Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
  • C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
  • C07D207/18—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having one double bond between ring members or between a ring member and a non-ring member
  • C07D207/22—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
  • C07D207/24—Oxygen or sulfur atoms
  • C07D207/26—2-Pyrrolidones
  • C07D207/273—2-Pyrrolidones with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to other ring carbon atoms
• • 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
  • 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

Definitions

• the present invention relates to a process for the catalytic preparation of (meth) acrylic acid esters of N-hydroxyalkylated lactams and their use.
• German patent application DE 10 2005 052 931.3 discloses a catalytic process for the preparation of (meth) acrylic acid esters of N-hydroxyalkylated lactams, in which the esterification or transesterification is carried out in the presence of a heterogeneous inorganic salt.
• the object has been achieved by a process for the preparation of (meth) acrylic acid esters (F) of N-hydroxyalkylated lactams, in which ring-shaped N-hydroxyalkylated lactams (L),
• R 1 may not have any atom other than a carbon atom directly adjacent to the lactam carbonyl group
• R 2 is C 1 -C 20 -alkylene, C 5 -C 12 -cycloalkyl, C 6 -C 12 -arylene or by one or more oxygen and / or sulfur atoms and / or one or more substituted or unsubstituted imino groups and / or by one or more cycloalkyl radicals , - (CO) -, -0 (CO) O-, - (NH) (CO) O-, -0 (CO) (NH) -, -0 (CO) - or - (CO) O groups interrupted C 2 -C 20 -alkylene, where the radicals mentioned may each be substituted by aryl, alkyl, aryloxy, alkyloxy, heteroatoms and / or heterocycles, or
• Ci-C 2 o-alkylene for example, methylene, 1, 2-ethylene, 1, 2-propylene, 1, 3-propylene, 1, 4- Butylene, 1,6-hexylene, 2-methyl-1,3-propylene, 2-ethyl-1,3-propylene, 2,2-dimethyl-1,3-propylene, 2,2-dimethyl-1,4 butylene,
• aryl optionally substituted by aryl, alkyl, aryloxy, alkyloxy, heteroatoms and / or heterocycles substituted C5-Ci len 2 cycloalkylene, for example cyclopropylene, cyclopentylene, cyclohexylene, cyclooctylene, cyclododecylene,
• aryl optionally substituted by aryl, alkyl, aryloxy, alkyloxy, heteroatoms and / or heterocycles C6-Ci2-arylene, for example, 1, 2-, 1, 3- or 1, 4-phenylene, 4,4'-biphenylene, tolylene or xylylene ,
• R 1 examples are 1, 2-ethylene, 1, 2-propylene, 1, 1-dimethyl-1, 2-ethylene, 1-hydroxymethyl-1, 2-ethylene, 2-hydroxy-1, 3-propylene, 1 , 3-propylene, 1, 4-butylene, 1, 5-pentylene, 2-methyl-1,3-propylene, 2-ethyl-1,3-propylene, 2, 2-dimethyl-1,3-propylene and 2 , 2-Dimethyl-1, 4-butylene, preferred are 1, 4-butylene, 1, 5-pentylene and 1, 3-propylene, more preferably 1, 3-propylene.
• R 2 examples are 1, 2-ethylene, 1, 2-propylene, 1, 1-dimethyl-1, 2-ethylene, 1-hydroxy-methyl-1, 2-ethylene, 2-hydroxy-1, 3-propylene , 1, 3-propylene, 1, 4-butylene, 1, 6-hexylene, 2-methyl-1, 3-propylene, 2-ethyl-1, 3-propylene, 2, 2-dimethyl-1, 3-propylene and 2,2-dimethyl-1,4-butylene, 1,2-cyclopentylene, 1,3-cyclopentylene, 1,2-cyclohexylene, 1,3-cyclohexylene, ortho-phenylene, 3-oxa-1,5-pentylene , 3,6-dioxa-1, 8-octylene and 3,6,8-trioxa-1, 8,11-undecylene, preferred are 1,2-ethylene, 1,2-propylene, 1,3-propylene, especially 1, 2-ethylene and 1, 2-propylene are preferred, and very particular preference is 1, 2-ethylene.
• N-hydroxyalkylated lactams (L) are optically active, they are preferably used racemically or as a mixture of diastereomers, but it is also possible to use them as pure enantiomers or diastereomers or as enantiomer mixtures.
• the esterification with (meth) acrylic acid (S) or preferably the transesterification with at least one, preferably exactly one (meth) acrylic ester (D) according to the invention in the presence of at least one catalyst (K) is selected from the group consisting of alkali metal hydroxides, alkaline earth metal hydroxides and metal acetylacetonates.
• (meth) acrylic acid (S) or for transesterification (meth) acrylic ester (D) of a saturated alcohol can be used, 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.
• C4-alkyl esters of (meth) acrylic acid 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.
• Examples of compounds (D) are (meth) acrylic acid, methyl, ethyl, n-butyl, isobutyl, tert-butyl, n-octyl and 2-ethylhexyl esters, 1,2-ethylene glycol di and mono (meth) acrylate, 1,4-butanediol di- and mono (meth) acrylate, 1,6-hexanediol di- and mono (meth) acrylate, trimethylolpropane tri (meth) acrylate and pentaerythritol tetra (meth) acrylate ,
• (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.
• Catalysts (K) which can be used according to the invention are selected from the group consisting of alkali metal hydroxides, alkaline earth metal hydroxides and metal acetyl acetonates.
• catalysts can be both homogeneous and heterogeneous.
• Heterogeneous catalysts are in the context of this document according to the invention such that friendliness 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 of not more than 0 , 25 g / l.
• alkali metal and alkaline earth metal hydroxides are understood to mean basic compounds which have a pKa value of not more than 7.0, preferably not more than 6.0 and more preferably not more than 4.0.
• the alkali metal and alkaline earth metal hydroxides may be used both in solid form and in the form of solutions, for example as aqueous solutions.
• the alkali metal and alkaline earth metal hydroxides are preferably added in solid form to the process according to the invention.
• Suitable alkali metal hydroxides are, for example, lithium hydroxide, sodium hydroxide and potassium hydroxide.
• Suitable alkaline earth metal hydroxides are, for example, magnesium hydroxide and calcium hydroxide. Preference is given to alkali metal hydroxides such as lithium hydroxide, sodium hydroxide and potassium hydroxide.
• metal acetylacetonates are metal chelates with the enolate anion of 2,4-pentanedione (acetylacetone) and have the general formula M n (CsH 7 C) n or M n (acac) n .
• Metals M are numerous metals, especially transition metals in question. Preference is given to metals M selected from the group of transition metals, alkali metals, alkaline earth metals and aluminum. Suitable alkali and alkaline earth metals are, for example, lithium, sodium, potassium, magnesium and calcium. Preference is given to using aluminum, lithium, sodium, potassium and calcium.
• Titanium, zirconium, chromium, manganese, cobalt, nickel and copper are preferably used as transition metals.
• Preferred representatives of this group are lithium acetylacetonate (Li (acac)), sodium acetylacetonate (Na (acac)) and potassium acetylacetonate (K (acac)) as well as calcium acetylacetonate
• the esterification or transesterification catalyzed by the catalyst (K) is generally carried out at from 30 to 140 ° C., preferably from 30 to 100 ° C., more preferably from 40 to 90 ° C., and very preferably from 50 to 80 ° C. ,
• the reaction is carried out under a slight vacuum of, for example, 200 hPa to atmospheric pressure, preferably 200 to 600 hPa and particularly preferably 300 to 500 hPa, if the water released in the esterification or that formed in the transesterification low-boiling alcohol, optionally as an azeotrope, to be distilled off.
• a slight vacuum of, for example, 200 hPa to atmospheric pressure, preferably 200 to 600 hPa and particularly preferably 300 to 500 hPa, if the water released in the esterification or that formed in the transesterification low-boiling alcohol, optionally as an azeotrope, to be distilled off.
• the molar ratio between (meth) acrylic acid (S) or (meth) acrylic acid ester (D) and N-hydroxyalkylated lactam (L) in the catalyzed by a catalyst (K) esterification or transesterification is usually 1-6: 1 mol / mol, preferably 1 - 5: 1 mol / mol and more preferably 1 - 4: 1 mol / mol.
• the reaction time in the case of the esterification or transesterification catalyzed by a catalyst (K) is generally 45 minutes to 18 hours, preferably 2 hours to 12 hours and particularly preferably 3 to 10 hours.
• the content of catalyst (K), which is selected from the group of alkali metal hydroxides, alkaline earth metal hydroxides and metal acetylacetonates, in the reaction medium is generally in the range of about 0.01 to 5 mol%, preferably 0.1-3 and especially ders preferably 0.3 to 2 mol% based on the sum of the N-hydroxyalkylated lactams (L) used.
• an oxygen-containing gas is continuously introduced into the reaction mixture during the reaction.
• continuous oxygen introduction is likewise preferred.
• 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 approaches are usually largely anhydrous, d. H.
• the water content is preferably less than 10, more preferably less than 5, more preferably less than 1 and most preferably less than 0.5 wt.%.
• the water content is between 100 and 5000 ppm, preferably between 500 and 1000 ppm.
• 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-butyl
• the reaction is carried out in the (meth) acrylic acid ester (D) used as starting material.
• the product (F) after Termination of the reaction as about 10 - 80 wt .-% solution in the starting material used as (meth) acrylic acid ester (D) is obtained, in particular as 20 to 50 wt .-% solution.
• the educts are either dissolved, suspended as solids or in emulsion in the reaction medium before.
• the catalyst (K) which is selected from the group of alkali metal hydroxides, alkaline earth metal hydroxides and metal acetylacetonates, is used in the absence of solvents and preferably as a solid.
• the reaction can be carried out continuously, for example in a tubular reactor or in a stirred reactor cascade, or discontinuously. In a preferred embodiment of the process according to the invention, however, all starting materials, as well as stabilizers and the catalyst (K) are completely added 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 water in the case of esterification or alcohols which are released in a transesterification of the (meth) acrylic acid esters (D) is carried out continuously or stepwise in a conventional manner, e.g. by vacuum, azeotropic removal, stripping, absorption, pervaporation and diffusion via membranes or extraction.
• the esterification or transesterification is advantageously carried out in the presence of an oxygen-containing gas, preferably air or air-nitrogen mixtures.
• This stripping can be carried out, for example, by passing an oxygen-containing gas, preferably an air or air-nitrogen mixture, through the reaction mixture, if appropriate in addition to a distillation.
• an oxygen-containing gas preferably an air or air-nitrogen mixture
• molecular sieves or zeolites for absorption, molecular sieves or zeolites (pore size, for example, in the range of about 3-10 angstroms) are preferred, separation by distillation or by means of suitable semipermeable membranes.
• reaction mixture obtained from the esterification or transesterification can be used without further purification or, if necessary, purified in a further step.
• a separation from the catalyst (K) is generally carried out by filtration, electro-filtration, absorption, centrifugation or decantation or by distillation or rectification.
• the separated catalyst (K) can then be used for further reactions.
• the separation from the organic solvent is usually carried out by distillation, rectification or solid reaction products by filtration.
• the optionally purified reaction mixture is preferably subjected to a distillation in which the (meth) acrylic acid ester (F) of the N-hydroxyalkylated lactams is separated by distillation from unreacted (meth) acrylic acid (S) or unreacted (meth) acrylic acid ester (D) and optionally formed by-products ,
• the continuous introduction of oxygen is also preferred.
• the distillation units are usually rectification columns of a conventional design with circulation evaporator and condenser.
• the feed is preferably in the bottom region, 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 esters (F) of the N-hydroxyalkylated lactams 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. From the bottoms, bell bottoms, sieve trays, valve trays, Thormann trays and / or dual-flow trays are preferred, of the trays are those with rings, spirals, saddles, Raschig, Intos or Pall rings, Barrel or Intalox Saddling, top Pak etc. or braids preferred.
• the desired product is distilled batchwise, initially low-boiling components are removed from the reaction mixture, usually solvent or unreacted (meth) acrylic acid (S) or (meth) acrylic acid ester (D). After separation of these low boilers, the distillation temperature is increased and / or reduced the vacuum and the desired product distilled off.
• initially low-boiling components are removed from the reaction mixture, usually solvent or unreacted (meth) acrylic acid (S) or (meth) acrylic acid ester (D).
• the distillation temperature is increased and / or reduced the vacuum and the desired product distilled off.
• the remaining distillation residue is usually discarded.
• reaction conditions in the esterification or transesterification according to the invention are mild. Due to the low temperatures and other mild conditions, the formation of by-products in the reaction is avoided, which may otherwise be derived, for example, from strongly acidic or basic catalysts or may be caused by undesired radical polymerization of the (meth) acrylic compound (B) used otherwise it can only be prevented by adding stabilizers.
• additional stabilizer can be added to the reaction mixture via the storage stabilizer which is present anyway in the (meth) acrylic compound (B), for example hydroquinone monomethyl ether, phenothiazine, phenols, such as 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 Aktiengesellschaft or amines such as BPD Kerobit ® from BASF Aktiengesellschaft (N, N'-di-sec-butyl-p-phenylenediamine), for example in quantities of 50 to 2000 ppm ,
• the catalysts (K) used according to the invention show only a slight tendency to side reactions.
• reaction under the reaction conditions according to the invention is very selective, it is generally less than 10%, preferably less than 5% by-products (based on the conversion).
• the (meth) acrylic esters (F) of N-hydroxyalkylated lactams prepared 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 Paper application.
• 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) 400 rpm and the air inlet 1, 5 L / h.
• distillate (azeotrope of MMA and methanol) was continuously added. away. After 300 min, the reaction was stopped and the vacuum was released. The suspension was cooled and then filtered through a pressure suction filter. 494 g of crude product were obtained.
• Example 1 was followed analogously, but instead of lithium hydroxide 1, 2 g (30 mmol, 2.0 mol% based on hydroxyethyl imidazole) of solid sodium hydroxide were used as the catalyst. The reaction was stopped after 120 min and the vacuum was released. The suspension was cooled and then filtered through a pressure suction filter. 644 g of crude product were obtained.
• the crude product 200 ppm Kerobit BPD ® (BASF Aktiengesellschaft, N, N'-di-sec-butyl-p-phenylenediamine) was added for stabilization.
• the mixture was distilled under vacuum, initially removing excess methyl methacrylate, and then the desired product was obtained (142-144 0 C at 2.8 mbar). During the distillation, oxygen was introduced into the mixture to be distilled.
• the crude product 200 ppm Kerobit BPD ® (BASF Aktiengesellschaft, N, N'-di-sec-butyl-p-phenylenediamine) was added for stabilization.
• the mixture was distilled under vacuum, initially excess methyl methacrylate was removed, and then the desired product was obtained (156-158 0 C at 5.5 mbar). During the distillation, oxygen was introduced into the mixture to be distilled.
• Example 1 was followed analogously, but instead of lithium hydroxide 4.2 g (30 mmol, 2.0 mol% based on hydroxyethylimidazole) of solid sodium acetylacetonate were used as the catalyst. The reaction was stopped after 180 min and the vacuum was released. The suspension was cooled and then filtered through a pressure suction filter. This gave 457 g of crude product.

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• 2008
  • 2008-02-11 CN CN2008800051881A patent/CN101631760B/zh not_active Expired - Fee Related
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