RO-[(CH2)mO]n-H dans laquelle m est un entier de 1 à 10, n est un entier de 1 à 100 et R est un alcool droit, saturé ou insaturé, portant 1 à 30 atomes de C, avec au moins un ester d'acide (méth)acrylique (D) en présence d'au moins un sel inorganique (S).
EP10715208A 2009-04-24 2010-04-16 Procédés de fabrication d'esters d'acides (méth)acryliques d'alcools contenant des groupes polyalkoxy Withdrawn EP2421908A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US17223709P 2009-04-24 2009-04-24
DE102009002632A DE102009002632A1 (de) 2009-04-24 2009-04-24 Verfahren zur Herstellung von (Meth)acrylsäureestern von Polyalkoxylgruppen enthaltenden Alkoholen
PCT/EP2010/055024 WO2010121962A1 (fr) 2009-04-24 2010-04-16 Procédés de fabrication d'esters d'acides (méth)acryliques d'alcools contenant des groupes polyalkoxy

Publications (1)

Publication Number Publication Date
EP2421908A1 true EP2421908A1 (fr) 2012-02-29

Family

ID=42779514

Family Applications (1)

Application Number Title Priority Date Filing Date
EP10715208A Withdrawn EP2421908A1 (fr) 2009-04-24 2010-04-16 Procédés de fabrication d'esters d'acides (méth)acryliques d'alcools contenant des groupes polyalkoxy

Country Status (5)

Country Link
US (1) US20100274042A1 (fr)
EP (1) EP2421908A1 (fr)
CN (1) CN102414250A (fr)
DE (1) DE102009002632A1 (fr)
WO (1) WO2010121962A1 (fr)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE202013008301U1 (de) 2013-09-20 2013-11-25 Basf Se Härtbare Beschichtung hergestellt mit einem aus (Meth)acrylaten von Polyalkoxygruppen enthaltenden Alkoholen aufgebauten Copolymer
DE102014202963A1 (de) * 2014-02-18 2015-08-20 Basf Se Verfahren zur Herstellung von (Meth)acrylsäureestern von Polyalkoxygruppen enthaltenden Alkoholen
PL3262129T3 (pl) * 2015-02-26 2019-11-29 Basf Se Sposób wytwarzania di(met)akrylanu etoksylowanego izosorbidu
EP4293010A1 (fr) * 2022-06-15 2023-12-20 Evonik Operations GmbH Procédé de (trans)estérification discontinue de composés (méth)acrylates

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS635054A (ja) * 1986-06-26 1988-01-11 Mitsui Toatsu Chem Inc アクリル酸またはメタクリル酸のシクロヘキシルエステルの製造方法
JPH0466555A (ja) 1990-07-03 1992-03-02 Mitsubishi Gas Chem Co Inc （メタ）アクリル酸エステルの製造法
DE19602035C2 (de) * 1996-01-20 1998-04-02 Roehm Gmbh Verfahren zur Herstellung von Alkoxypolyglycol(meth)acrylaten
EP0837049B1 (fr) 1996-10-17 2002-07-31 Rohm And Haas Company Procédé de préparation de monomères
AU743962B2 (en) 1997-08-29 2002-02-14 Rohm And Haas Company Transesterification process
DE102004036930A1 (de) * 2004-07-29 2006-03-23 Basf Ag Katalysiertes Verfahren zur Herstellung von(Meth)acrylaten von N-hydroxyalkylierten Amiden
DE102005052931A1 (de) * 2005-11-03 2007-05-10 Basf Ag Katalytisches Verfahren zur Herstellung von (Meth)acrylaten von N-hydroxyalkylierten Lactamen

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2010121962A1 *

Also Published As

Publication number Publication date
DE102009002632A1 (de) 2010-10-28
WO2010121962A1 (fr) 2010-10-28
CN102414250A (zh) 2012-04-11
US20100274042A1 (en) 2010-10-28

Similar Documents

Publication Publication Date Title
EP2294048B1 (fr) Procédé de production d'esters d'acide (méth)acrylique
EP1465859A1 (fr) Procede de fabrication continue d'alkyl(meth)acrylates
EP1399408A1 (fr) Procede de production d'esters d'acide (meth)acrylique
EP1583733A1 (fr) Amelioration apportee a un procede de production en continu d'alkyl(meth)acrylates avec recyclage multiple du catalyseur
EP2162423A1 (fr) Procede de production de (meth)acrylates
DE19604267A1 (de) Verfahren zur kontinuierlichen Herstellung von Alkylestern der (Meth)acrylsäure
DE102007031473A1 (de) Verfahren zur Herstellung von Ethylenglycoldimethacrylat
DE19536178A1 (de) Verfahren und Vorrichtung zur kontinuierlichen Herstellung von Alkylestern der (Meth)acrylsäure
EP0874870B1 (fr) Procede de production de polyglycol(meth)acrylates
WO2017102675A1 (fr) Procédé de préparation du (méth)acrylate de polyglycol éther d'hydroxybenzophénone
EP1490326B1 (fr) Procede de production d'esters d'acide (meth)acrylique
WO2010121962A1 (fr) Procédés de fabrication d'esters d'acides (méth)acryliques d'alcools contenant des groupes polyalkoxy
DE19851983A1 (de) Verfahren zur kontinuierlichen Herstellung von Alkylestern der (Meth)acrylsäure
EP1399409B1 (fr) Procede de production d'esters d'acide (meth)acrylique
DE10353934A1 (de) Verfahren zur Herstellung von Metallsalzen der Trifluormethansulfonsäure und deren Verwendung als Veresterungskatalysatoren
EP2619173B1 (fr) Procédé de production d'esters d'acides (méth)acryliques d'alcools aminés à substitution n,n
DE60016409T2 (de) Verfahren zum führen von gleichgewichtsbegrenzten reaktionen
DE102007031474A1 (de) Verfahren zur Herstellung von Butandioldimethacrylaten
EP1299345B1 (fr) Procede de production d'aminoalkyl(meth)acrylates
DE102008043810A1 (de) Verfahren zur Herstellung von (Meth)acrylsäureestern von Prenol und Isoprenol
DE60319624T2 (de) Zersetzung eines Michael-Adduktes von Acrylsäure oder Acrylsäureester
EP1284954B1 (fr) Procede de production d'esters d'acides carboniques insatures
EP2139863A2 (fr) Procédé de production d'esters d'acide (méth)acrylique d'imidazoles n-hydroxyalkylés
WO2015124403A1 (fr) Procédé de préparation d'esters (méth)acryliques à partir d'alcools polyalcoxylés
DE102010000945A1 (de) Verfahren zur Herstellung von (Meth)acrylsäureestern

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20111124

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO SE SI SK SM TR

DAX Request for extension of the european patent (deleted)
STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN

18D Application deemed to be withdrawn

Effective date: 20120710