Enzymatic production of (meth)acrylic esters

FIELD: chemistry.

SUBSTANCE: invention relates to a method of producing (meth)acrylic esters (F) based on alcohols having at least one carbon-carbon triple bond, characterised by that at least one alcohol having at least one carbon-carbon triple bond of formula (1) where R1 denotes hydrogen, alkyl having 1-18 carbon atoms; alkyl having 2-18 carbon atoms, aryl having 6-12 carbon atoms, cycloalkyl having 5-12 carbon atoms, interrupted, if necessary, by one or more oxygen and/or sulphur atoms and/or one or more substituted or unsubstituted amino groups, or a 5-6-member heterocycl having oxygen, nitrogen and/or sulphur atoms, wherein said residues can be substituted with aryl, alkyl, aryloxy, alkyloxy, heteroatoms/or heterocycles, respectively, and R2 denotes alkylene having 1-20 carbon atoms, cycloalkylene having 5-12 carbon atoms, arylene having 6-12 carbon atoms, or alkylene having 2-20 carbon atoms interrupted by one or more oxygen and/or sulphur atoms and/or one or more substituted or unsubstituted amino groups and/or one or more cycloalkyl groups, -(CO)-, -O(CO)O, -(NH)(CO)O-, -O(CO)(NH)-, -O(CO)- or -(CO)O, where the names of the residues can be replaced with aryl, alkyl, aryloxy, alkyloxy, heteroatoms and/or heterocycles respectively, n is a whole number from 0 to 3, preferably from 0 to 2 and more preferably from 1 to 2 and X; for each i=0 to n can be independently selected from a group comprising -CH2-CH2-O-, -CH2-CH(CH3)-O-, -CH(CH3)-CH2-O-, -CH2-C(CH3)2-O-, -C(CH3)2-CH2-O-, -CH2-CHVin-O-, -CHVin-CH2-O-, -CH2-CHPh-O- and -CHPh-CH2-O-, preferably from a group comprising -CH2-CH2-O-, -CH2-CH(CH3)-O- and -CH(CH3)-CH2-O-, and more preferably CH2-CH2-O-, where Ph denotes phenyl and Vin denotes vinyl, wherein the hydroxy groups of the alcohol are primary or secondary, esterified in the presence of at least one enzyme (E) with (meth)acrylic acid or re-esterified with at least one (meth)acrylic ester (D).

EFFECT: use of the present method enables to obtain esters of an acid based on alcohols which have carbon-carbon triple bonds with good output and low colour indices.

5 cl, 3 ex

 

The proposed invention relates to a method for producing esters of (meth)acrylic acid-based alcohols with carbon-carbon triple bonds, method of their production and their use.

Production of esters of (meth)acrylic acids occurs mainly by kataliziruemoi acids or bases the esterification of (meth)acrylic acids or transesterification of other esters of (meth)acrylic acid with alcohols or by the reaction of alcohols with (meth)acryloyl-chloride in the presence of bases.

Esters of (meth)acrylic acid-based alcohols with carbon-carbon triple bonds, in principle, known. In classical esterification of such alcohols, for example acids, induced by acid adverse reactions, in particular isomerization triple bond, get, however in most cases, heterogeneous, at least, but highly colored product mixture.

Similarly as when moving the carbon-carbon double bonds by rearrangement of allyl you can move in alkynes carbon-carbon triple bond (regrouping alkyne-Allen). Such isomerization often are equilibrium reactions. The rearrangement occurs, for example, by moving the anion or cation and is catalyzed by acids or bases (Houben-Weyl, Methods der organischen Chemie vol V/2a, Izdat the construction Thieme 1977, str FF.). Due to this instability of the triple bond of alkynes under acidic or basic conditions prone to the formation of by-products (for example, allene and consistent products)that you want to remove from the reaction mixture with high costs or by extraction.

In European patent application EP 508491 (Wacker Chemie, 1992) 2-projeksiyon azeotropic etherification with acrylic acid in toluene as a separating agent in the catalysis of sulfuric acid. After 4 h at a temperature of 120°With excess acid is neutralized NaHCO3and washed with water. Then the toluene is distilled off and 2-propargyloxy-acrylate purified by distillation. Get a slightly yellowish product with a yield of 85%.

When base catalyzed interesterification or other syntheses, for example, metal complexes, for similar reason, also have complex mixture and painted product. To remove the paint and not turned reagent mixture of the product treated by expensive alkaline washing.

Also known from akriloilkhlorida in the presence of bases:

In U.S. patent 3254115 (Thiokol Chemical Corp., 1966) describe getting propargyl-acrylate of propargilovyh alcohol and akriloilkhlorida. The catalyst is triethylamine and the solvent used benzene. Product distil irout in vacuum at the outlet 60%.

Harvey et al. (J. Am. Chem. Soc., 1992, 114, 8424-8434) is Pro-Vergil-acrylate from propargilovyh alcohol and akriloilkhlorida. The catalyst is triethylamine and the solvent used dichloromethane. The product several times successively extracted with HCl, Panso3and water with the release of 90%.

Production of esters of (meth)acrylic acid by enzymatic esterification or interesterification known.

Kumar and Gross describe in J. Am. Chem. Soc. 2002, 124, 1850-1851 catalisano lipase transformation of sugars, isopropylidene protected, by transformation with vanillacream. Complete metamorphosis reach special thanks to educt vanillacream, as released vinyl alcohol removed from the reaction equilibrium in the form of acetaldehyde. The disadvantage of this method is that vanillacream as a special monomer expensive and commercially available only in small quantities.

..J.W. de Goede et al. Describe in Biocatalysis, 1994, 9, 145-155 the transesterification of α-O-octyl-glucoside with acrylate to obtain a complex of 6-O-acrylic ester in the presence of lipases. The disadvantage of this method is that it is limited glucosides and glycosidic bonds and is sensitive to steric effects glucoside. In addition, due to non-selective adverse reactions get higher acrylic is rowanne products.

In European patent application EP-A1 999229 describe the enzymatic esterification and transesterification of polyoxyalkylene with (meth)acrylic acid and esters of (meth)acrylic acid.

From international patent application WO 03/042227 known natalizumab the lipase transesterification of alkylacrylate with sugars.

In U.S. patent 5240835 describe the transesterification of alkylacrylate with alcohols in the catalysis of the enzyme from Corynebacterium oxydans. There lead, for example, the reaction 96-fold molar excess of ethyl acrylate with 2,2-dimethyl-1,3-propane diol. Get access to 21% after only 3 days at 30°C.

Athawale and Manjrekar (Tetrahedron Lett. 2001, 42 4541-4543) describe catalisano lipase calironia alkaloids by 2,3-butandiol-monooxygenase. The monomer polymerizing and used for the induction of enantioselective join Michael.

Athawale and Gaonkar (Makromolecules 1999, 32, 6065-6068) describe catalisano lipase calironia 2-phenylethanol by 2,3-butandiol-monooxygenase. The monomer in conclusion, let polimerizuet.

Ghogare and Kumar (J. Chem. Soc. 1989, 1533-1535) describe catalisano lipase calironia various alcohols, including 2-ethylhexane-1,3-diol, activated 2,3-butandiol-monooxygenation.

The disadvantage of these reactions is often neo is the divergence in the application of activated acrylate, such as, for example, oximes or complex vinyl ethers, which are expensive and poorly available industrially.

The objective of the proposed invention is to provide a way by which simple doctow it is possible to obtain esters of (meth)acrylic acid-based alcohols, which have a carbon-carbon triple bond, with good output and low index coating. The synthesis should proceed under mild conditions, so that you get the products with a low color index and high purity. Specifically we need to renounce the use of acidic or basic catalysts, to prevent the occurrence of side products. In the result, you can eliminate the costly go distillation extractive purification of the product. In addition, it is necessary to renounce the use of expensive, activated derivatives of (meth)acrylic acids, such as, for example, monooxime or vinyl(meth)acrylate.

Problem solving is a method of obtaining esters of (meth)acrylic acid (F) on the basis of alcohols having at least one carbon-carbon triple bond, wherein at least one alcohol having at least one carbon-carbon triple bond, etherification in the presence of at least one enzyme (E) and (meth)acrylic acid or preterition, at least, one of them a complex ester of (meth)acrylic acid - (D).

Using proposed according to the invention the method may receive such complex esters of (meth)acrylic acid (F) in high chemical yield and space-time and under mild conditions with good color indexes in the rejection of the protective groups and using simple starting materials.

In this document (meth)acrylic acid means methacrylic acid and acrylic acid, preferably acrylic acid.

According to the invention is suitable alcohols (C) are alcohols that contain at least one carbon-carbon triple bond and at least one hydroxy-group.

Such alcohols may include, for example, from 1 to 3, preferably from 1 to 2 and particularly preferably precisely one carbon-carbon triple bond.

The alcohols (S) can contain from one to six, preferably one to four, particularly preferably from one to three, most preferably from one to two and in particular exactly one hydroxy-group.

According to the invention applied alcohols (C) may contain other heteroatoms, for example nitrogen atoms and/or sulfur, preferably they consist of atoms of carbon, hydrogen and oxygen.

According to the invention applied alcohols (C) may contain other functional groups, for example of carbon is carbon double bond, amino group, carboxypropyl, groups, ethers or group of esters of carboxylic acids. Preferably in addition to the carbon-carbon triple bond and a hydroxy-group, they do not contain any of the following functional groups.

Hydroxy-group used according to the invention alcohols (C) can be primary, secondary or tertiary, preferred are alcohols with primary or secondary and particularly preferably primary hydroxyl groups. Also in alcohol can be a variety of hydroxy-group, such as primary and secondary.

Primary hydroxy groups are hydroxy-group, which is associated with exactly one carbon atom, which is associated with exactly one of the following carbon atom. Similarly, when the secondary hydroxy groups linking their carbon atom respectively connected with two and tertiary hydroxy groups with three carbon atoms.

The preferred alcohols (C) are alcohols of the formula (1)

where

R1means hydrogen, alkyl having from 1 to 18 carbon atoms; alkyl having from 2 to 18 carbon atoms, aryl having from 6 to 12 carbon atoms, cycloalkyl having from 5 to 12 carbon atoms, interrupted, if necessary, by one or more oxygen atoms and/or sulfur and/or one or more of replacing the military or unsubstituted aminopropane, or the five-to six-membered heterocycle having oxygen atoms, nitrogen and/or sulfur, with the mentioned residues can be substituted, respectively, by aryl, alkyl, aryloxy, alkyloxy, heteroatoms and/or heterocycles, and

R2means alkylene having from 1 to 20 carbon atoms, cycloalkyl having from 5 to 12 carbon atoms, Allen having from 6 to 12 carbon atoms, or alkylene having from 2 to 20 carbon atoms, interrupted by one or more oxygen atoms and/or sulfur and/or one or more substituted or unsubstituted aminopropane and/or one or more groups cycloalkyl, -(CO)-, -O(CO)O-, -(NH)(CO)O-, -O(CO)(NH)-, -O(CO)- or -(CO)O-, with the mentioned residues can be substituted, respectively, by aryl, alkyl, aryloxy, alkyloxy, heteroatoms and/or heterocycles,

n means an integer from 0 to 3, preferably from 0 to 2 and particularly preferably from 1 to 2 and

Xifor each i=0 to n independently of one another can be selected from the group-CH2-CH2-O-, -CH2-CH(CH3)-O-, -CH(CH3)-CH2-O-, -CH2- (CH3)2-O-, -C(CH3)2-CH2-O-,

-CH2-CHVin-O-, -CHVin-CH2-O-, -CH2-CHPh-O - and-h-CH2-O-, preferably from the group-CH2-CH2-O-, -CH2-CH(CH3)-O - and-CH(CH3)-CH2-O-, particularly preferably-CH2/sub> -CH2-O-,

where PH means phenyl and Vin means vinyl. Especially preferred alcohols (C) are alcohols of the formula (2)

where n, Xiand R1can have the above values and

R3-R6independently of one another denote hydrogen, alkyl having from 1 to 18 carbon atoms; alkyl having from 2 to 18 carbon atoms, aryl having from 6 to 12 carbon atoms, cycloalkyl having from 5 to 12 carbon atoms, interrupted, if necessary, by one or more oxygen atoms and/or sulfur and/or one or more substituted or unsubstituted aminopropane, five-membered or-six-membered heterocycle having oxygen atoms, nitrogen and/or sulfur, with the mentioned residues can be substituted, respectively, by aryl, alkyl, aryloxy, alkyloxy, heteroatoms and/or heterocycles.

Highly preferred are the alcohols (S) of formula (3)

where n, Xiand R1can have the above values and

R7and R8independently of one another denote hydrogen, alkyl having from 1 to 18 carbon atoms; alkyl having from 2 to 18 carbon atoms, aryl having from 6 to 12 carbon atoms, cycloalkyl having from 5 to 12 carbon atoms, interrupted, if necessary, by one or more oxygen atoms and/or ser and/or one or more substituted or unsubstituted aminopropane, or the five-to six-membered heterocycle having oxygen atoms, nitrogen and/or sulfur, with the mentioned residues can be substituted, respectively, by aryl, alkyl, aryloxy, alkyloxy, heteroatoms and/or heterocycles,

where R7and R8together may form a ring.

In the above definitions mean

alkylene having from 1 to 20 carbon atoms, substituted, if necessary, aryl, alkyl, aryloxy, alkyloxy, heteroatoms and/or heterocycles, for example methylene, 1,1-ethylene, 1,2-ethylene, 1,1-propylene, 1,2-propylene, 1,3-propylene, 1,1-butylene, 1,2-butylene, 1,3-butylene, 1,4-butylene, 1,6-hexylen, 2-methyl-1,3-propylene, 2-ethyl-1,3-propylene, 2,2-dimethyl-1,3-propylene, 2,2-dimethyl-1,4-butylene,

cycloalkyl having from 5 to 12 carbon atoms, substituted, if necessary, aryl, alkyl, aryloxy, alkyloxy, heteroatoms and/or heterocycles, such as cyclopropyl, cyclopentyl, cyclohexyl, cyclooctyl, cyclododecyl,

alkylene having from 2 to 20 carbon atoms, optionally substituted by aryl, alkyl, aryloxy, alkyloxy, heteroatoms and/or heterocycles, aborted or more oxygen atoms and/or sulfur and/or one or more substituted or unsubstituted aminopropane, and/or one or more groups of cycloalkyl, -(CO)-, -O(CO)O-, -(NH)(CO)O-, -O(CO)(NH)-,

-O(CO)- or -(CO)is-, for example, 1-oxa-1,3-propylene, 1,4-dioxa-1,6-hexylen, 1,4,7-trioxa-1,9-neilen, 1-oxa-1,4-butylene, 1,5-dioxa-1,8-octile, 1-oxa-1,5-pentile, 1-oxa-1,7-heptylene, 1,6-dioxa-1,10-decile, 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-pentile, 1,4-dioxa-3,6-dimethyl-1,6-hexylen, 1-oxa-2-methyl-1,3-propylene, 1,4-dioxa-2,5-dimethyl-1,6-hexylen, 1-oxa-1,5-Penta-3-Anilin, 1-oxa-1,5-Penta-3-injen, 1,1-cyclohexyl, 1,2-cyclohexyl, 1,3-cyclohexyl or 1,4-cyclohexyl, 1,2-cyclopentyl or 1,3-cyclopentane, 1,2-phenylene, 1,3-phenylene or 1,4-phenylene, 4,4'-biphenylene, 1,4-diaza-1,4-butylene, 1-Aza-1,3-propylene, 1,4,7-triaza-1,7-heptylene, 1,4-diaza-1,6-hexylen, 1,4-diaza-7-oxa-1,7-heptylene, 4,7-diaza-1-oxa-1,7-heptylene, 4-Aza-1-oxa-1,6-hexylen, 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-hexylen, 4-Aza-1,7-dioxa-4-methyl-1,7-heptylene, 4-Aza-1,7-dioxa-4-(2'-hydroxyethyl)-1,7-heptylene, 4-Aza-1-oxa-(2'-hydroxyethyl)-1,6-hexylen or 1,4-piperazinyl,

aralen having from 6 to 12 carbon atoms, substituted, if necessary, aryl, alkyl, aryloxy, alkyloxy, heteroatoms and/or heterocycles, for example, 1,2-phenylene, 1,3-phenylene or 1,4-phenylene, 4,4'-bi-phenylene, toluylene or xylylene,

alkyl having from 1 to 18 carbon atoms, or alkyl having from 2 to 18 carbon atoms, interrupted, when necessary, one or more oxygen atoms and/or sulfur and/or one or more substituted or unsubstituted aminopropane, 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, getdecl, octadecyl, 1,1-dimethyl-propyl, 1,1-dimethylbutyl, 1,1,3,3-TETRAMETHYLBUTYL, benzyl, 1-phenylethyl, 2-phenylethyl, α,α-dimethylbenzyl, benzhydryl, p-trimethyl,1-(p-butylphenyl)-ethyl, p-chloro-benzyl, 2,4-dichlorobenzyl, p-methoxybenzyl, m-ethoxybenzyl, 2-cyanoethyl, 2-cyano-propyl, 2-methoxycarbonylethyl, 2-ethoxycarbonylethyl, 2-butoxycarbonylmethyl, 1,2-di-(methoxycarbonyl)-ethyl, 2-methoxyethyl, 2-ethoxyethyl, 2-butoxyethyl, diethoxy-methyl, diatexites, 1,3-dioxolane-2-yl, 1,3-dioxane-2-yl, 2-methyl-1,3-dioxolane-2-yl, 4-methyl-1,3-dioxolane-2-yl, 2-isopropoxyethanol, 2-butoxypropyl, 2-octyloxyphenyl, chloromethyl, 2-chloroethyl, trichloromethyl, trifluoromethyl, 1,1-dimethyl-2-chloroethyl, 2-methoxyethyl, 2-ethoxyethyl, butylthioethyl, 2-dodecylthiomethyl, 2-phenylthiomethyl, 2,2,2-triptorelin, 2-phenoxyethyl, 2-phenoxypropan, 3-phenoxypropan, 4-phenoxybutyl, 6-phenoxyethyl, 2-methoxyethyl, 2-methoxypropyl, 3-methoxypropyl, 4-methoxybutyl, 6-methoxyphenyl, 2-ethoxyethyl, 2-ethoxypropan, 3-ethoxypropan, 4-ethoxymethyl or 6-atoxigenic, and preferably methyl, ethyl, propyl, isopropyl, n-butyl, in which the PR-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, 2,4,4-trimethylpentyl, decyl, dodecyl, tetradecyl, getdecl, octadecyl, 1,1-dimethylpropyl, 1,1-dimethylbutyl, 1,1,3,3-TETRAMETHYLBUTYL, benzyl, 1-phenylethyl, 2-phenylethyl, α,α-dimethylbenzyl, benzhydryl, p-trimethyl,1-(p-butylphenyl)-ethyl, p-Chlorobenzyl, 2,4-dichlorobenzyl, 2-cyanoethyl, 2-cyanopropyl, chloromethyl, 2-chloroethyl, trichloromethyl, trifluoromethyl, 1,1-dimethyl-2-chloroethyl and 2,2,2-triptorelin,

aryl having from 6 to 12 carbon atoms, interrupted, if necessary, by one or more oxygen atoms and/or sulfur and/or one or more substituted or unsubstituted aminopropane, such as phenyl, tolyl, xylyl, α-naphthyl, β-naphthyl, 4-diphenylol, chlorophenyl, dichlorophenyl, trichlorophenyl, differenl, were, dimetilfenil, trimetilfenil, ethylphenyl, diethylphenyl, ISO-propylphenyl, tert-butylphenyl, dodecylphenyl, methoxyphenyl, acid, ethoxyphenyl, hexyloxyphenyl, Meilahti, isopropylated, chloronaphthyl, ethoxyethyl, 2,6-dimetilfenil, 2,4,6-trimetilfenil, 2,6-acid, 2,6-dichlorophenyl, 4-bromophenyl, 2 - or 4-nitrophenyl, 2,4-dinitrophenyl or 2,6-dinitrophenyl, 4-dimethylaminophenyl, 4-acetylphenyl, methoxyethanol or ethoxyethanol, and preferably phenyl, tolyl, xylyl, α-naphthyl, β-naphthyl, 4-diphenylol, chlorophenyl, dichlorophenyl, trichlorophenyl, differenl, were, dim terphenyl, trimetilfenil, ethylphenyl, diethylphenyl, ISO-propylphenyl, tert-butylphenyl, dodecylphenyl, chloronaphthyl, 2,6-dimetilfenil, 2,4,6-trimetilfenil, 2,6-acid, 2,6-dichlorophenyl, 4-bromophenyl, 2 - or 4-nitrophenyl, 2,4-dinitrophenyl or 2,6-dinitrophenyl; cycloalkyl having from 5 to 12 carbon atoms, interrupted

if necessary, one or more oxygen atoms and/or sulfur and/or one or more substituted or unsubstituted aminopropane, such as cyclopentyl, cyclohexyl, cyclooctyl, cyclododecyl, methylcyclopentene, dimethylcyclobutyl, methylcyclohexyl, dimethylcyclohexyl, diethylsiloxane, butylcyclohexyl, methoxycyclohexyl, dimethoxysilane, deoxycycline, butylcyclohexyl, chlorcycloguanil, dichlorocyclohexyl, dichlorocyclopentane, and saturated or unsaturated bicyclic system such as, for example, norbornyl or norbornanyl, and preferably cyclopentyl, cyclohexyl, cyclooctyl, cyclododecyl, methylcyclopentene, dimethylcyclobutyl, methylcyclohexyl, dimethylcyclohexyl, diethylsiloxane, butylcyclohexyl, chlorcycloguanil, dichlorocyclohexyl, dichlorocyclopentane, and saturated or unsaturated bicyclic system such as, for example, norbornyl or norbornanyl

and

interrupted, if necessary, by one or more oxygen atoms and/ilitary and/or one or more substituted or unsubstituted aminopropane, five-six-membered heterocycle having oxygen atoms, nitrogen and/or sulphur, such as furyl, thiophenyl, peril, pyridyl, indolyl, benzoxazolyl, dioxole, dioxin, benzimidazolyl, benzothiazolyl, dimethylpyridin, methilhill, dimethylpyrrole, methoxyphenyl, dimethoxyphenyl, giftability, methylthiophenyl, isopropylidene or tert-butylthiophenol.

Examples R2are methylene, 1,1-ethylene, 1,2-ethylene, 1,1-propylene, 2,2-propylene, 1,2-propylene, 1,3-propylene, 1,1-dimethyl-1,2-ethylene, 1,4-butylene, 1,6-hexylen, 2-methyl-1,3-propylene, 2-ethyl-1,3-propylene, 2,2-dimethyl-1,3-propylene and 2,2-dimethyl-1,4-butylene, 3-methyl-1,5-pentile, 3,5-heptylene, 1,2-cyclopentyl, 1,3-cyclopentyl, 1,2-cyclohexyl, 1,3-cyclohexene and ortho-phenylene, preferred are methylene, 1,1-ethylene, 1,2-ethylene, 1,1-propylene and 2,2-propylene, especially preferred are methylene, 1,1-ethylene, 1,2-ethylene, 2,2-propylene, and particularly preferred is methylene.

Preferred examples of R1and R3-R7independently of one another are hydrogen, alkyl having from 1 to 4 carbon atoms, 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. Preferred R1and R3-R7are independently the t of each hydrogen and methyl, especially preferably hydrogen.

Within this document, the alkyl having from 1 to 4 carbon atoms, means methyl, ethyl, ISO-propyl, n-propyl, n-butyl, ISO-butyl, sec-butyl or tert-butyl, preferably methyl, ethyl, n-propyl and n-butyl, particularly preferably methyl, ethyl and n-butyl, most preferably methyl and ethyl and in particular methyl.

Preferred examples of the alcohols (C) are 3-methyl-1-pentyn-3-ol, 2-propyne-1-ol (propargilovyh alcohol), 3-butyn-2-ol, 2-methyl-3-butyn-2-ol, 4-pentyn-1-ol, 1-ethynylcyclohexanol, 3-buten-1-ol, 2-butyn-1-ol and 1-octyn-3-ol, and their once or twice ethoxylated products. Especially preferred are 2-propyne-1-ol (propargilovyh alcohol), 2-butyn-1-ol, 3-butyn-2-ol and 2-methyl-3-butyn-2-ol and once or twice ethoxylated products and highly preferred is 2-propyne-1-ol (propargilovyh alcohol) and once or twice ethoxylated products, and particularly preferred is once or twice amoxillian-tion propargilovyh alcohol, and mixtures thereof.

In the reaction stage, the esterification with (meth)acrylic acid or preferably the transesterification of the alcohol (C) With at least one, preferably one (meth)acrylate (D) in the presence of at least one, preferably of the aqueous enzyme in the presence of at least one, preferably one enzyme (S)catalyzing the transesterification.

Compounds (D) can be (meth)acrylic acid or esters of (meth)acrylic acid with a saturated alcohol, preferably saturated complex alkilany ether having from 1 to 10 carbon atoms, or a complex of cyclo-alkilany ether having from 3 to 12 carbon atoms, (meth)acrylic acid, particularly preferably a saturated complex alkilany ether having from 1 to 4 carbon atoms, (meth)acrylic acid.

Within this document saturated means compounds without carbon-carbon complex relationships (except, of course, the carbon-carbon double bonds in the elements of (meth)acrylic).

Examples of compounds (D) are complex, methyl, ethyl, n-butyl, ISO-butyl, n-oktilovom and 2-ethylhexylamine esters of (meth)acrylic acid, 1,2-etilenglikoli(meth)acrylate and 1,2-etilenglikolevye(meth)acrylate, 1,4-butanediol(meth)acrylate and 1,4-butanediamine(meth)acrylate, 1,6-hexanediol(meth)acrylate and 1,6-hexanediamine(meth)-acrylate, trimethylolpropane(meth)acrylate and Penta-altrichter(meth)acrylate.

Especially preferred are complex, methyl, ethyl, n-butyl and 2-ethyl-hexyl esters of (meth)acrylic acids and particularly preferably a complex of methyl, ethyl, n-butyl esters of (meth)is Kirilovich acids.

If these spirits are optically active, they are used preferably in the form of racemates or as mixtures of diastereomers, however, it is also possible to apply them in the form of pure enantiomers or diastereomers or as mixtures of diastereomers.

Enzymatic esterification or transesterification with (meth)acrylate is in General at temperatures from 0 to 100°C., preferably from 20 to 80°C., particularly preferably from 20 to 70°C., highly preferably from 20 to 60°C.

Used according to the invention, the enzyme (S) selected from, for example, hydrolases (Y.S. 3.-.-.-), and among them especially esterases (Y.S. 3.1.-.-), lipases (Y.S. 3.1.1.3), glycosides (Y.S. 3.2.-.-) and proteases (Y.S. 3.4.-.-) in free form or in the form of chemically or physically immobilized on a carrier, preferably lipases, esterases or proteases, and particularly preferably esterase (Y.S. 3.1.-.-). Especially preferred are Novozyme 435 (lipase from Candida antarctica B) or lipase from Alcaligenes sp., Aspergillus sp., Mucor sp., Penicilium sp., Geotricum sp., Rhizopus sp., Burkholderia sp., Candida sp., Pseudomonas sp., Thermomyces sp. or the pancreas of pigs, in particular, are preferred lipase from Candida antarctica In or from Burkholderia sp.

The enzyme content in the reaction medium is generally in the range from about 0.1 to 10 wt. -%, in the calculation of the used alcohol (S).

The reaction time depends Chi the Les of temperature, the applied amount and the active enzyme catalyst and the necessary transformations, as well as from alcohol. Preferably the reaction time coordinate so that the transformation is not turned in the alcohol (C), that is, lower substituted functions is hydroxy, at least 70%, preferably at least 80, particularly preferably at least 90, highly preferably at least 95%, particularly at least 97% and especially at least 98%. As a rule, it is enough 1 to 72 hours, preferably from 3 to 36, and particularly preferably from 3 to 24 hours.

The molar ratio of the compound (meth)acrylic acid - (D) (elements (meth)-acrylic to alcohol (S) (based on a hydroxy-group) can be adjusted in a wide range as, for example, in a ratio of from 100:1 to 1:1, preferably from 50:1 to 1:1, particularly preferably from 20:1 to 1:1 and highly preferably from 10:1 to 1:1.

The reaction may proceed in organic solvents or their mixtures or without addition of solvents. Preferably do not add any solvent. Adding, as a rule, are of absolutely anhydrous (i.e. at 10, preferably to 5, particularly preferably with 1 and highly preferably at 0.5% of the mass. add water).

Suitable organic solvents are solvents which are known for this purpose, for example tertiary monooly, such as alcohols having from 3 to 6 carbon atoms, preferably tert-butanol, tert-amyl alcohol, pyridine, simple poly-C1-C4-alkylenglycol-C1-C4-alkilany ether, preferably a simple polyethylene-glycolide-C1-C4-alkilany ether, such as, for example, 1,2-dimethoxyethan, simple diethylethylenediamine ether, simple polietilenglikolmonostearat ether 500, simple methyl tert-butyl ether, simple, ethyl tert-butyl ether, alkalescency having from 1 to 4 carbon atoms, in particular propylene carbonate, ester alkyloxy acid having from 3 to 6 carbon atoms, in particular an ester of tert-butyl acetic acid, THF, toluene, 1,3-dioxolane, acetone, ozone-butyl-ketone, ethylmethylketone, 1,4-dioxane, tert simple-butyl methyl ether, cyclohexane, methylcyclohexane, toluene, hexane, dimethoxymethane, 1,1-dimethoxyethane, acetonitrile, as well as their single-phase and multiphase mixture. It may be preferable to separate the released water or alcohol through binary or triple heteroatom, boiling more close to the temperature optimum of the applied enzyme. Remote so the alcohol can then be removed through time the bookmark phase / membrane vapor separation.

Selectively to organic solvents can be added aqueous solvent, so that, depending on the organic solvent, there are single-phase or multiphase reaction solutions. Aqueous solvents are, for example, water and water diluted (e.g., 10-100 mm) buffers, for example, with a pH in the range from about 6 to 8, such as potassium phosphate or the buffer is TRIS-HCl.

The water content of the reaction the mixture is typically at 0 to 10% of the mass. Preferably the reagents used without pre-treatment (drying, the introduction of water).

The substrates are present or dissolved, suspended as a solid or in emulsion in the reaction medium. Preferably, the initial concentration of the reactants is in the range 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 performed continuously, for example in a tubular reactor or in a cascade of tubular reactors, or periodically.

The transformation can be carried out in any reactor suitable for such transformations. Such reactors are known to the person skilled in the art. Preferably, the transformation occurs in a reactor with a stirrer or in a reactor with a fixed bed.

For stirring the reaction the mixture can be applied any means. Does not require special is s device for mixing. The reaction medium may be single phase or multiphase and reagents it is dissolved, suspended or emuleret, if necessary, represent together with the molecular sieve and to initiate the reaction, and optionally, one or more times during the reaction, is mixed with an enzyme preparation. The temperature during the reaction set to the desired value and can, if desired, during the course of the reaction to increase or decrease.

If the reaction is carried out in a reactor with a fixed bed, a reactor with a fixed bed is preferably equipped with immobilized enzymes, while the reaction mixture can be pumped through the column filled with the enzyme. It is also possible to carry out the conversion in the fluidized bed reactor, and the enzyme used immobilized on the carrier. The reaction mixture can be continuously pumped through the column with the flow rate to adjust the time of transformation and thus the desired transformation. It is also possible to pump the reaction mixture in circulation through the column, while at the same time, you can drive off under vacuum released alcohol.

The removal of water in the case of esterification or alcohols, which are released when the transesterification of the alkyl(meth)acrylate, continuously or gradually known way is, for example, by vacuum, azeotropic removal, absorption, pervaporation and diffusion through the membrane.

Candidates preferably molecular sieves or zeolites (size of pores, for example, in the area of about 3-10 angstroms), separation by distillation or with the aid of suitable semipermeable membranes.

However, it is also possible to add the separated mixture of alkyl(meth)acrylate and its underlying spirit, which often forms an azeotrope, directly into the device to obtain the alkyl(meth)acrylate, again to be used in the esterification with (meth)acrylic acid.

After the reaction, the reaction mixture resulting from the esterification or interesterification can be used further without further purification or, if necessary, clean the next phase.

As a rule, at the stage of purification of the reaction mixture is separated only by the applied enzyme and the reaction product is separated from the optionally used organic solvent.

Department of the enzyme occurs, usually by filtration, absorption, centrifugation or desantirovaniya. The separated enzyme can then be used for the following reactions.

Separation from the organic solvent occurs, usually by distillation, rectification or solid reaction products by filtration.

For the next purification of the reaction product it is possible to perform chromatography.

However, preferably the cleanup phase is separated only by the applied enzyme and, optionally used solvent or an excess of (meth)acrylic acid or (meth)acrylate.

The reaction conditions for enzymatic esterification or interesterification are soft. On the basis of low temperatures and other mild conditions to avoid formation of by-products during the reaction, which can occur otherwise, for example from chemical catalysts or due to unwanted free-radical polymerization of (meth)acrylates, which otherwise can only be prevented by adding stabilizers.

When proposed according to the invention the reaction of the compound (meth)acrylic (D) can be added in excess and thus already contained dry bulk catalyst additional stabilizer, for example a simple gidrokolonoteraphy ether, penetratin, phenols, such as, for example, 2-tert-butyl-4-METHYLPHENOL, 6-tert-butyl-2,4-dimethyl-phenol or N-oxely, such as 4-hydroxy-2,2,6,6-tetramethyl-piperidine-N-oxyl, 4-oxo-2,2,6,6-tetramethyl-piperidine-N-oxyl, for example, in quantities from 50 to 2000 ppm. Preferably the esterification or transesterification is carried out in the presence of oxygen-containing gas is, preferably air or mixtures of air is nitrogen.

Next, the enzyme catalyst can be removed from the final product

The reaction mixture can, if necessary, be cleaned, for example by filtration, distillation, fractional distillation, chromatography, treatment with ion exchangers, adsorbents, neutral, acidic and/or alkaline washing, steaming or crystallization.

As the subject of the proposed invention are (meth)acrylates derived from alcohols (C) by enzymatic esterification or interesterification. Thanks proposed according to the invention the terms (meth)acrylates have an index of coloring below 100 ARNA according to DIN ISO 6271, preferably below 80. In addition, they contain, as a rule, less than 1.0% by-products from the reactions of the double bond rearrangement of natalizumab acids or bases adverse reactions.

The advantage thus obtained is proposed according to the invention by way of esters of (meth)acrylic acid is that based on their low color index can preferably be used in applications of varnishes and there, in particular, in the colorless varnishes, as they are due to their low color cause slight color coatings in comparison with alcohol, obtained in the usual way.

Additionally, the coating obtained according to the proposed invention esters can have a very high resistance to scratching, hardness, resistance to chemical reagents, flexibility and adhesion, both on hydrophilic and hydrophobic substrates.

Obtained according to the invention esters of (meth)acrylic acid (F) can be used preferably as monomers or comonomers in a poly(meth)acrylates or as reactive diluents in a poly(meth)acrylates, thermally curable, radiation and/or two-way thermotherapies. Such poly(meth)acrylates are suitable, for example, as binders in coating materials, thermally curable, radiation and/or two-way thermotherapies, as well as in adhesives, such as acrylate adhesives, and sealing compounds.

Therefore, the next subject of this invention is the use of esters of (meth)acrylic acid obtained is proposed according to the invention method, as reactive diluents or adhesives in compositions for coatings, radiation-curable or double sided thermotherapies, preferably in a protective coating, particularly preferably colorless transparent varnishes. Of course proposed according to the invention esters of (meth)acrylic acid can also be used as monomers in polymerization, if necessary together with other polymerized monomers, tecimical, for example, (meth)acrylic acid, esters of (meth)acrylic acid, styrene, butadiene, Acrylonitrile, vinyl acetate, N-vinyl pyrrolidone, a simple 4-hydroxybutyl-vinyl ether or M-vinylformamide.

Under the "two-way thermotherapies" understand that the coating compounds utverjdayut thermally or with actinic radiation. Under the proposed invention under actinic irradiation understand electromagnetic radiation as visible light, UV radiation or x-ray radiation, in particular UV radiation, and corpuscular radiation such as electron radiation.

Curing irradiation adhesives are those which are curable with actinic radiation, as defined above, in particular by means of UV irradiation.

As the subject of the proposed invention are compositions of varnishes containing esters of (meth)acrylic acid obtained is proposed according to the invention method. While esters of (meth)acrylic acid can be used as basic lacquers and coating lacquers. On the basis of their special characteristics, in particular their low color index, their application is preferably in the protective coatings and radiation-curable coating of transparent varnish.

Along with esters of (meth)acrylic acid (F), received the proposal is i.i.d. according to the invention method, proposed according to the invention radiation-curable masses can contain the following components:

(G) at least one curable compound with several copolymerizable, ethyleneamine groups,

(H) optionally, a reactive diluent,

(I) if necessary, photoinitiator, and

(J) if necessary, the following additives typical for varnishes.

As the compounds (G) apply curing irradiation, radically curable compounds with multiple, i.e. at least two, copolymerizable, ethyleneamine groups.

Preferably in the compounds (G) refers to the simple compounds, vinyl ether or (meth)acrylate, particularly preferred are the compounds of acrylates, i.e. derivatives of acrylic acid.

The preferred connection is simple vinyl ether and (meth)acrylate (G) contain from 2 to 20, preferably 2 to 10, and highly preferably from 2 to 6 copolymerizing, Ethylenediamine double bonds.

Especially preferred are such compounds (G) content Ethylenediamine double bonds from 0.1 to 0.7 mol /100 g, particularly preferably from 0.2 to 0.6 mol/100 g

Srednekislye molecular mass Mpcompounds (G) is, unless otherwise specified, PR is doctitle at 15000, particularly preferably at 300-12000, highly preferably at 400-5000 and in particular when 500-3000 g/mol (determined by gel chromatogaphy with polystyrene as standard and tetrahydrofuran as eluent).

As compounds (meth)acrylate called esters of (meth)acrylic acid and, in particular, esters of acrylic acids, as well as simple vinyl ether multifunctional alcohols, in particular such that, together with the hydroxyl groups do not contain any of the following functional groups or at least groups of ethers. Examples of such alcohols are, for example, bifunctional alcohols, such as ethylene glycol, propylene glycol and their more highly condensed representatives, such as diethylene glycol, triethylene glycol, dipropyleneglycol, tripropyleneglycol etc., 1,2-butanediol, 1,3-butanediol or 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, neopentylglycol, alkoxysilane phenolic compounds, such as ethoxylated or propoxycarbonyl bisphenola, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol or 1,4-cyclohexanedimethanol, trifunctionally and highly functional alcohols, such as glycerin, trimethylolpropane, butanetriol, trimethylacetyl, pentaerythrit, detromethorphan, dipentaerythritol, with the bit, the mannitol and the corresponding alkoxysilane, in particular ethoxylated and/or propoxycarbonyl alcohols.

Products alkoxysilane get in a known manner by turning the above-mentioned alcohols with acceleratedly, in particular with ethylene oxide or propylene oxide. Preferably the degree of alkoxysilane the hydroxyl group is from 0 to 10, that is, 1 mol of hydroxyl groups can be alkoxylated 10 mol alkalisation.

As compounds (meth)acrylate, also referred to as polyester(meth)acrylates, in this case we are talking about complex esters of (meth)acrylic acids or simple vinyl ether polifenoles, and urethane(meth)acrylate, epoxide(meth)acrylates or melamine(meth)acrylates.

The urethane(meth)acrylates receive, for example, obtained by transformation of the polyisocyanates with hydroxyalkyl(meth)acrylates and, if necessary, means for lengthening chains, such as diols, polyols, diamines, polyamine or developed or politely.

The urethane(meth)acrylates are preferably srednekamennogo molar mass Mnfrom 500 to 20,000, in particular from 750 to 10,000, particularly preferably from 750 to 3000 g/mol (determined by gel chromatography with polystyrene as standard).

The urethane(meth)acrylates preferably have a content of groups with (meth)acrylic from 1 to 5, especially site is preferably from 2 to 4 mol per 1000 g of urethane(meth)acrylate.

Epoxide(meth)acrylates obtained by conversion of epoxides with (meth)acrylic acid. As epoxides used, for example, epoxydecane olefins or simple glycidyloxy ether, for example a simple bisphenol-diglycidyl ether or aliphatic simple glycidyloxy ether, such as simple potentialapplications ether.

Melamine(meth)acrylates obtained by conversion of melamine with (meth)acrylic acids or their esters.

Epoxide(meth)acrylates and melamine(meth)acrylates are preferably srednekamennogo the molar mass Mnfrom 500 to 20,000, particularly preferably from 750 to 10,000 g/mol and highly preferably from 750 to 3000 g/mol; the content of the groups, (meth)acrylate is preferably from 1 to 5, particularly preferably from 2 to 4 per 1000 g of epoxide(meth)acrylate or melamine(meth)acrylate (determined by gel chromatography with polystyrene as standard and tetrahydrofuran as eluent).

Also suitable are the carbonate(meth)acrylates, which contain in the tool, preferably from 1 to 5, in particular from 2 to 4, particularly preferably from 2 to 3 groups of the (meth)acrylate and highly preferably group 2 (meth)acrylate.

Srednekislye molecular mass Mnthe carbonate(meth)acrylates preferably less than 3000 g/mol, particularly preferred is considerable less than 1500 g/mol, especially preferably less than 800 g/mol (determined by gel chromatography with polystyrene as standard, the solvent is tetrahydrofuran).

The carbonate(meth)acrylates get a simple way by the transesterification of esters of carbonic acid with polyhydric, preferably diatomic alcohols (dialami, for example, hexandiol) and subsequent esterification of free groups with (meth)acrylic acid or the transesterification with esters of (meth)acrylic acids, such as, for example, described in European patent application EP-A 92 269. Also they are obtained by conversion of phosgene, urea derivatives with polyhydric, for example, diatomic, alcohols.

As reactive diluents (compounds (N)) apply curing irradiation, radical or cation polymerized compounds with only one ethyleneamines, copolymerizable group.

Called, for example, alkyl(meth)acrylates having from 1 to 20 carbon atoms, vinylaromatic compounds having up to 20 carbon atoms, complex vinyl ester of carboxylic acids containing up to 20 carbon atoms, Ethylenediamine NITRILES, simple vinyl ether alcohols containing from 1 to 10 carbon atoms, α,β-unsaturated carboxylic acids and their anhydrides, and aliphatic hydrocarbons having from 2 to 8 atoms ug is erode and 1 or 2 double bonds.

As difficult alilovic esters of (meth)acrylic acid are preferred are those having one alkyl residue having from 1 to 10 carbon atoms, like methyl methacrylate, methyl acrylate, n-butyl acrylate, acrylate and 2-cilexetil.

In particular, also suitable mixture of complex alilovic esters of (meth)acrylic acid.

Complex vinyl esters of carboxylic acids having from 1 to 20 carbon atoms are, for example, vanillaware, ministart, finalproject and vinyl acetate.

α, β-unsaturated carboxylic acids and their anhydrides may be, for example, acrylic acid, methacrylic acid, fumaric acid, crotonic acid, taconova acid, maleic acid or the anhydride of maleic acid, preferably acrylic acid.

As vinylaromatic compounds are used, for example, vinyltoluene, α-butalbiral, 4-n-butalbiral, 4-n-decillion and preferably styrene.

The NITRILES include Acrylonitrile and Methacrylonitrile.

Suitable simple vinyl esters are, for example, a simple vinylmations ether, simple minimizebutton ether, simple vinyljelly ether and simple vigilantly ether.

As a non-aromatic hydrocarbon having from 2 to 8 carbon atoms, and one or two olefinic double bonds, called the bout is a diene, isoprene, and ethylene, propylene and isobutylene.

In addition, the use of N-vinylformamide, N-vinyl pyrrolidone, and N-vinylcaprolactam.

As photoinitiators (I) can be applied photoinitiator known to the person skilled in the art, such as UV photoinitiator, for example, which are named in "Advances in Polymer Science", Volume 14, Springer Berlin 1974 or in K. K. Dietliker, Chemistry and Technology of UV-and EB-Formulation for Coatings, Inks and Paints, Volume 3; Photoinitiators for Free Radical and Cationic Polymerization, P. K. T. Oldring (Eds), SITA Technology Ltd, London.

Used, for example, monoolefinic or besatisfied-led Irgacure 819 (bis(2,4,6-tri-methylbenzoyl)phenylphosphonate), such as described, for example, in European patent applications EP-7508, EP-A 57474, German patent application DE-A 19618720, European patent applications EP-A 495751 or EP-A 615980, for example 2,4,6-trimethylbenzenesulfonamide (Lucirin®TPO), ethyl-2,4,6-trimethylbenzenesulfonyl, benzophenone, hydroxyacetophenone, phenylglyoxylic acid and its derivatives or mixtures of these photoinitiators. As examples referred to as benzophenone, acetophenone, ACE-thanatogenos, methyl ethyl ketone, valerophenone, hexanophenone, α-phenylbutyrate, p-morpholinopropan, dibenzosuberone, 4-morpholinobutyrophenone, 4-morfolinoetilrutin, p-diacetylbenzene, 4-amino-benzophenone, 4'-methoxyacetophenone, β-methylanthraquinone, tert-butylanthraquinone, challenging the IDF anthracenemethanol acid, the benzaldehyde, α-tetralone, 9-acetylphenanthrene, 2-acetylphenanthrene, 10-thioxanthine, 3-acetylphenanthrene, 3-acetylindole, 9-forenoon, 1-indanone, 1,3,4-treceiver, thioxanthen-9-he, xanthene-9-he, 2,4-dimethyl-thioxanthone, 2,4-dietitican, 2,4-di-ISO-proportionate, 2,4-dichlorodioxane, benzoin, simple benzoin-ISO-butyl ether, chloroxylenol, simple benzoin-tetrahydropyranyloxy ether, simple benzoin methyl ether, simple benzoin ethyl ether, simple, benzoin butyl ether, simple benzoin-ISO-propyl ether, a simple 7-N-benzoin methyl ether, benzo[de]anthracene-7-it, 1-naphthaldehyde, 4,4'-bis(dimethylamino)benzophenone, 4-phenylbenzophenone, 4-chlorobenzophenone, michler ketone, 1-acetonaphthone, 2-acetonaphthone, 1-benzoylchloride-1-ol, 2-hydroxy-2,2-dimethylacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 1-hydroxyacetophenone, acetamidomethyl, o-methoxybenzophenone, triphenylphosphine, tri-o-tolylphosphino, Benz[a]anthracene-7,12-dione, 2,2-diethoxyacetophenone, benzylacetone, such as benzyldimethylamine, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-he, anthraquinones, such as 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 1-chloro-anthraquinone, 2-Melantrich and 2,3-butandiol.

Also suitable are non yellowing or slightly yellowish photoinitiator type ester is in phenylglyoxylic acid, such as described in German patent applications DE-A 19826712, DE-A 19913353 or in the international patent application WO 98/33761.

Among these photoinitiators are preferred phosphine oxides, α-hydroxyketone and benzophenone.

In particular, it is also possible to use mixtures of different photoinitiators.

Photoinitiator can be used alone or in combination with the promoter of photopolymerization, for example benzoic acid, amine or similar type.

Is also possible to use infrared photoinitiators.

Photoinitiator contain a mixture of sensitizer-coinitiator. As the sensitizing dye is often used dyes, in particular cyanine dyes, xanthylium dyes or triazine dyes and as coinitiators, for example, salts boronate, salt sulfone, salt iodone, sulfones, peroxides, pyridine-M-oxides or galogensoderjasimi.

As the following additives typical varnishes (J), can be applied, for example, antioxidants, oxidation inhibitors, stabilizers, accuracy (accelerators), fillers, pigments, dyes, means for degassing bishopshostel, antistatic agents, fire tools, thickeners, thixotropic agents, AIDS, contributing to the spreading, binders, antifoams, d is Chistye substances, surface-active agents, viscosity modifiers, softeners, plasticizers, resins, which increases the adhesion (a substance that imparts stickiness), complexing agents or tools for compatibility (Miscibility).

As an accelerator for thermal dauvergne can be applied, for example, octoate tin, octoate zinc, winner dibutylamine or diaza[2.2.2]bicicletta.

In addition, you can add one or more photochemically and/or thermally activatable initiators, such as peroxodisulfate potassium, Dibenzoyl peroxide, cyclohexanedione, di-tert-butylperoxide, azobis-ISO-butyronitrile, cyclohexyldiazeniumdioxy, di-ISO-propylparaben, tert-BUTYLPEROXY or benzopinacol, as well as, for example, thermally activated initiators which have a half-life at a temperature of 80°C more than 100 hours as di-tert-butylperoxide, cumonherface, dicumylperoxide, tert-butylperbenzoate, siciliane penacoli, which are commercially available, for example, under the trade names ADDID 600 Wacker or containing hydroxyl groups amine-N-oxides, such as 2,2,6,6-tetramethylpiperidine-N-oxyl, 4-hydroxy-2,2,6,6-Tetra-methylpiperidin-N-oxyl, etc.

The following are examples of suitable thermally activated initiators are described in "Polymer Handbook", 2nd edition, Wiley & Sons, new York.

In the operation of thickeners along with the radically (co)polymerized (co)polymerizate, apply the usual organic and inorganic thickeners, such as hydroxymethylcellulose or bentonites.

As complexing agents can be used, for example, ethylene-diaminooctane acid and its salts, and β-diketones.

Suitable fillers include silicates, such as silicates obtained by hydrolysis of silicon tetrachloride, such as Aerosil® company Degussa, krasnozem, talc, aluminum silicates, magnesium silicates, calcium carbonates, etc.

Suitable stabilizers include typical UV absorbers such as oxanilide, triazine and benzotriazole (the latest available as trademark Tinuvin® company Ciba-Spezialitätenchemie) and benzophenone. They can be used alone or together with suitable acceptors of free radicals, such as spatial dull amines such as 2,2,6,6-tetramethylpiperidine, 2,6-di-tert-butylpiperazine or their derivatives, such as bis-(2,2,6,6-Tetra-methyl-4-piperidyl)sebacina. Stabilizers generally used in quantities of from 0.1 to 5.0 wt. -%, in the calculation of the solid components present in the composition.

Following suitable stabilizers are, for example, N-oxely, such as, for example, 4-hydroxy-2,2,6,6-tetramethyl-piperidine-N-oxyl, 4-oxo-2,2,6,6-tetramethyl-piperidine-N-oxyl, 4-acetoxy-2,2,6,6-tetramethyl-piperidine-N-oxyl, 2,2,6,6-tetramethyl-piperidine-N-oxyl, 4,4',4"-the Fig(2,2,6,6-tetramethyl-piperidine-N-oxyl)-pofit or 3-oxo-of 2.2.5.5-tetramethyl-pyrrolidin-N-oxyl, phenols and Naftali, such as, for example, p-aminophenol, p-nitrosophenol, 2-tert-butylphenol, 4-tert-butylphenol, 2,4-di-tert-butylphenol, 2-methyl-4-tert-butylphenol, 4-methyl-2,6-tert-butylphenol (2,6-tert-butyl-p-cresol) or 4-tert-butyl-2,6-dimethylphenol, quinones, such as hydroquinone or simple gidrokolonoteraphy ether, aromatic amines, such as, for example, N,N-diphenylamine, N-nitroso-diphenylamine, phenylenediamine, such as, for example, N,N'-dialkyl-para-phenylenediamine, with the remains of the alkyl may be the same or different and can be independently from each other from 1 to 4 carbon atoms and can be straight or branched, hydroxylamine, such as, for example, N,N-diethylhydroxylamine, derivatives of urea, such as, for example, urea or thiourea, phosphorus-containing compounds, such as, for example, triphenylphosphine, triphenylphosphite or triethylphosphite, or sulfur containing compounds such as, for example, diphenylsulfide or phenothiazin.

Typical compositions for curing by irradiation of the masses are, for example,

(F) 20-100 wt. -%, preferably 40-90, particularly preferably 50 to 90 and in particular 60-80 wt. -%,

(G) 0-60 wt. -%, preferably 5-50, particularly preferably 10 to 40 and in particular 10-30% of mass.,

(H) 0-50 wt. -%, preferably 5-40, particularly preferably 6-30 and in particular 10-30% of mass.,

(I) 0-20 wt. -%, before occhialino 0.5 to 15, particularly preferably 1-10, and in particular 2-5 wt. -%, and

(J) 0-50 wt. -%, preferably 2-40, particularly preferably 3 to 30 and in particular 5 to 20 wt. -%,

provided that (F), (G), (H), (I) and (J) together give the 100% of the mass.

The coating of the substrates is customary methods known to the person skilled in the art, with at least one composition for the coating applied to the coated substrate in the desired concentration and, if necessary, contained volatile components of the mass to cover, if necessary, removed by heating. This process is optionally repeated one or more times. Coating the substrate can occur in a known manner, for example by spraying, painting, coating using a doctor blade, brush, rolling, rolling, spillages, laminating, podrazdeleniya or coextruder-tion. The concentration of the coating is typically in the range from about 3 to 1000 g/m2and preferably from 10 to 200 g/m2.

In addition, describe the method of applying coatings to substrates on which the composition for a coating applied to the substrate and, if necessary, dried, utverjdayut by electron irradiation or UV exposure in oxygen-containing atmosphere or preferably under inert gas, if necessary, at temperatures up to the level of the drying temperature.

Drying t is the train may occur in addition or instead of thermal drying by NIR irradiation, thus in the form of NIR-radiation here indicate electromagnetic radiation in wavelengths of from 760 nm to 2.5 μm, preferably from 900 to 1500 nm.

If necessary, may, if several layers of composition for coating put one above the other, after each coating process to happen thermal and/or NIR-drying and curing radiation.

As sources of radiation for curing irradiation are suitable, for example, mercury irradiator operating at low pressure, mercury irradiator operating at medium pressure with the irradiator operating at high pressure, and also fluorescent tubes, pulsed irradiators, halides of metals emitters, electronic lighting device of the instant action, resulting in cure irradiation without photoinitiator, or excimer irradiators. Curing by irradiation by exposure to high-energy radiation, i.e. UV radiation or daylight, preferably light irradiated in the region of wavelengths from λ=200 to 700 nm, particularly preferably from λ=200 to 500 nm and highly preferably from λ=250 to 400 nm, or by irradiation with high energy electrons (electron irradiation; 150 to 300 keV). As irradiation sources are, for example, mercury lamps, high pressure, laser, ulcerous the e lamp (light flash), halogen lamps or excimer irradiators. Doses sufficient, as a rule, for stitching, UV curing are in the range from 80 to 3000 MJ/cm2.

Of course, curing is also used multiple sources of exposure, such as from two to four. They can also be irradiated in respectively different areas of wavelengths.

Irradiation can be performed, if necessary, also with the exclusion of oxygen, for example in an atmosphere of inert gas. As the inert gases are suitable are preferably nitrogen, noble gases, carbon dioxide or combustion gases. Further exposure can occur while the masses to cover the transparent media. Prozrachnymi environments are, for example, plastic films, glass or liquids, for example water. Especially preferred is the exposure in a manner such as described in German patent application DE-A1 19957900.

In addition, the subject of the proposed invention is a substrate coated with proposed according to the invention a multilayer coating.

Thickness, such as describe, curable layer may be from 0.1 μm to several mm, preferably from 1 to 2000 μm, particularly preferably from 5 to 1000 μm, most preferably from 10 to 500 μm and in particular from 10 to 250 microns.

According to the invention obtained esters of (meth)acrylic acid can be applied on the basis of their minor staining preferably also thermally induced (radical) (co)polymerization.

As monomers, which, for example, can be copolymerizate obtained according to the invention esters of (meth)acrylic acids, as, for example alkyl(meth)-acrylates having from 1 to 20 carbon atoms, vinylaromatic compounds having up to 20 carbon atoms, complex vinyl ester of carboxylic acids containing up to 20 carbon atoms, Ethylenediamine NITRILES, simple vinyl ether alcohols containing from 1 to 10 carbon atoms, α,β-unsaturated carboxylic acids and their anhydrides, and aliphatic hydrocarbons having from 2 to 8 carbon atoms and 1 or 2 double bonds.

As difficult alilovic esters of (meth)acrylic acid are preferred are those having one alkyl residue having from 1 to 10 carbon atoms, like methyl methacrylate, methyl acrylate, n-butyl acrylate, acrylate and branched derivatives of alkyl, such as 2-ethyl hexyl acrylate.

In particular also suitable mixture of complex alilovic esters of (meth)acrylic acid.

Complex vinyl esters of carboxylic acids having from 1 to 20 carbon atoms are, for example, vanillaware, ministart, Winnie the propionate and vinyl acetate.

As vinylaromatic compounds are used, for example, vinyltoluene, α-butalbiral, 4-n-butalbiral, 4-n-decillion and preferably styrene.

The NITRILES include Acrylonitrile and Methacrylonitrile.

Suitable simple vinyl esters are, for example, a simple vinylmations ether, simple minimizebutton ether, simple vinyljelly ether and simple vigilantly ether.

As a non-aromatic hydrocarbon having from 2 to 8 carbon atoms, and one or two olefinic double bonds, referred to as butadiene, isoprene, and ethylene, propylene and isobutylene.

Frequent but not the only method of obtaining such with(polymerization) is a radical or ionic (co)polymerization in a solvent or diluent.

The radical (co)polymerization of such monomers is, for example, in aqueous solution in the presence of polymerization initiators which, under the polymerization conditions break down into radicals, such as peroxodisulfate, H2O2-radarsysteme or hydroxyperoxide, such as, for example, tert-butylhydroperoxide or cumene hydroperoxide. (Co)polymerization can occur in a wide temperature region, if necessary, under reduced or increased pressure, usually at temperatures up to 100°C. the pH of the reaction mixture is usual set in the range from 4 to 10.

(Co)polymerization can also be carried out by other well-known specialist in this field by way of continuously or periodically, such as polymerization in solution, precipitation polymerization, emulsion polymerization water-in-oil inverse emulsion, suspension or reversed suspension polymerization.

When this monomer/monomers (co)will polimerizuet when using radical polymerization initiators, such as azo compounds, RapidEye on radicals, such as 2,2'-azo-bis(isobutyronitrile), 2,2'-azobis-(2-amidinopropane)hydrochloride or 4,4'-azo-bis-(4'-lenitanoa acid) or dialkylamide, such as di-tert-AMYLPEROXY, aryl-alkylperoxide, such as tert-butyl-semiprocessed, alkyl-allproxy, such as tert-butyl peroxy-2-ethylhexanoate, PEROXYDICARBONATE, such as di-(4-tert-butylcyclohexyl)PEROXYDICARBONATE or hydroperoxides.

These compounds are in most cases used in the form of aqueous solutions or aqueous emulsions, the lower the concentration determined through the amount of water that is acceptable in the (co)polymerization, and the upper concentration through the solubility of the respective compound in water.

As solvent or diluent can be, for example, water, alcohols, such as methanol, ethanol, n-propanol or ISO-propanol, n-butanol or ISO-butanol, is whether ketones, such as acetone, ethylmethylketone, diethylketone or ODS-butylmethylether. Particularly preferred are non-polar solvents, such as xylene and his izmerenie mixture, Shellsol®And solvent-naphtha.

In a preferred embodiment, the monomer pre-mix and add the initiator, if necessary, the following additives dissolved in the solvent. Particularly preferred implementation described in international patent application WO 01/23484 and there especially on page 10, 3 - 24.

If necessary, the (co)polymerization can be carried out in the presence of growth regulators chain, such as, for example, salts of hydroxylamine, chlorinated hydrocarbons and tizaidine, such as, for example, tert-butylmercaptan, complex acrylic ester of thioglycolic, mercaptoethanol, mercaptopropionylglycine, dodecylmercaptan, tert-dodecylmercaptan or hypophosphite alkali metals. When the (co)polymerization of these regulators can be used, for example, in amounts of from 0 to 0.8 wt. -%, per 100% wt. (co)polymerized monomers, which reduce the molar mass of the resulting (co)polymer.

The emulsion polymerization can be applied dispersants, ionic and/or nonionic emulsifiers and/or protective colloids or stabilizers as surface is chestno-active compounds. As such used as protective colloids used, generally, for carrying out emulsion polymerization, and emulsifiers.

Protective colloids are, for example, copolymerizate containing polyvinyl alcohols, cellulose derivatives or vinyl pyrrolidone. Detailed description of the following suitable protective colloids is found in Houben-Weyl, Methods der organischen Chemie, Band XIV/1, makromolekulare Stoffe, publisher Georg-Thieme, Stuttgart, 1969, s-420. Of course, you can also apply a mixture of emulsifiers and/or protective colloids. Preferably as dispersant use exclusively emulsifiers, whose relative molecular weights are in contrast to the protective colloids, are usually below 1000. They can be either anionic, cationic and non-ionic origin. Of course, in the case of mixtures of surface-active substances, the individual components must be compatible with each other, which in the case of doubt can be checked, guided by preliminary tests. In General, anionic emulsifiers are compatible with each other and with non-ionic emulsifiers.

Such also serves to cationic emulsifiers, whereas anionic and cationic emulsifiers are mostly incompatible with each other. Used emulsifiers are, for example, amoxilina-bath monoalkylphenol is, dialkylphenol and dialkylphenol (degree of EO: 3 to 100: 4 to 12 carbon atoms), ethoxylated fatty alcohols (degree of EO: 3 to 100, the remaining alkyl: from 8 to 18 carbon atoms), and also alkali metal salts and ammonium salts on the basis of alkyl sulphates (the remainder of alkyl: from 8 to 16 carbon atoms) based on complex profirov sulfuric acid, the ethoxylated ALKYLPHENOLS (degree of EO: 3 to 100, the remaining alkyl: from 4 to 12 carbon atoms), based on alkylsulfonic acid (remainder of alkyl: from 12 to 18 carbon atoms) and on the basis of alkylarylsulfonate acid (remainder of alkyl: from 9 to 18 carbon atoms). The following are suitable emulsifying agents, such as esters sulfonterol acid, are found in Houben-Weyl, Methods der organischen Chemie, Band XIV/1, Makromolekulare Stoffe, publisher Georg-Thieme, Stuttgart, 1961, p.á192-208.

Generally, the amount used of the dispersant is from 0.5 to 6, preferably from 1 to 3% of the mass. in the calculation of the radically curable monomers.

Examples of the (meth)galatsaray dispersions are dispersions of n-butyl acrylate/Acrylonitrile, which are used as adhesives, n-butyl acrylate/butadiene/styrene-.

Polymer dispersion, in which use is obtained according to the invention esters of (meth)acrylic acids, can be further chemically and/or physically deodorizing.

The copolymers obtained obtained coz the ACLs to the invention esters of (meth)acrylic acid, have, as a rule, low color index, which is preferred in the lacquer field. Described copolymers can then be turned into a known manner, for example, aminos, such as, for example, melamine, crosslinked resins for varnishes, such as, for example, described in European patent applications EP 738740 or EP 675141.

Particularly preferably proposed according to the invention, the compositions for coatings are suitable as or in exterior coatings, i.e. those applications that are exposed to daylight, preferably of buildings or parts of buildings, internal coating, pavement markings, coatings on vehicles and aircraft. In particular, the coatings used in the form of wood coatings, paper coatings or plastic coatings, for example for flooring or furniture.

Next subject is the use according to the invention the products obtained as intermediates for bishopapostles electroplating. Thanks to them, compared with usually the resulting products, low color index, they are especially suitable for this application.

Using proposed according to the invention, a method is possible to obtain esters of (meth)acrylic acid (F) in high chemical purity and the output of the space-time and under mild conditions with good color indexes. Despite the refusalof the activated compounds of (meth)acrylic acid purposefully get the desired products with high selectivity, which are substantially free from by-products.

The following examples serve to explain the characteristics of this invention, but in no way limit its scope.

Examples

In this document as "parts", unless otherwise specified, see "mass parts".

Golpanol® PME is a commercially available product of BASF AG, Ludwigshafen. While we are talking about a mixture of singly and doubly ethoxylated propargilovyh alcohol.

Example 1

Etherification Golpanol® PME with different excess methyl acrylate

Golpanol® PME (5 mmol, 501 mg) is shaken with methyl acrylate, 25 mg of Novozym® 435 (lipase from Candida antartica) and 1.0 g of molecular sieve 5 Å for 24 h at 40°C and the conversion was determined by gas chromatography.

The number of methyl acrylate [mmol]Conversion [%]
50100
40100
30100
2099
20 (without enzyme)10
1092

p> Example 2

Preparative composition with Golpanol PME

In a 4-liter round flask equipped with a reflux condenser are placed 1377 g of methyl acrylate (16.0 mol), 400,5 g Golpanol® PME (4.0 mol, color index 47 according to Hazen (APHA)), 800 g of molecular sieve 5 Å and 50 mg simple gidroaerodinamicheskogo ether and the reaction initiated by the addition of 20.0 g of Novozym® 435. After 7 h of stirring at a temperature of 40°C. the solids are removed through a suction filter. The excess methyl acrylate is removed on a rotary evaporators (40°C, 6 mbar). According to gas chromatographic analysis of alcohol was esterified to 99.5%. Receive 557 g (yield 93%) of 2-prophylactically in the form of a clear liquid slightly yellowish color with the color index 79 according to Hazen (APHA, DIN ISO 6271).

Example 3

Turning propargilovyh alcohol

Propargilovyh alcohol (5 mmol, 295 ml) is shaken with 50 mmol of methyl acrylate (4,51 ml), 25 mg of Novozym® 435 and possibly 1.0 g of molecular sieve 5 Å for 24 h at 40°C and the conversion was determined by GC.

Molecular sieve additiveConversion [%]
No58
95

1. SP is a way to obtain esters of (meth)acrylic acid (F) on the basis of alcohols, having at least one carbon-carbon triple bond, wherein at least one alcohol having at least one carbon-carbon triple bond, of the formula (1)

where R1means hydrogen, alkyl having from 1 to 18 carbon atoms;
alkyl having from 2 to 18 carbon atoms, aryl having from 6 to 12 carbon atoms, cycloalkyl having from 5 to 12 carbon atoms, interrupted, if necessary, by one or more oxygen atoms and/or sulfur and/or one or more substituted or unsubstituted aminopropane, five-membered or-six-membered heterocycle having oxygen atoms, nitrogen and/or sulfur, with the mentioned residues can be substituted, respectively, by aryl, alkyl, aryloxy, alkyloxy, heteroatoms and/or heterocycles, and R2means alkylene having from 1 to 20 carbon atoms, cyclo-alkylene having from 5 to 12 carbon atoms, Allen having from 6 to 12 carbon atoms, or alkylene having from 2 to 20 carbon atoms, interrupted by one or more oxygen atoms and/or sulfur and/or one or more substituted or unsubstituted aminopropane and/or one or more groups of cycloalkyl, -(CO)-, -O(CO)O-, -(NH)(CO)O-, -O(CO)(NH)-, -O(CO)- or -(CO)O-, with the mentioned residues can be substituted, respectively, by aryl, alkyl, aryloxy, Ala is lexi, heteroatoms and/or heterocycles,
n means an integer from 0 to 3, preferably from 0 to 2 and particularly preferably from 1 to 2 and
Xifor each i=0 to n independently of one another can be selected from the group-CH2-CH2-O-, -CH2-CH(CH3)-O-, -CH(CH3)-CH2-O-, -CH2-C(CH3)2-O-, -C(CH3)2-CH2-O-, -CH2-CHVin-O-, -CHVin-CH2-O-, -CH2-CHPh-O - and-CHPh-CH2-O-, preferably from the group-CH2-CH2-O-, -CH2-CH(CH3)-O - and-CH(CH3)-CH2-O-, particularly preferably-CH2-CH2-O-,
where Ph means phenyl and Vin denotes vinyl and hydroxy-group of the alcohol is primary or secondary,
etherification in the presence of at least one enzyme (E) with (meth)acrylic acid or preterition with at least one complex ester of (meth)acrylic acid (D).

2. The method according to claim 1, characterized in that the alcohols (S) are alcohols of the formula (2)

where n, Xiand R1can have the above values and
R3-R6independently of one another denote hydrogen, alkyl having from 1 to 18 carbon atoms; alkyl having from 2 to 18 carbon atoms, aryl having from 6 to 12 carbon atoms, cycloalkyl having from 5 to 12 carbon atoms, interrupted, if necessary, one or more atoms kislorod/or sulfur and/or one or more substituted or unsubstituted aminopropane, or the five-to six-membered heterocycle having oxygen atoms, nitrogen and/or sulfur, with the mentioned residues can be substituted, respectively, by aryl, alkyl, aryloxy, alkyloxy, heteroatoms and/or heterocycles.

3. The method according to one of claims 1 or 2, characterized in that the alcohols (S) are alcohols of the formula (3)

where n, Xi, R1can have the above values and
R7and R8independently of one another denote hydrogen, alkyl having from 1 to 18 carbon atoms; alkyl having from 2 to 18 carbon atoms, aryl having from 6 to 12 carbon atoms, cycloalkyl having from 5 to 12 carbon atoms, interrupted, if necessary, by one or more oxygen atoms and/or sulfur and/or one or more substituted or unsubstituted aminopropane, five-membered or-six-membered heterocycle having oxygen atoms, nitrogen and/or sulfur, with the mentioned residues can be substituted, respectively, by aryl, alkyl, aryloxy, alkyloxy, heteroatoms and/or heterocycles,
where R7and R8together may form a ring.

4. The method according to one of claims 1 or 2, characterized in that the alcohol (S) selected from the group consisting of 3-methyl-1-pentyn-3-ol, 2-propyne-1-ol (propargilovyh alcohol), 3-butyn-2-ol, 2-methyl-3-butyn-2-ol, 4-pentyn-1-ol, 1-ethynylcyclohexanol, 3-bout the n-1-ol, 2-buten-1-ol and 1-octyn-3-ol, and their once or twice ethoxylated products.

5. The method according to one of claims 1 or 2, characterized in that the enzyme (S) selected from esterase (ES.-.-), lipases (EC), glycosides (ES.-.-) and proteases (ES.-.-).



 

Same patents:

FIELD: chemistry.

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46 cl, 8 ex

FIELD: chemistry; biochemistry.

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41 cl, 23 dwg

FIELD: chemistry.

SUBSTANCE: invention relates to biotechnology and can be used for producing esters of such compounds as carbohydrates, proteins, protein subunits and hydroxyacids. The method involves mixing an acyl group donor, acyl group acceptor and water with formation of a medium with high water content, containing 5 to 98% water. The acyl group donor used is a lipid substrate, chosen from phospolipid, lysophospholipid, triacylglyceride, diglyceride, glycolipid or lysoglycolipid, and the acyl group acceptor used is carbohydrate, protein, protein subunitor hydroxyacid. The mixture is brought into contact with lipidacyltransferase, which catalyses alcoholysis and/or re-esterification and is an enzyme which has acyltransferase activity, containing a GDSX fragment of amino acid sequence, where X stands for one or more of the following amino acid residues L, A, V, I, F, Y, H, Q, T, N, M or S.

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18 cl, 51 dwg, 10 tbl, 13 ex

FIELD: chemistry.

SUBSTANCE: invention relates to method of obtaining ethers of fatty acids, which can be applied as biodiesel - alternative biofuel. Described is method of rapeseed oil processing by its re-etherification with ethyl alcohol, with separation of obtained products into fractions, obtained barbotage with carbon dioxin of immobilised granulated yeasts biomass, is realised in reactor at 350-400°C and pressure 35-50 MPa with following cooling of mixture, oven control in extractor to 250°C, extraction with carbon dioxide in overcritical conditions at 350°C and pressure 35 MPa. Obtained homogenous mixture is supplied into first separator for separation of glycerin from target product, and then target product is supplied to second separator for separation of fatty acid ethyl ether from carbon dioxin, which is directed to recycling.

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2 cl, 2 ex

FIELD: chemistry.

SUBSTANCE: invention relates to the field of biotechnology, namely, to isolation of polyhydroxibutyrate (PHB) from dry biomass of microorganism obtained by fermentative synthesis. The method involves extracting dry biomass of microorganism of genus Azotobacter with content of PHB of 50 to 75%, that of nitrogen of 1.2 to 3.5% and ash of 10 to 25% by chloroform at temperature 30-40°C and concentration of PHB in chloroform of 0.3 to 0.55 g/l, supplying PHB solution in chloroform to isopropyl alcohol evenly with rate of 1 to 3 l/hour with further separation and drying of target product.

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1 tbl, 19 ex

FIELD: organic chemistry, in particular stereoselective method for production of dihydroxyesters and derivatives thereof.

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19 cl, 1 tbl, 4 ex

FIELD: organic chemistry, chemical technology, microbiology.

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5 ex

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56 cl, 1 dwg, 8 ex

FIELD: biotechnology, biochemistry, pharmacy.

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70 cl, 8 tbl, 42 ex

Road marking paint // 2425076

FIELD: chemistry.

SUBSTANCE: road marking paint contains acrylic film-forming agent in form of a copolymer of n-butylmethacrylate with glycidylmethacrylate, calcite as filler, chloroparaffin CP-470 as plasticiser, toluene and ethyl acetate as an organic solvent, titanium dioxide as a pigment, an organic montmorillonite derivative Bentone SD-2 as a thickener, a dispersant in form of a mixture of natural phospholipids Soya lecithin, an anti-sedimentation agent in form of 20% solution of an organic compound in xylene M-P-A - 2000X, with the given ratio of components.

EFFECT: paint has high wear resistance of the film while retaining the rest of the characteristics.

2 tbl, 10 ex

FIELD: medicine.

SUBSTANCE: invention refers to a method of preparing a colour mass for vascular system filling in pathologic examinations which involves premixing a dye - a water-soluble acrylic colour and water in the ratio 0.9-1.1 portions to 0.18-0.21 portions to form a homogeneous mass, adding 9.7-9.9 portions of water and 0.18-0.21 portions of 96 % alcohol. It is followed with retempering and adding 9.7-9.9 portions of 96% alcohol, keeping for 12 hours and filtering.

EFFECT: improved colour mass for vascular system filling and simplified manufacturing procedure.

1 dwg, 1 ex

FIELD: construction.

SUBSTANCE: compound for road marking comprises main resins - n-butylacrylate and methyl methacrylate and hardener. Additionally it contains reactive resin on the basis of acrylic resins, hardener and accelerant of hardening reaction, containing the following components: 2-ethyl hexyacrylate, N,N-dihydroxyethyl-r-toluidine, N,N-dimethyl-r-toluidine, 2 (2-hydroxy-3,5-ditret-butylphenyl) benzotriazol, heavy hydrosulfonated oil, at the same time ratio of main resins and reactive resin is in the range from 1:3 to 3:1.

EFFECT: expansion of possibility to use compound in climatic conditions with low temperatures, which increases efficiency of marking operation with preservation of high speed of hardening.

FIELD: chemistry.

SUBSTANCE: invention relates to compositions for protective coating for window glass. The invention discloses a composition which contains a) one or more film-forming resins which contain acrylic and/or methacrylic functional fragments; b) one or more reactive diluents which contain an acrylate functional group; c) one or more compounds which promote adhesion of the composition to glass, which contain a product of a Michael reaction, having four or more siloxane groups, at least one acrylate group and a tertiary amine group; d) one or more filler substances, capable of endowing compositions with wear-resistance in solidified state; and e) one or more compounds which can react with a film-forming resin, which contain at least one acid fragment.

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16 cl, 5 dwg, 28 tbl, 38 ex

FIELD: chemistry.

SUBSTANCE: invention relates to impregnation and hermetisation of porous products with thermally hardened compositions based on (meth)acrylic monomers. Claimed is thermally hardened composition for impregnation and hermetisation of porous products, containing (in mass fraction): 100 (meth)acrylic monomer, 0.1-0.5 nitronitrile, 0.01-0.04 hydrohynone, 0.004-0.03 disodium salt of ethylendiaminetetraacetic acid, 0.001-0.03 2,2,6,6-tetramethyl-4-oxopiperidin-1-oxyl and 0.5-5.0 non-ionogenic emulsifying agent. Method of impregnation and hermetisation of porous products includes their vacuum processing with further impregnation under vacuum and atmospheric pressure with abovementioned composition and hardening at temperature ≥90°C. Thermally-hardened composition has higher serviceability and allows to increase productivity of impregnation and hermetisation method essentially.

EFFECT: increasing productivity of method of impregnation and hermetisation of porous products by means of thermally-hardened compositions.

2 cl, 1 tbl, 15 ex

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention relates to photoinitiating agents of phenylglyoxylic acid order used in polymerizing compositions to be subjected for hardening. Invention describes a photoinitiating agent of the formula (I): wherein Y means (C3-C12)-alkylene, butenylene, butinylene or (C4-C12)-alkylene that are broken by groups -O- or -NR2- and not following in sequence; R1 means a reactive group of the following order: -OH, -SH, -HR3R4, -(CO)-OH, -(CO)-NH2, -SO3H, -C(R5)=CR6R7, oxiranyl, -O-(CO)-NH-R8-NCO and -O-(CO)-R-(CO)-X; R2 means hydrogen atom, (C1-C4)-alkyl, (C2-C4)-hydroxyalkyl; R3 and R4 mean hydrogen atom, (C1-C4)-alkyl, (C2-C4)-hydroxyalkyl; R, R and R mean hydrogen atom or methyl; R8 means linear or branched (C4-C12)-alkylene or phenylene; R9 means linear or branched (C1-C16)-alkylene, -CH=CH-, -CH=CH-CH2-, C6-cycloalkylene, phenylene or naphthylene; X, X1 and X2 mean -OH, Cl, -OCH3 or -OC2H5. Also, invention describes a method for synthesis of a photoinitiating agent, polymerizing composition and substrate covered by its. Proposed photoinitiating agent possesses the effective introducing capacity and absence of migration in thermal treatments.

EFFECT: improved and valuable properties of agent.

13 cl, 1 tbl, 16 ex

FIELD: rocketry; production of the potting composition for armoring the charge made out of the ballistite propellant.

SUBSTANCE: the invention is pertaining to the field of rocketry and presents the potting composition for armoring the charge made out of the ballistite propellant. The potting composition includes polybutylmethacrylate, butylmethacrylate, methylmethacrylateand in the capacity of the initiator and activator of the hardening - benzoyl peroxide and dimethylaniline. At that polybutylmethacrylate is dissolved in the mixture of butylmethacrylate and methylmetacrylate. The invention ensures manufacture of the qualitative products with the required level of the physical-mechanical and adhesive properties, as well as to reduce smokiness of the gases, and to reduce temperature of the waste gases from 2200°С to 800°С.

EFFECT: the invention ensures manufacture of the qualitative products with the required level of the physical-mechanical and adhesive properties, as well as to reduce smokiness of the gases, and significantly to reduce temperature of the waste gases.

2 tbl

Composition makeup // 2277552

FIELD: polymer materials.

SUBSTANCE: invention relates to polymer composition based on binder, namely unsaturated polyether resin or oligoether acrylates, and may be used in medicine, in production of paint and lacquer materials, etc. Composition comprises, wt parts: unsaturated polyether resin or oligoether acrylates or mixtures thereof, 100; polymerization promoter, in particular complex compound prepared by reaction of vanadium derivatives (vanadium pentoxide, ammonium methavanadate, of methavanadic acid) with orthophosphoric acid/water/butanol mixture, 0.3-0.88; polymerization initiator: cumene hydroperoxide, 0.3-0.44; and modifying additives, 0-20.

EFFECT: optimized makeup involving inexpensive, easily available, and highly efficient promoter.

1 tbl, 6 ex

The invention relates to a method for producing polymer coatings with high protective physico-chemical properties, low toxicity, suitable for implantation in tissue of living organisms

FIELD: chemistry.

SUBSTANCE: oligoesters can be used as oligomers for synthesis of polycondensation polymers and are compounds of general formula: , where n = 1-20. Aromatic oligoesters care obtained in two steps. At the first step, disodium salt of 1,1-dichloro-2,2-di(3,5-dibromo-n-oxyphenyl)ethylene, obtained from treating 1,1-dichloro-2,2-di(3,5-dibromo-n-oxyphenyl)ethylene with an alkali solution and dehydration of the formed product with 4,4'-dichlorodiphenylketone at 140°C for 1 hour. At the second step, the formed oligoketone reacts with 4,4'-dichlorodiphenylsulphone at temperature 170°C for 5 hours. Both steps take place in dimethylsulphoxide.

EFFECT: wide range of oligomers suitable for polycondensation reaction to obtain high-molecular block-copolyester sulphone ketones with good mechanical and thermal properties.

2 cl, 4 ex

FIELD: chemistry.

SUBSTANCE: invention relates to a novel method of producing 6-[3-(1-adamantyl)-4-methoxyphenyl]-2-naphthoic acid of formula (I) through a Suzuki reaction between 3-adamantyl-4-methoxyphenylcarboxylic acid of formula (II) and 6-bromo-2-naphthoic acid of formula (III), wherein the reaction between compounds (II) and (III) is carried out at temperature between 60 and 110°C for between 30 minutes and 24 hours in an inert gas atmosphere in the presence of a palladium catalyst and a base in a polar solvent, followed by treatment with an acid. The invention also relates to use of compounds of formulae (II) and (III) to produce a compound of formula (I).

EFFECT: single-step method enables to obtain desired product with high output.

13 cl, 2 dwg, 3 ex

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