RU2415133C2 - Catalytic method of producing (meth)acrylates of n-hydroxyalkylated amides - Google Patents

Abstract

FIELD: chemistry. ^ SUBSTANCE: present invention relates to a method of producing (meth)acrylates of N-hydroxy-alkylated amides, in which cyclic N-hydroxyalkylated amides (C): , where Z1 denotes unsubstituted or mono-substituted nitrogen (N-R3); R1 and R2, in each case independently denote an alkylene with 2-20 carbon atoms, cycloalkylene with 5-12 carbon atoms, arydene with 6-12 carbon atoms; R3 denotes hydrogen, alkyl with 1-18 carbon atoms, alkenyl with 2-18 carbon atoms, aryl with 6-12 carbon atoms or cycloalkyl with 5-12 carbon atoms; etherified with methacrylic acid or reesterified with at least one (meth)acrylic ester (D) in the presence of at least one heterogeneous catalyst selected from a group consisting of inorganic salts (Co), having pKb not higher than 7.0 and not lower than 1.0, and its solubility in the reaction medium at 25C is not more than 1 g/l, and enzymes (F) selected from a group comprising esterase (E.C.3.1.-.-), lipase (E.C.3.1.1.3), glycosylase (E.C.3.2. -.-) and protease (E.C.3.4. -.-), where the heterogeneous catalyst is separated from the reaction mixture through filtration, electrofiltration, absorption, centrifuging or decantation. ^ EFFECT: efficient method of producing (meth)acrylates of N-hydroxyalkylated amides. ^ 6 cl, 5 ex

Description

The present invention relates to a method for the catalytic preparation of (meth) acrylates of N-hydroxyalkylated amides and their use.

The preparation of esters of (meth) acrylic acid is most often carried out by catalytic esterification of (meth) acrylic acid or transesterification of other esters of (meth) acrylic acid with alcohols in the presence of strong acids or strong bases. Moreover, as a rule, an ester of (meth) acrylic acid, which is sensitive to acid or base, often cannot be purposefully obtained by esterification or transesterification.

In the sense of the present invention, ureidoalcohols are those compounds which contain at least one N- (C = O) -N group and at least one hydroxyl group (-OH). Similarly, N-hydroxyalkylated amides in the sense of the present invention are those compounds which contain at least one Z ¹ - (C = O) -N group and at least one hydroxyl group (-OH), wherein the hydroxyl group bound to a nitrogen atom of the group Z ¹ - (C = O) -N, and Z ¹ has the meanings given below.

Such ureidoalcohols and N-hydroxyalkylated amides are hydrolyzed very easily under the action of acids and bases. In this case, especially in the reaction with the base in the presence of (meth) acrylate, side reactions take place, for example, such as the Michael addition reaction (see, for example, European application EP-A1236994, p. 3, column 47 and subsequent pages) .

EP-A1236994 describes the preparation of ureido (meth) acrylates by transesterification of (meth) acrylate in the presence of titanium alcoholates or titanium, zirconium, iron or zinc 1,3-dicarbonyl chelates.

The disadvantage of these compounds is that the metal compounds are sensitive to moisture and therefore easily deactivated. In addition, traces of catalysts remaining in the product can cause irregular polymerization in the future and therefore must be removed from the product, which requires additional costs. Most often, this removal is carried out by washing with water, which requires subsequent drying of the product.

Japanese patent applications JP-A 62-185059 and JP-A 62-175448 describe the interaction of (meth) acrylates with alkyl alcohols in the presence of alkali metal carbonates. Japanese Patent Application JP-A 62-230755 describes the interaction of (meth) acrylates with alkyl alcohols in the presence of alkali metal phosphates.

Only alkyl and dialkyl amino alcohols are indicated and there is no indication of ureidoalcohols or N-hydroxyalkylated amides.

U.S. Pat. No. 2,871,223 discloses the preparation of ureido (meth) acrylates by reacting ureidoalcohols with (meth) acrylic acid chloride.

The use of (meth) acrylic acid chloride in this reaction leads to the formation of salts and, due to their high reactivity, to non-selective reactions, such as, for example, diacrylation.

The preparation of esters of (meth) acrylic acid by enzymatic esterification or transesterification is generally known, for example, from European application EP-A 999229.

Derango et al. In Biotechnol. Lett. 1994, 16, 241-246 describe lipase-catalyzed production of carbamoyloxyethyl methacrylate by transesterification of 2-hydroxyethyl carbamate with vinyl methacrylate. Complete conversion is achieved due to the use of a special vinyl methacrylate educt, since the released vinyl alcohol shifts the reaction equilibrium towards acetaldehyde. The disadvantage of this method is the commercial inaccessibility of vinyl methacrylate. In addition, O-hydroxyalkylated carbamoyls are indicated in this reference, and therefore, the reaction system is different from the ureidoalcohols and N-hydroxyalkylated amides undergoing conversion according to the invention.

In international application WO 2004/50888, other O-hydroxyalkylated carbamoyls are subjected to enzymatic esterification and transesterification. Here we are also talking about a different reaction system than the ureidoalcohols and N-hydroxyalkylated amides undergoing conversion according to the invention.

An object of the present invention was to provide a process for the production of (meth) acrylates of N-hydroxyalkylated amides with a high degree of conversion and a high degree of purity from simple educts. The synthesis should proceed under mild conditions, resulting in products with a low color index and high purity. In particular, the fraction of repeatedly (meth) acrylated products should be suppressed. In addition, the catalyst used should then be easily separated so that subsequent processing of the reaction product is not necessary, for example, in the processing stages.

This problem is solved by the method of producing (meth) acrylates of N-hydroxyalkylated amides, in which cyclic N-hydroxyalkylated amides (C):

or N-hydroxyalkylated amides (O) with an open chain:

Where

Z ¹ means oxygen, sulfur, unsubstituted or substituted phosphorus or unsubstituted or monosubstituted nitrogen (NR ³ ),

R ¹ and R ² , in each case independently of one another, are alkylene with 2-22 carbon atoms, cycloalkylene with 5-12 carbon atoms, arylene with 6-12 carbon atoms or alkylene with 2-20 carbon atoms, interrupted by one or by several oxygen and / or sulfur atoms, and / or one or more substituted or unsubstituted imino groups, and / or one or more cycloalkyl groups, groups: - (CO) -, -O (CO) O-, - (NH) ( CO) O-, -O (CO) (NH) -, -O (CO) - or - (CO) O-, and these radicals can be replaced each time with aryl, alkyl, aryloxy group, alkyloxy group, g teroatomami and / or heterocycles, or

R ² —OH means a group of the formula - [X _i ] _k —H,

R ³ , R ⁴ and R ⁵ , independently of each other in each case, mean hydrogen, alkyl with 1-18 carbon atoms or alkyl with 2-18 carbon atoms, optionally interrupted by one or more oxygen atoms and / or sulfur, and / or one or more substituted or unsubstituted imino groups, alkenyl with 2-18 carbon atoms, aryl with 6-12 carbon atoms, cycloalkyl with 5-12 carbon atoms or a five- or six-membered heterocycle containing oxygen, nitrogen and / or sulfur atoms wherein said radicals may be substituted each time with aryl, alkyl, aryloxy- Rupp, alkyloxy, heteroatoms and / or heterocycles, wherein R ³ and R ⁵ together may also form a five to twelve-membered ring,

with the proviso that when Z ¹ is oxygen, R ⁵ is exclusively unsubstituted alkyl with 1-18 carbon atoms, aryl with 6-12 carbon atoms or cycloalkyl with 5-12 carbon atoms,

k means a number from 1 to 50 and

X _i for each value i = from 1 to k, independently of each other, can be selected from the group:

—CH ₂ —CH ₂ —O—, —CH ₂ —CH ₂ —N (H) -, —CH ₂ —CH ₂ —CH ₂ —N (H) -, —CH ₂ —CH (NH ₂ ) -, CH ₂ —CH (NHCHO) -, —CH ₂ —CH (CH ₃ ) —O— —CH (CH ₃ ) —CH ₂ —O—, —CH ₂ —C (CH ₃ ) ₂ —O—, —C (CH ₃ ) ₂ —CH ₂ —O—, —CH ₂ —CH ₂ —CH ₂ —O—, —CH ₂ —CH ₂ —CH ₂ —CH ₂ —O—, —CH ₂ —CHVin — O—, —CHVin — CH ₂ —O—, —CH ₂ —CHPh — O— and —CHPh — CH ₂ —O—,

where Ph is phenyl and Vin is vinyl,

esterify with methacrylic acid or transesterify with at least one (meth) acrylic acid ester (D) in the presence of at least one heterogeneous catalyst selected from the group consisting of inorganic salts (C) and enzymes (F).

By the method of the invention, it is possible to obtain (meth) acrylates of N-hydroxyalkylated amides in high yield, under mild conditions, with good color indices and without a washing step for cleaning products.

According to the invention, the term “(meth) acrylic acid” means methacrylic acid and acrylic acid, preferably methacrylic acid.

For the above radicals:

alkylene with 2-20 carbon atoms, optionally substituted with aryl, alkyl, aryloxy group, alkyloxy group, heteroatoms and / or heterocycles, are, for example, 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;

cycloalkylene with 5-12 carbon atoms, optionally substituted with aryl, alkyl, aryloxy group, alkyloxy group, heteroatoms and / or heterocycles, are, for example, cyclopropylene, cyclopentylene, cyclohexylene, cyclooctylene, cyclododecylene;

alkylene with 2-20 carbon atoms, optionally substituted with aryl, alkyl, aryloxy group, alkyloxy group, heteroatoms and / or heterocycles interrupted by one or more oxygen and / or sulfur atoms, and / or one or more substituted or unsubstituted by imino groups and / or one or more groups: cycloalkyl, - (CO) -, -O (СО) O-, - (NH) (СО) O-, -O (СО) (NH) -, -O (СО ) - or - (CO) O-, are, for example, 1-oxa-1,3-propylene, 1,4-dioxa-1,6-hexylene, 1,4,7-trioxa-1,9-nonylene, 1-oxa-1,4-butylene, 1,5-dioxa-1,8-octylene, 1-oxa-1,5-pentylene, 1-oxa-1,7-heptylene, 1,6-dio ca-1,10-decylene, 1-oxa-3-methyl-1,3-propylene, 1-oxa-3-methyl-1,4-butylene, 1-oxa-3,3-dimethyl-1,4- butylene, 1-oxa-3,3-dimethyl-1,5-pentylene, 1,4-dioxa-3,6-dimethyl-1,6-hexylene, 1-oxa-2-methyl-1,3-propylene, 1,4-dioxa-2,5-dimethyl-1,6-hexylene, 1-oxa-1,5-pent-3-enylene, 1-oxa-1,5-pent-3-inylene, 1,1- , 1,2-, 1,3- or 1,4-cyclohexylene, 1,2- or 1,3-cyclopentylene, 1,2-, 1,3- or 1,4-phenylene, 4,4'-biphenylene 1,4-diaza-1,4-butylene, 1-aza-1,3-propylene, 1,4,7-triaz-1,7-heptylene, 1,4-diaza-1,6-hexylene, 1 4-diaza-7-oxa-1,7-heptylene, 4,7-diaza-1-oxa-1,7-heptylene, 4-aza-1-oxa-1,6-hexylene, 1-aza-4 -oxa-1,4-butylene, 1-aza-1,3-propylene, 4-aza-1-oxa- 1,4-butylene, 4-aza-1,7-dioxa-1,7-heptylene, 4-aza-1-oxa-4-methyl-1,6-hexylene, 4-aza-1,7-dioxo 4-methyl-1,7-heptylene, 4-aza-1,7-dioxa-4- (2'-hydroxyethyl) -1,7-heptylene, 4-aza-1-oxa (2'-hydroxyethyl) - 1,6-hexylene or 1,4-piperazinylene;

arylene with 6-12 carbon atoms, optionally substituted with aryl, alkyl, aryloxy group, alkyloxy group, heteroatoms and / or heterocycles, are, for example, 1,2-, 1,3- or 1,4-phenylene, 4 4'-biphenylene, toluene or xylylene;

alkyl with 1-18 carbon atoms or alkyl with 2-18 carbon atoms, optionally interrupted by one or more oxygen and / or sulfur atoms, and / or one or more substituted or unsubstituted imino groups, are, for example, methyl, ethyl, propyl , isopropyl, n-butyl, sec. butyl, tert.butyl, pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, 2,4,4-trimethylpentyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl, 1,1-dimethylpropyl 1,1-dimethylbutyl, 1,1,3,3-tetramethylbutyl, benzyl, 1-phenylethyl, 2-phenylethyl, α, α-dimethylbenzyl, benzhydryl, p-tolylmethyl, 1- (p-butylphenyl) ethyl, p-chlorobenzyl, 2,4-di-chlorobenzyl, p-methoxybenzyl, m-ethoxybenzyl, 2-cyanoethyl, 2-cyanopropyl, 2-methoxycarbonylethyl, 2-ethoxycarbonylethyl, 2-butoxycarbonylpropyl, 1,2-di (methoxycarbonyl) ethyl, 2-methoxyethyl, 2-ethoxyethyl, 2-butoxyethyl, diethoxymethyl, diethoxyethyl, 1,3-dioxolan-2-yl, 1,3-dioxan-2-yl, 2-methyl -1,3-dioxolan-2-yl, 4-methyl-1,3-dioxolan-2-yl, 2-isopropoxyethyl, 2-butoxypropyl, 2-octyloxyethyl, chloromethyl, 2-chloroethyl, trichloromethyl, trifluoromethyl, 1 , 1-dimethyl-2-chloroethyl, 2-methoxyisopropyl, 2-ethoxyethyl, butylthiomethyl, 2-dodecylthioethyl l, 2-phenylthioethyl, 2,2,2-trifluoroethyl, 2-hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl, 4-hydroxybutyl, 6-hydroxyhexyl, 2-aminoethyl, 2-aminopropyl, 3-aminopropyl, 4- aminobutyl, 6-aminohexyl, 2-methylaminoethyl, 2-methylaminopropyl, 3-methylaminopropyl, 4-methylaminobutyl, 6-methylaminohexyl, 2-dimethylaminoethyl, 2-dimethylaminopropyl, 3-dimethylaminopropyl, 4-dimethylaminobutyl, 6-dimethyl-2-methyl-2-methyl 2,2-dimethylethyl, 2-phenoxyethyl, 2-phenoxypropyl, 3-phenoxypropyl, 4-phenoxybutyl, 6-phenoxyhexyl, 2-methoxyethyl, 2-methoxypropyl, 3-methoxypropyl, 4-methoxy ibutyl, 6-methoxyhexyl, 2-ethoxyethyl, 2-ethoxypropyl, 3-ethoxypropyl, 4-ethoxybutyl or 6-ethoxyhexyl;

alkenyl with 2-18 carbon atoms, optionally interrupted by one or more oxygen and / or sulfur atoms, and / or one or more substituted or unsubstituted imino groups, are, for example, vinyl, 1-propenyl, allyl, metal, 1,1 dimethylallyl, 2-butenyl, 2-hexenyl, octenyl, undecenyl, dodecenyl, octadecenyl, 2-phenylvinyl, 2-methoxyvinyl, 2-ethoxyvinyl, 2-methoxyallyl, 3-methoxyallyl, 2-ethoxyallyl, 3-ethoxyallyl or 1- 2-vinyl chloride;

aryl with 6-12 carbon atoms, optionally interrupted by one or more oxygen and / or sulfur atoms, and / or one or more substituted or unsubstituted imino groups, are, for example, phenyl, tolyl, xylyl, α-naphthyl, β-naphthyl , 4-diphenyl, chlorophenyl, dichlorophenyl, trichlorophenyl, difluorophenyl, methylphenyl, dimethylphenyl, trimethylphenyl, ethylphenyl, diethylphenyl, isopropylphenyl, tert.butylphenyl, dodecylphenyl, methoxyphenyl, ethylphenylphenyl, phenylphenyl, phenyl, phenyl, phenyl, phenyl, phenyl children lphenyl, 2,4,6-trimethylphenyl, 2,6-dimethoxyphenyl, 2,6-dichlorophenyl, 4-bromophenyl, 2-or 4-nitrophenyl, 2,4- or 2,6-dinitrophenyl, 4-dimethylaminophenyl, 4- acetylphenyl, methoxyethylphenyl or ethoxymethylphenyl;

cycloalkyl with 5-12 carbon atoms, optionally interrupted by one or more oxygen and / or sulfur atoms, and / or one or more substituted or unsubstituted imino groups, are, for example, cyclopentyl, cyclohexyl, cyclooctyl, cyclododecyl, methylcyclopentyl, dimethylcyclopentyl, methylcyclohexyl , dimethylcyclohexyl, diethylcyclohexyl, butylcyclohexyl, methoxycyclohexyl, dimethoxycyclohexyl, diethoxycyclohexyl, butylthiocyclohexyl, chlorocyclohexyl, dichlorocyclohexyl, dichlorocyclopentyl, as well as saturated and whether unsaturated bicyclic systems, such as, for example, norbornyl or norbornenyl; and

a five- or six-membered heterocycle containing oxygen, nitrogen and / or sulfur atoms, optionally interrupted by one or more oxygen and / or sulfur atoms, and / or one or more substituted or unsubstituted imino groups, are, for example, furyl, thiophenyl, pyrryl , pyridyl, indolyl, benzoxazolyl, dioxolyl, dioxyl, benzimidazolyl, benzthiazolyl, dimethylpyridyl, methylquinolyl, dimethylpyrryl, methoxyfuryl, dimethoxypyridyl, difluoropyridyl, methylthiophenyl, isopropylthiophenyl or tert. butyl.

Examples of R ¹ 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, 1,6-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 and ortho-phenylene, preferably 1,2-ethylene, 1,2-propylene , 1,3-propylene, particularly preferably 1,2-ethylene and 1,2-propylene and most preferably 1,2-ethylene.

Examples of R ² 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, 1,6-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 and ortho-phenylene, preferably 1,2-ethylene, 1,2-propylene , 1,3-propylene, particularly preferably 1,2-ethylene and 1,2-propylene and most preferably 1,2-ethylene.

Examples of R ³ and R ⁵ are, independently of one another, hydrogen or alkyl with 1-4 carbon atoms, which means, within the scope of this description, methyl, ethyl, isopropyl, n. Propyl, n. Butyl, isobutyl, sec. Butyl or tert . butyl, preferably hydrogen, methyl, ethyl, n-propyl and n-butyl, particularly preferably hydrogen, methyl, ethyl and n-butyl, and most preferably hydrogen, methyl and ethyl, and especially hydrogen.

If R ³ and R ⁵ together form a cycle, then together they can mean 1,4-butylene, 1,5-pentylene or 3-oxa-1,5-pentylene.

Examples of R ⁴ are hydrogen, methyl, ethyl, isopropyl, n. Propyl, n. Butyl, isobutyl, sec. Butyl, tert.butyl, n. Hexyl, n. Heptyl, n. Octyl, n. Decyl, n. Dodecyl, N. tetradecyl, N. hexadecyl, N. octadecyl, N. eicosyl, 2-ethylhexyl, cyclopentyl, cyclohexyl, cyclooctyl, cyclododecyl, phenyl, naphthyl or benzyl.

Z ¹ preferably means O or NR ³ , particularly preferably NR ³ .

Cyclic alcohols (C) are preferred over open chain alcohols (O).

Preferred representatives of compounds (C) are 2'-hydroxyethyl-ethylene urea, 3'-hydroxypropyl-ethylene urea, 2'-hydroxypropyl-ethylene urea, 2'-hydroxyethyl-1,3-propylene urea, 2'-hydroxypropyl-1,3-propylene urea, 3'-hydroxypropyl-1,3-propylene urea, 2'-hydroxyethyl-1,2-propylene urea, 2'-hydroxypropyl-1,2-propylene urea, 3'-hydroxypropyl-1,2-propylene urea, 1 '- (2' -hydroxyethyl) -imidazolidin-2,4-dione, 1- (2'-hydroxyethyl) -dihydropyrimidin-2,4-dione or 3- (2-hydroxyethyl) oxazolidin-2-one. Particularly preferred are 2'-hydroxyethylethylene urea, 3'-hydroxypropyl-ethylene urea, 2'-hydroxyethyl-1,3-propylene urea and 3'-hydroxypropyl-1,3-propylene urea.

Preferred representatives of the compounds (O) are N- (2-hydroxyethyl) urea, N- (2-hydroxypropyl) urea, N- (3-hydroxypropyl) urea, N ', N'-dimethyl-N- (2-hydroxyethyl ) urea, N ', N'-dimethyl-N- (2-hydroxypropyl) urea, N', N'-dimethyl-N- (3-hydroxypropyl) urea, N ', N'-diethyl-N- (2- hydroxyethyl) urea, N ', N'-diethyl-N- (2-hydroxypropyl) urea, N', N'-diethyl-N- (3-hydroxypropyl) urea, N ', N'-di-n-butyl -N- (2-hydroxyethyl) urea, N ', N'-di-n-butyl-N- (2-hydroxypropyl) urea and N', N'-di-n-butyl-N- (3-hydroxypropyl) urea, particularly preferably N- (2-hydroxyethyl) -mo Evin, N- (2-hydroxypropyl) urea and N- (3-hydroxypropyl) urea.

In step (c), (meth) acrylic acid is esterified or preferably transesterified with (C) or (O) at least one (meth) acrylate, preferably one (meth) acrylate (D), in the presence of at least , one heterogeneous catalyst selected from the group consisting of inorganic salts (C) and enzymes (F).

Compounds (D) can be (meth) acrylic acid or a saturated methanol (meth) acrylic acid ester, preferably a saturated methanolic ester of (meth) acrylic acid containing 1-10 carbon atoms, particularly preferably a (meth) ester acrylic acid with saturated aliphatic alcohol containing 1-4 carbon atoms.

The term "saturated" in the text of the present description means compounds containing only simple C — C bonds (needless to say, except for the C = C double bond in the units of (meth) acrylic acid).

Examples of compounds (D) are methyl, ethyl, n. Butyl, isobutyl, tert.butyl, n. Octyl and 2-ethylhexyl esters of (meth) acrylic acid, 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, trimethylol propanetri (meth) acrylate and pentaerythritol tetra (meth) acrylate.

Particularly preferred are methyl, ethyl, n. Butyl and 2-ethylhexyl esters of (meth) acrylic acid, more preferably methyl, ethyl and n. Butyl esters of (meth) acrylic acid, in particular methyl and ethyl esters of (meth) acrylic acid and especially methyl ester of (meth) acrylic acid.

Inorganic salts (C) suitable for use according to the invention are those salts which have a pK _B value of not higher than 7.0, preferably not higher than 6.1 and particularly preferably not higher than 4.0. At the same time, the pK _B value should not be lower than 1.0, preferably not lower than 1.5, and particularly preferably not lower than 1.6.

Heterogeneous catalysts within the scope of the present description of the invention are those catalysts which have a solubility in the reaction medium at 25 ° C of not more than 1 g / l, preferably not more than 0.5 g / l and particularly preferably not more than 0.25 g / l.

The inorganic salt preferably contains at least one anion selected from the group consisting of the following anions: carbonate (CO ₃ ^2- ), bicarbonate (HCO ₃ ^- ), phosphate (PO ₄ ^3- ), hydrogen phosphate (HPO ₄ ^2- ), dihydrogen phosphate (H ₂ PO ₄ ^- ), sulfate (SO ₄ ^2- ), sulfite (SO ₃ ^2- ) and carboxylate (R ⁶ -COO ^- ), where R ⁶ means alkyl with 1-18 carbon atoms or alkyl with 2-18 carbon atoms, optionally interrupted by one or more oxygen and / or sulfur atoms, and / or one or more substituted or unsubstituted imino groups, or aryl with 6-12 carbon atoms .

Carbonate and phosphate are preferred, phosphate is particularly preferred.

Phosphate should also be understood as condensation products, such as, for example, diphosphates, triphosphates and polyphosphates.

The inorganic salt preferably contains at least one cation selected from the group consisting of cations of alkali metals, alkaline earth metals, ammonium, cerium, iron, manganese, chromium, molybdenum, cobalt, nickel and zinc.

Preferred are alkali metal cations and most preferred lithium, sodium or potassium.

Particularly preferred inorganic salts are lithium phosphate (Li ₃ PO ₄ ), potassium phosphate (K ₃ PO ₄ ), sodium phosphate (Na ₃ PO ₄ ), potassium carbonate (K ₂ CO ₃ ) and sodium carbonate (Na ₂ CO ₃ ), as well as their hydrates, most preferred is potassium phosphate (K ₃ PO ₄ ).

Potassium phosphate (K ₃ PO ₄ ) according to the invention can be used in anhydrous form, as well as in the form of tri-, hepta- or nonahydrates.

The esterification or transesterification catalyzed by an inorganic salt is usually carried out at a temperature of from 50 to 140 ° C, preferably from 50 to 100 ° C, particularly preferably from 60 to 90 ° C and most preferably from 60 to 80 ° C.

If necessary, the reaction can be carried out under a small vacuum, for example, from 300 hectoPa (PRa) to normal pressure, while the water released during esterification or the low boiling alcohol formed during transesterification should be removed by distillation, if necessary in the form of an azeotrope.

The molar ratio between the (meth) acrylic acid or ester of (meth) acrylic acid and the compound (C) or (D) during the inorganic salt catalyzed esterification or transesterification reaction is typically 2-6: 1 mol / mol, preferably 2 -3.5: 1 mol / mol and most preferably 2.5-3.0: 1 mol / mol.

The reaction time for the esterification or transesterification catalyzed by an inorganic salt is typically from 30 minutes to 24 hours, preferably from 45 minutes to 18 hours, particularly preferably from 3 to 12 hours and most preferably from 5 to 10 hours.

The content of inorganic salts in the reaction medium, as a rule, is in the range from 0.01 to 5 mol. %, preferably from 0.1 to 1.8 mol. % and most preferably from 0.3 to 1.5 mol. % of the total number of components used (C) or (O).

In the process of esterification or transesterification, polymerization inhibitors are necessary (see below).

During the inorganic salt-catalyzed esterification or transesterification reaction, the presence of oxygen-containing gases is preferred (see below).

In the inorganic salt-catalyzed esterification or transesterification reactions, typically products with a color index below 500 APHA, preferably below 200 and most preferably below 150 (according to DIN ISO 6271) are obtained.

Enzymes (F) suitable for use according to the invention are selected, for example, from hydrolases (E.C.3. -.-.-) and especially from esterases (E.C.3.1. -.-), lipases (E.C. 3.1.1.3), glycosylases (E.C.3.2. -.-) and proteases (E.C.3.4. -.-) in free form, or as chemically or physically immobilized, on a carrier, preferably lipases, esterases or proteases and particularly preferably esterases (E.C. 3.1. -.-). Most preferred are Novozyme® 435 (lipase from Candida antarctica B) or lipase from Alcaligenes sp., Aspergillus sp., Mucor sp., Penecilium sp., Geotricum sp., Rhizopus sp., Burkholderia sp., Candida sp., Pseudomonas sp. ., Thermomyces sp. or pancreatic pig enzymes. Particularly preferred are lipase from Canada antarctica B or from Burkholderia sp.

Enzymatic esterification or transesterification of (meth) acrylate is usually carried out at a temperature of from 20 to 100 ° C, preferably from 20 to 80 ° C, particularly preferably from 30 to 70 ° C and most preferably from 40 to 60 ° C.

In this case, the upper temperature limit is, of course, the boiling point of the solvent or the boiling point of the alcohol released during transesterification.

If necessary, the reaction can be carried out under a small vacuum, for example, from 300 hectoPa (PRa) to normal pressure, while it is necessary to distill off the water released during esterification or the low boiling alcohol formed during transesterification, if necessary in the form of an azeotrope.

The content of the enzyme in the reaction medium, as a rule, is in the range from about 0.1 to 10 wt.%, Calculated on the total content of the components used (C) or, respectively, (O) and (D).

The molar ratio between the (meth) acrylic acid or ester of (meth) acrylic acid and the compound (O) or (D) in an enzymatically catalyzed esterification or transesterification is typically 1-50: 1 mol / mol, preferably 5-20: 1 mol / mol.

The time of the enzymatically catalyzed esterification or transesterification reaction is typically from 6 hours to 3 days, preferably from 8 hours to 2 days, and particularly preferably from 12 hours to 24 hours.

Preferably, the reaction time is set so that the conversion of all the hydroxyl groups contained in the alcohol is at least 70%, preferably at least 80%, particularly preferably at least 90% and most preferably at least , 95% and in particular at least 97%.

In some cases, an enzymatically catalyzed reaction can also be carried out in the absence of stabilizers (see below), preferably it is carried out in the presence of at least one stabilizer.

The products obtained by the enzymatically catalyzed reaction typically have a color index of less than 100 APHA, preferably less than 80 APHA.

The indicated reaction parameters are valid, unless otherwise indicated, both for the enzymatically catalyzed reaction and for the reaction catalyzed by inorganic salts.

The reaction can proceed in organic solvents, or in mixtures thereof, or without the addition of solvents. The starting reaction mixtures are generally substantially anhydrous (i.e., have a water content of less than 10 wt.%, Preferably less than 5 wt.%, Particularly preferably less than 1 wt.% And most preferably less than 0.5 wt.%) . In addition, the starting compounds substantially do not contain primary and secondary alcohols, i.e. their alcohol content is less than 10 wt.%, preferably less than 5 wt.%, particularly preferably less than 1 wt.% and most preferably less than 0.5 wt.%.

Suitable organic solvents are solvents known for these purposes, for example tertiary monools, such as alcohols with 3-6 carbon atoms, preferably tert-amyl alcohol, tert-butanol, pyridine, polyalkylene glycol-dialkyl ether with 1-4 carbon atoms in alkyl and 1-4 carbon atoms in alkylene, preferably polyethylene glycol-dialkyl ether with 1-4 carbon atoms in alkyl, for example, such as 1,2-dimethoxyethane, diethylene glycol dimethyl ether, polyethylene glycol dimethyl ether 500, alkylene carbonate with 1-4 atoms hydrocarbon in alkylene, especially propylene carbonate, an alkyl ester of acetic acid with 3-6 carbon atoms in the alkyl, especially tert-butyl ester of acetic acid, tetrahydrofuran (THF), toluene, 1,3-dioxolane, acetone, isobutyl methyl ketone, ethyl methyl ketone, 1,4-dioxane, tert-butyl methyl ether, cyclohexane, methylcyclohexane, toluene, hexane, dimethoxymethane, 1,1-dimethoxyethane, acetonitrile, as well as their single and multiphase mixtures.

In a particularly preferred embodiment, the transesterification reaction is carried out in the (meth) -acrylic acid ester used as an educt. Most preferably, the reaction is carried out in such a way that, after the completion of the reaction, compound (C) or (O) remains in the form of a solution in the (meth) acrylic acid ester used as an educt with a concentration of 10-80 wt.%, In particular with a solution concentration of 20 -50 wt.%.

The educts are either dissolved, or suspended as a solid phase, or emulsified in the reaction medium. The initial concentration of the reagents is preferably from about 0.1 to 20 mol / L, in particular from 0.15 to 10 mol / L or from 0.2 to 5 mol / L.

The reaction can be carried out continuously, for example, in a tubular reactor or in a cascade of reactors with stirring or periodically.

The process can be carried out in all reactors suitable for such a reaction. Such reactors are known to those skilled in the art. Preferably, the process is carried out in a mixing boiler or in a fixed bed reactor.

Any method may be used to stir the reaction mixture. No special mixing devices are required. Stirring can be carried out, for example, by supplying a gas, preferably an oxygen-containing gas (see below). The reaction medium can be single-phase or multiphase, and the reagents are supplied as dissolved, suspended or emulsified in it, if necessary together with a molecular sieve, and an enzyme preparation is fed once or repeatedly during the reaction, if necessary. During the reaction, the required temperature is set, and if necessary, during the process it can be increased or decreased.

If the reaction is carried out in a fixed-bed reactor, preferably immobilized enzymes are fed into the reactor, the reaction mixture being pumped through an enzyme-filled column. You can also interact in the fluidized bed, and the enzyme is used immobilized on a carrier. The reaction mixture can be continuously pumped through the column, and the reaction time and therefore the desired degree of conversion can be controlled by the flow rate. It is also possible, by pumping, to circulate the reaction mixture through the column, and it is also possible to simultaneously distill off the evolving alcohol under vacuum.

The removal of water in the case of esterification or alcohols released from alkyl (meth) acrylates during transesterification is carried out in a known manner continuously or periodically, for example, under vacuum, azeotropic removal, distillation, absorption, evaporation through a permeable septum and diffusion through membranes or extraction.

Stripping can be carried out, for example, by blowing through a reaction mixture of an oxygen-containing gas, preferably air or a mixture of air with nitrogen, if necessary, in addition to distillation.

Molecular sieves or zeolites (with pore sizes, for example, in the range of about 3-10 Å), are preferably suitable for absorption. Separation is carried out by distillation or by using appropriate semipermeable membranes.

However, it is also possible to direct the isolated mixture of the alkyl (meth) acrylate and the alcohol in its base, which often forms an azeotrope, directly to the installation for the production of alkyl (meth) acrylate for re-esterification of (meth) acrylic acid.

In an enzymatically catalyzed reaction, it may also be expedient to separate the liberated water or alcohol by means of a binary or triple heteroazeotrope boiling at a temperature as close as possible to the optimum temperature of the enzyme used. The alcohol removed in this way can be isolated by phase separation or membrane vapor separation.

At the end of the reaction, the reaction mixture obtained in stage (c) can then be used without additional purification or, if necessary, further purified in the subsequent stage (g).

Typically, in step (d), only the used heterogeneous catalyst is separated from the reaction mixture and the reaction product is separated from the organic solvent used if necessary.

The separation of a heterogeneous catalyst is usually carried out by filtration, electrostatic filtration, absorption, centrifugation or decantation. The isolated heterogeneous catalyst can then be used for other reactions.

The separation of the organic solvent is usually carried out by distillation, rectification or, in the case of solid reaction products, filtration.

Additional post-treatment of the reaction product can also be carried out by chromatography.

However, it is preferred that only the heterogeneous catalyst and the solvent used if necessary are separated in step (d).

The reaction conditions according to the invention, especially enzymatic esterification or transesterification, are mild. Due to the low temperature and other mild conditions in stage (c), the formation of by-products that otherwise could be formed, for example, from chemical catalysts or due to undesired radical polymerization of the (meth) -acrylate used, which can only be avoided by the addition of stabilizers, is avoided. When carrying out the reaction according to the invention, in addition to the storage stabilizer contained in the (meth) -acrylic compound (D), an additional stabilizer, for example hydroquinone methyl ester, phenothiazine, phenols, for example, can be added to at least the used (meth) acrylate or the reaction mixture such as 2-tert.butyl-4-methylphenol, 6-tert.butyl-2,4-dimethylphenol or N-oxides, such as 4-hydroxy-2,2,6,6-tetramethylpiperidin-N-oxyl, 4- oxo-2,2,6,6-tetramethylpiperidin-N-oxyl or Uvinul® 4040P manufactured by BASF AG (BASF Aktien-gesellschaft, for example, in an amount of 50 up to 2000 ppm

Preferably, the esterification or transesterification is carried out in the presence of an oxygen-containing gas, preferably air or a mixture of air and nitrogen.

The heterogeneous catalyst used according to the invention can be removed from the final product without any problems. Due to the low solubility of the heterogeneous catalyst according to the invention, a maximum of minor traces of the catalyst remain in the reaction medium in the product. As a result, for processing the reaction product, as a rule, simple filtration or decantation is sufficient, and thanks to the method according to the invention, it is possible to abandon the costly stages of washing, neutralization, etc. to separate the catalyst.

The catalysts used according to the invention show a slight tendency to carry out adverse reactions. Inorganic salts have sufficient basicity to catalyze the esterification and transesterification reaction, but insufficient basicity to catalyze side reactions, for example the Michael reaction mentioned above, as a result of which the Michael adducts can be significantly reduced in comparison with the reactions known from the prior art .

In addition, the reaction under the conditions according to the invention proceeds very selectively, while, as a rule, the formation of less than 10%, mainly less than 5% of by-products (based on the total yield).

Typical by-products of the reaction of compounds (C) and (O) in which Z ¹ is NH, with (meth) acrylic acid or (meth) acrylic acid esters are the (meth) acrylamide attached through this nitrogen atom attached through this atom nitrogen adduct according to Michael, attached through a free hydroxyl group, Michael adduct, as well as products obtained by intra- or intermolecular cleavage of the group R ⁵ -Z ¹ from compounds (C) or (O), which can then again be subjected to esterification or transesterification .

A particular advantage of the catalysts of the invention is that a fraction of at least twice (meth) acrylated products can be suppressed. Such products are very difficult to separate from mono (meth) acrylated target products. Since the target product should be used as a monomer or reactive diluent (see below), the content of repeatedly (meth) acrylated products is undesirable, since such products lead to crosslinking, which during polymerization can unpredictably increase the molecular weight of the product.

The (meth) acrylates of N-hydroxyalkylated amides obtained according to the invention are used, for example, as monomers or comonomers in the preparation of dispersions, for example acrylic dispersions, as a reactive diluent, for example, in radiation-curable coating materials or in paints, preferably in paints for external coatings, as well as in dispersions for use in paper production.

The following examples should illustrate the properties of the invention, but without limiting it.

Examples

The term "parts" in this description, unless otherwise indicated, should be understood as mass parts.

The equipment consisted of a 500 ml round-bottom four-neck flask with an air supply tube, a separation column, a sampling device and a sensing element for measuring the internal temperature. Stirring was carried out with a magnetic stirrer with an intensity of 300 rpm.

A 20 cm Vigreux column with Raschig rings (5 × 5 mm) was used as a separation column. The separation column was equipped with a head with a backflow regulator and a Liebig refrigerator, and in all experiments it was possible to work without polymer deposits.

Each time, the preparation process was carried out according to the following general procedure: 2-hydroxyethyl-ethylene urea (HEEM, 130 g, 1.0 mol) was melted and the corresponding amount of methyl methacrylate (MMA) was applied to the melt (5.0 moles, 560 g). When heated to an internal temperature of 100 ° C, a catalyst was added (0.8 mol% based on urea). The resulting azeotrope from methyl methacrylate (MMA) and methanol was distilled off at a reflux ratio of 2: 1 (65 ° C). Samples of the distillate and the contents of the bottom of the reactor were regularly taken and analyzed. After the formation of methanol, the process was still continued with a reflux ratio of 10: 1 until the duration of the experiment was six hours. Then the distillation was stopped and the contents of the bottom of the reactor were examined by gas chromatography for the content of the product - 2- (2-oxo-imidazolidin-1-yl) -ethyl ester of methacrylic acid, as well as the resulting side components (in total). Among others, the following side components were discovered: N- [2- (2-oxo-oxazolidin-3-yl) ethyl] methacrylamide, N- {2- [3- (methacryloyl) -2-oxo-imidazolidin-1- yl] -ethyl} -methacrylamide, 2-methyl-3- {3- [2- (methacryloyl-amino) -ethyl] -2-oxo-imidazolidin-1-yl} -propionic acid and 2-methyl-3- [ 2- (2-oxo-imidazolidin-1-yl) -ethoxy] propionic acid.

Example 1: Potassium Phosphate

The catalyst (mol.%) MMA -%] HEEM [Jew. -%] Product [Jew. -%] Dimethacrylate [Jew. -%] Potassium Phosphate (1.5) 79.05 2.24 16.38 0.31 Potassium Phosphate (1.0) 77.55 2,34 17.93 0.32 Potassium Phosphate (0.5) 73.55 2.42 20.21 0.57

Example 2: Potassium Carbonate

The catalyst (mol.%) MMA -%] HEEM [Jew. -%] Product [Jew. -%] Dimethacrylate [Jew. -%] Potassium carbonate (0.2) 78.65 1.38 16.16 0.48

Comparative Example 1: Dibutyltin Oxide (ODBO)

The catalyst (mol.%) MMA -%] HEEM [Jew. -%] Product [Jew. -%] Dimethacrylate [Jew. -%] ODBO (0.8) 71.21 7.2 20,13 1,07

Comparative Example 2: Potassium Methylate

Catalyst MMA -%] HEEM [Jew. -%] Product [Jew. -%] Dimethacrylate [Jew. -%] K-methylate (1 mol.%) 79.17 8.24 9.97 0.11

A comparison of the experimental results clearly shows that potassium phosphate as a catalyst surpasses existing known systems. With at least a doubled yield in volume and time, as well as with a small amount of a crosslinking agent, the transesterification proceeds with high selectivity and a high degree of conversion. The catalyst precipitates upon cooling in the form of well-filtered crystals, and the washing step disappears.

Example 3: Enzymatic Catalysis

10 mmol of 2-hydroxyethylethylene urea (HEEM, 1.3 g), 100 or 400 mmol of methyl methacrylate, 2.0 g of molecular sieve (5 Å) and 65-260 mg of Novozym® 435 (immobilized lipase from Candida antarctica B, Novozymes) were shaken for 72 hours at 40 ° C in a glass with a screw cap. Colorless solutions were obtained. For analysis, homogeneous samples were prepared in which, if necessary, precipitates were dissolved by adding 10 ml of 1,4-dioxane. The conversion of 2-hydroxyethylethylene urea (HEEM) with respect to methacrylate was determined by the aforementioned gas chromatography method.

Experience with 100 mmol MMA

The amount of enzyme used HEEM [Jew. -%] Product [Jew. -%] The amount of side components. [Jew. -%] The degree of conversion [%] 130 mg 46.1 52.9 1,0 53 260 mg 33.3 65.8 0.8 66

Experience with 400 mmol MMA

The amount of enzyme used HEEM [Jew. -%] Product [Jew. -%] The amount of side components. [Jew. -%] The degree of conversion [%] 65 mg 41.7 57.1 0.8 58 130 mg 43,4 55.7 0.7 56 260 mg 13,2 86.1 0.6 87

Claims (6)

1. A method of producing (meth) acrylates of N-hydroxyalkylated amides, in which cyclic N-hydroxyalkylated amides (C):

where Z ¹ means unsubstituted or monosubstituted nitrogen (NR ³ ),
R ¹ and R ² , in each case, independently from each other, mean alkylene with 2-20 carbon atoms, cycloalkylene with 5-12 carbon atoms, arylene with 6-12 carbon atoms,
R ³ means hydrogen, alkyl with 1-18 carbon atoms, alkenyl with 2-18 carbon atoms, aryl with 6-12 carbon atoms or cycloalkyl with 5-12 carbon atoms, esterified with methacrylic acid or transesterified with at least one ether (meth) acrylic acid (D) in the presence of at least one heterogeneous catalyst selected from the group consisting of inorganic salts (Co) having a pKv value of not higher than 7.0 and not lower than 1.0, and its solubility in the reaction medium at 25 ° C no more than 1 g / l, and enzymes (Ф) selected from the group containing ester basics (E.C.3.1. -.-), lipases (E.C.3.1.1.3), glycosylases (E.C.3.2. -.-) and proteases (E.C.3.4. -.-), moreover, the heterogeneous catalyst is separated from the reaction mixture by filtration, electrostatic filtration, absorption, centrifugation or decantation. 2. The method according to claim 1, characterized in that the inorganic salt contains at least one anion selected from the group consisting of carbonate (CO ₃ ^2- ), bicarbonate (HCO ₃ ^- ), phosphate (PO ₄ ^3- ), hydrogen phosphate (HPO ₄ ^2- ), dihydrogen phosphate (H ₂ PO ₄ ^- ), sulfate (SO ₄ ^2- ), sulfite (SO ₃ ^2- ). 3. The method according to claim 1, characterized in that the inorganic salt contains at least one cation selected from the group consisting of cations of alkali metals, alkaline earth metals, ammonium, cerium, iron, manganese, chromium, molybdenum, cobalt, nickel or zinc . 4. The method according to claim 1, characterized in that the inorganic salt is selected from the group consisting of lithium phosphate (Li ₃ PO ₄ ), potassium phosphate (K ₃ PO ₄ ), sodium phosphate (Na ₃ PO ₄ ), potassium carbonate (K ₂ CO ₃ ) and sodium carbonate (Na ₂ CO ₃ ), as well as their hydrates. 5. The method according to claim 1, characterized in that the enzyme is selected from the group consisting of Novozyme® 435 (lipase from Candida antarctica B), lipases from Alcaligenes sp., Aspergillus sp., Mucor sp., Penecilium sp., Geotricum sp. , Rhizopus sp., Burkholderia sp., Candida sp., Pseudomonas sp., Thermomyces sp. Or porcine pancreatic enzymes. 6. The method according to one of claims 1 to 5, characterized in that the reaction is carried out in such a way that, at the end of the reaction, the product (C) is in the form of a solution in the (meth) acrylic acid ester used as an educt with a concentration of about 10-80 wt.%.