EP2419434A2

EP2419434A2 - Method for producing unsaturated acylamidoalkyl polyhydroxy acid amides

Info

Publication number: EP2419434A2
Application number: EP10711418A
Authority: EP
Inventors: Harald Keller; Mario Emmeluth; Tim Balensiefer; Paola Uribe Arocha; Francesca Aulenta
Original assignee: BASF SE
Current assignee: BASF SE
Priority date: 2009-04-15
Filing date: 2010-03-30
Publication date: 2012-02-22
Also published as: WO2010118950A2; JP5645919B2; US20120088891A1; WO2010118950A3; CN102421787B; CA2758759A1; JP2012524041A; CN102421787A

Abstract

The invention relates to a method for producing unsaturated acylamidoalkyl polyhydroxy acid amides, in which the reaction product from polyhydroxy acid lactone and aliphatic diamine is reacted with the anhydride of a simple unsaturated carboxylic acid. The invention also relates to unsaturated acylamidoalkyl polyhydroxy acid amides and to a method for producing polymers from unsaturated acylamidoalkyl polyhydroxy acid amides.

Description

Process for the preparation of unsaturated Acylamidoalkylpolyhydroxysäureamiden

description

The invention relates to a process for the preparation of unsaturated Acylamidoalkylpoly- hydroxysäureamiden, the unsaturated Acylamidoalkylpolyhydroxysäureamide and a process for the preparation of polymers of unsaturated Acylamidoalkylpoly- hydroxysäureamiden.

A process for the preparation of 1-amino-2-D-gluconoylaminoethane is described in H.U. Geyer, Chem. Ber. 1964, 2271 described.

US 2,084,626 describes a process for the preparation of monoallylamide of gluconic acid. For the preparation, the lactone of gluconic acid with allylamine in ethanol is converted into the gluconic acid amide.

Analogously, we describe the preparation of the monoallylamine of lactobionic acid and its copolymerization with acrylamide by M. Chiara, M. Cretich, S. Riva, M. Casali, Electrophoesis (2001), 22, 699-706. The solvents used in this case must then be removed by complex distillation.

DE 1 048 574 teaches the reaction of gluconolactone with aminoalkyl vinyl ethers to give the corresponding amides.

The targeted chemical synthesis of unsaturated acylamidoalkyl polyhydroxy acid amides is difficult because of the high functionality of the sugar residues.

The object of the invention was to develop a process for the preparation of unsaturated acylamidoalkylpolyhydroxysäureamiden which avoids the above-described disadvantages of the prior art at least partially. The synthesis should, especially in good yield of desired unsaturated acylamidoalkyl-polyhydroxy acid amides selectively, d. H. without formation of multiple amides or multiple esters and thus without the formation of several free-radically polymerizable double bonds in a cost effective manner be feasible. The attachment of the unsaturated carboxylic acid and the polyhydroxy acid lactone should have a high stability to hydrolysis. Furthermore, the production process should have a good space-time yield.

Accordingly, a process for the preparation of unsaturated acylamidoalkyl polyhydroxy acid amides has been found by reacting the reaction product of polyhydroxy acid lactide and aliphatic diamine with the anhydride of a monounsaturated carboxylic acid. Furthermore, new unsaturated Acylamidoalkylpolyhydroxysäureamide found and polymers containing Acylamidoalkylpolyhydroxysäureamidgruppen in einpoly- merisierter form.

Preference is given to a process in which one or more Polyhydroxysäurelactone is reacted with one or more aliphatic diamines in an aqueous medium and the reaction product, preferably without intermediate isolation, with the anhydride of a monounsaturated carboxylic acid.

Schematically, the preparation takes place in two steps: in the first step of the reaction of the Polyhydroxysäurelactons with the aliphatic diamine to the corresponding aminoalkylaldonamide and in the second step of the reaction of the Aminoalkylaldona- mids with the anhydride of a monounsaturated carboxylic acid to the inventive unsaturated Acylamidoalkylpolyhydroxysäureamid. Optionally, an intermediate insulation may be advantageous. However, the two process steps are preferably carried out directly one after the other, ie without intermediate insulation.

Unless otherwise stated, in this application Ci-Cs-alkyl is methyl, ethyl, n- or i-propyl, n-, sec- or tert-butyl, n- or tert-amyl, and n- Hexyl, n-heptyl and n-octyl and the mono- or polysubstituted analogs thereof. C 2 -C 10 -alkylene is preferably ethylene, propylene or 1- or 2-butylene.

The term "polyhydroxy acid lactone" below refers to lactones of saccharides oxidized only on the anomeric carbon from a natural and synthetic source. Such polyhydroxy acid lactones may also be referred to as lactones of aldonic acids. The Polyhydroxysäurelactone can be used individually or in their mixtures.

The saccharides are selectively oxidized only at the anomeric center. Methods for selective oxidation are well known and are described, for example, in J. Lönnegren, I.J. Goldstein, Methods Enzymology, 242 (1994) 116. Thus, one can perform the oxidation with iodine in an alkaline medium or with copper (II) salts.

The saccharides used to prepare the polyhydroxy acid lactones are open-chain and cyclic mono- or oligosaccharides of natural or synthetic origin which carry an aldehyde group in their open-chain form. In particular, the saccharides are selected from mono- and oligosaccharides in optically pure form. They are also suitable as a stereoisomer mixture.

Monosaccharides are selected from aldoses, in particular aldo-pentoses and preferably aldo-hexoses. Suitable monosaccharides are, for example, arabinose, Ribose, xylose, mannose, galactose and especially glucose. Since the monosaccharides are reacted in aqueous solution, they are due to Mutarotation in both annular hemiacetal form as well as to some extent in open-chain aldehyde form.

Oligosaccharides are understood as meaning compounds having 2 to 20 repeat units. Preferred oligosaccharides are selected from di-, tri-, tetra-, penta-, and hexa-, hepta-, octa, nono- and decasaccharides, preferably saccharides having 2 to 9 repeat units. The linkage within the chains takes place 1, 4-glycosidic and optionally 1, 6-glycosidic.

Preference is given to using compounds of the general formula (I) as saccharides,

in which n stands for the number 0, 1, 2, 3, 4, 5, 6, 7 or 8. The resulting lactones have the following formula (II)

in which n stands for the number 0, 1, 2, 3, 4, 5, 6, 7 or 8.

The oligosaccharides in which n is an integer from 1 to 8 are particularly preferred. It is possible to use oligosaccharides with a defined number of repeat units. Examples which may be mentioned as oligosaccharides lactose, maltose, isomaltose, maltotriose, maltotetraose and maltopentaose.

Preferably, mixtures of oligosaccharides having different numbers of repeating units are chosen. Such mixtures are obtainable by hydrolysis of a polysaccharide, for example enzymatic hydrolysis of cellulose or starch or acid-catalyzed hydrolysis of cellulose or starch. Plant starch consists of amylose and amylopectin as the main component of the starch. amylose It consists of predominantly unbranched chains of glucose molecules which are 1, 4-glycosidically linked together. Amylopectin consists of branched chains in which, in addition to the 1, 4-glycosidic linkages, there are additional 1, 6-glycosylic linkages leading to branching. Also suitable according to the invention are hydrolysis products of amylopectin as starting compound for the process according to the invention and are included in the definition of oligosaccharides.

Suitable aliphatic diamines according to the invention may be linear, cyclic or branched. Aliphatic diamines in the context of this invention are diamines having two primary or secondary amino groups, preferably having one primary and one further primary or secondary amino group, which are joined together by an aliphatic, preferably saturated divalent radical. The bivalent radical is generally an alkylene radical, preferably having 2 to 10 carbon atoms, which may be interrupted by oxygen atoms and may optionally carry one or two carboxyl groups, hydroxyl groups and / or carboxamide groups. Furthermore, aliphatic diamines are also understood as meaning cycloaliphatic diamines.

Suitable aliphatic diamines according to the invention which are substituted by hydroxyl, carboxyl or carboxamide are, for example, N- (2-aminoethyl) -ethanolamine, 2,4-diaminobutyric acid or lysine.

The aliphatic diamines which are suitable according to the invention and whose alkylene radical is interrupted by oxygen are preferably .alpha.,. Omega.-polyetherdiamines in which the two amino groups are at the chain ends of the polyether. Polyether diamines are preferably the polyethers of ethylene oxide, propylene oxide and tetrahydrofuran. The molecular weights of the polyetherdiamines are in the range from 200 to 3000 g / mol, preferably in the range from 230 to 2000 g / mol.

Aliphatic C 2 -C 8 -diynes and cycloaliphatic diamines are preferably used, such as 1, 2-diaminoethane, 1, 3-diaminopropane, 1, 5-diaminopentane, 1, 6-diaminohexane, N-methyl-1, 3 diaminopropane, N-methyl-1, 2-diaminoethane, 2,2, dimethyl propan-1, 3-diamine, diamino-cyclohexane, isophoronediamine and 4,4 ^{'-Diaminodicyclo-} hexyl-methane.

The anhydrides of a monounsaturated carboxylic acid used according to the invention are preferably selected from the anhydrides of C 1 -C 6 -alkyl-substituted acrylic acid, in particular acrylic anhydride, methacrylic anhydride, itaconic acid anhydride and maleic anhydride.

The reaction of Polyhydroxysäurelacton with aliphatic diamine is usually carried out in an organic solvent or solvent mixture or in a mixture of at least one organic solvent with water. Suitable organic niche solvents are those which are at least limited with water, in particular completely miscible at 20 ⁰ C. This is understood miscibility of at least 10 vol% solvent, in particular at least 50 vol% solvent Examples which in water at 20 ⁰ C. Ci-C3-alcohols, for example methanol, ethanol, propanol, Isoproanol, ketones such as acetone, methyl ethyl ketone, mono-, Oligo- or Polyalkylenglyko- Ie or thioglycols having C2-C6-alkylene units, such as ethylene glycol, 1, 2 or 1, 3-propylene glycol, 1, 2 or 1, 4-butylene glycol, Ci-C4-alkyl ethers of polyhydric Alcohols, such as ethylene glycol monomethyl or monoethyl ether, diethylene glycol monomethyl or monoethyl ether, diethylene glycol monobutyl ether (butyl diglycol) or triethylene glycol monomethyl or monoethyl ether, C 1 -C 4 -alkyl esters of polyhydric alcohols, γ-butyrolactone or dimethyl sulfoxide or tetrahydrofuran. Preference is given to mixtures of the organic solvents with water, it being possible for the water content to be up to 95% by weight. A water content of 5-60% by weight is preferred.

The reaction of the diamines with the lactones is described in H.U. Geyer, Chem. Ber. 1964, 2271 described. The molar ratio of aliphatic diamine to Polyhydroxysäurelacton can vary within a wide range, such as. B. in the ratio 5: 1 to 0.3: 1, in particular 3: 1 to 0.4: 1, vary. Preferably, the aliphatic diamine is added to the polyhydroxy acid lactone in a molar ratio of about 2: 1 to 0.5: 1.

The inventive reaction of the diamines with the lactones is carried out in a Temperaturbereicht of -5 ° C to 50 ⁰ C preferably in a temperature range from 0 ° C to 25 ° C. The reaction time is in the range of 2 to 30 hours, preferably in the range of 5 to 25 hours.

The diamine which may be excessively present in the reaction of the diamines with the lactones may be removed from the reaction mixture in a suitable manner after the reaction. Molecular sieves (pore size for example in the range of about 3-10 Angstroms) or a separation by distillation or a separation by extraction with solvents or a separation with the aid of suitable semipermeable membranes are suitable for this purpose.

According to the invention, the molar ratio of anhydride to Aminoalkylaldonamid vary, for. B. in the ratio 1: 0.8 to 1: 1, 2. The anhydride is preferably used in an approximately equimolar amount to the aminoalkylaldonamide.

The reaction according to the invention of the aminoalkylaldonamide with the anhydride of a monounsaturated carboxylic acid is carried out in the abovementioned organic solvents or solvent mixtures or the mixture of at least one organic solvent with water. Preferably, both reaction steps are in one and the same solvent / mixture or the mixture of the solvent with water, in particular without intermediate isolation of the reaction product.

The inventive reaction of the Aminoalkylaldonamids with the anhydride of a monounsaturated carboxylic acid is carried out in a temperature range of -5 ° C to 50 ⁰ C preferably in a temperature range from 5 ° C to 25 ° C. The reaction time is in the range of 2 to 10 hours, preferably in the range of 3 to 5 hours.

In the reaction procedure according to the invention, additional stabilizer may be added to the reaction mixture beyond the storage stabilizer which is present in the anhydride compound, for example hydroquinone monomethyl ether, phenothiazine, phenols, such as 2-tert-butyl-4-methylphenol, 6-tert-butyl 2,4-dimethyl-phenol or N-oxyls such as 4-hydroxy-2,2,6,6-tetramethyl-piperidine-N-oxyl, 4-oxo-2,2,6,6-tetramethyl-piperidine-N oxyl or Uvinul ^® 4040P from BASF Aktiengesellschaft or amines such as BPD Kerobit ^® from BASF Aktiengesellschaft (N, N'-di-sec-butyl-p-phe nylendiamin), for example in quantities of 50 to 2000 ppm.

Advantageously, the reaction is carried out in the presence of an oxygen-containing gas, preferably air or air-nitrogen mixtures.

The stabilizer (mixture) is preferably used as the aqueous solution.

The acid which may be obtained from the acid anhydride during amide formation, for example in the case of acrylic anhydride or methacrylic anhydride, the acrylic acid or methacrylic acid, can be removed from the reaction mixture in a suitable manner after the reaction. Molecular sieves (pore size, for example, in the range of about 3-10 angstroms) or a separation by distillation or with the aid of suitable semipermeable membranes are suitable for this purpose. However, it is advantageous to use them directly as a comonomer for polymerization.

The inventive method is characterized by a simple and inexpensive reaction. In this way, elaborate isolation methods can be avoided before further implementation. Rather, it is possible to use the resulting reaction mixture directly for further polymerization.

Another object of the invention are novel unsaturated Acylamidoalkyl- polyhydroxysäureamide, which are obtainable by reacting the reaction product of Polyhydroxysäurelacton and aliphatic diamine with the anhydride of a monounsaturated carboxylic acid. The new unsaturated Acylamidoalkylpolyhydroxysäureamide obey the general formula III

Oz-N-Y-N FT

R 'FT in the

Z is the radical of a saccharide oxidized to the acid at the anomeric carbon, the bond of which is via the carbonyl function

R ¹ and R ² independently of one another are hydrogen or C 1 -C ₄ -alkyl or C 1 -C ₄ -hydroxyalkyl, in particular hydrogen or methyl R ^{3 is} a vinyl radical which is unsubstituted or substituted by C 1 -C 6 -alkyl or carboxyl Allyl radical which is optionally substituted by carboxyl, in particular vinyl or 2-propen-2-yl and

Y is C 2 -C 10 -alkylene, which may optionally be interrupted by oxygen in ether function and / or may be substituted by one or two carboxyl, hydroxyl and / or carboxamide groups, or a cycloaliphatic radical.

Z is preferably a radical of the general formula IV

in which n stands for the number 0, 1, 2, 3, 4, 5, 6, 7 or 8.

In particular, Z is a residue derived from aldo-hexoses, preferably arabinose, ribose, xylose, mannose, galactose and, in particular, glucose.

In particular, Z is a radical derived from oligosaccharides such as lactose, maltose, isomaltose, maltotriose, maltotetraose and maltopentaose.

In particular, Z is a derived radical from a saccharide mixture obtainable by hydrolysis of a polysaccharide, such as hydrolysis of cellulose or starch.

A further subject of the invention relates to a process for the preparation of polymers which comprise copolymerized acylamidoalkyl-polyhydroxysäureamidgruppen, comprising providing a prepared by the process according to the invention made unsaturated Acylamidoalkylpolyhydroxysäureamids and the subsequent free radical polymerization of the unsaturated Acylamidoalkyl-polyhydroxysäureamid optionally together with them copolymerizable monomers. According to the process for the preparation of polymers comprising acylamidoalkyl-polyhydroxy acid amide groups, at least one reaction product of polyhydroxy acid lactone and aliphatic diamine is reacted with the anhydride of a monounsaturated carboxylic acid, optionally separating off the unsaturated acylamidoalkyl polyhydroxy acid amide and optionally polymerizing the reaction product after addition of comonomers radically. The reaction product of reaction of the aminoalkylaldonamide and anhydride of a monounsaturated carboxylic acid is preferably used directly for the polymerization, if appropriate after addition of monomers copolymerizable with them.

Other suitable comonomers are: other unsaturated acylamidoalkylpolyhydroxysamides prepared according to the invention or polymerizable non-sugar monomers such as (meth) acrylic acid, maleic acid, itaconic acid, their alkali metal or ammonium salts and their esters, O-vinyl esters of C 1 -C 25 -carboxylic acids , N-vinylamides of C1-C25 carboxylic acids, N-vinylpyrroloidone, N-vinylcaprolactam, N-vinyl oxazolidone, N-vinylimidazole, (meth) acrylamide, (meth) acrylonitrile, ethylene, propylene, butylene, butadiene, styrene. Examples of suitable C 1 -C 25 -carboxylic acids are saturated acids, such as formic, acetic, propionic and n- and i-butyric acid, n- and i-valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, undecanoic acid, Lauric acid, tridecanoic acid, myristic acid, pentadecanoic acid, palmitic acid, margaric acid, stearic acid, nonadecanoic acid, arachidic acid, behenic acid, lignoceric acid, cerotic acid and melissic acid.

The preparation of such polymers is carried out, for example, in analogy to the methods generally described in "Ullmann's Encyclopedia of Industrial Chemistry, Sixth Edition, 2000, Electronic Release, keyword: Polymerization Process". Preferably, the (co) polymerization takes place as free-radical polymerization in the form of solution, suspension, precipitation or emulsion polymerization or by bulk polymerization, ie. H. without solvent.

The invention will now be explained in more detail with reference to the following examples.

Example 1 Methacylamidoethylgluconamide

150.1 g (0.630 mol) of 1-amino-2-D-gluconoylaminoethane (prepared according to: HU Geyer, Chem. Ber. 1964, 2271) and 1.45 g of hydroquinone monomethyl ether were dissolved in a mixture of 1080 g of methanol and 120 g of water solved. The mixture was cooled to 5 ° C and slowly added 97.15g (0.630 mol) of methacrylic anhydride. After finished The mixture was allowed to warm for 1 h, the mixture to a temperature of 20 ⁰ C and stirred at 20 ⁰ C for 2 hours on. The product was obtained in the form of a colorless suspension.

The chemical constitution of the product was determined by 1 H-NMR and 13 C-NMR spectroscopy. It was a mixture of methacylamidoethylgluconamide and methacrylic acid in a molar ratio of 1: 1.

Example 2

N-gluconyl-aminoethly-maleic acid amide

400.0 g (1.68 mol) of i-amino-2-D-gluconoylaminoethane (prepared according to: HU Geyer, Chem. Ber. 1964, 2271) were dissolved in 404 g of water and adjusted to a pH of 6 by addition of sulfuric acid , 5 set. 164.7 g (1.68 mol) of maleic anhydride was dissolved in 384.4 g of acetone and then slowly added dropwise to the aqueous solution of 1-amino-2-D-gluconoylaminoethane. By adding sodium hydroxide while the pH was maintained at 6.5. After the addition was stirred at 20 ° C for 2 hours. It formed two liquid phases. The lower phase was separated. In vacuo at 40-45 ⁰ C acetone and water was distilled off. 764 g of product were obtained in the form of a highly viscous liquid.

The chemical constitution of the product was determined by 1 H-NMR and 13 C-NMR spectroscopy.

Example 3 N-Gluconyl-3- (N-methyl) aminopropylmethacrylamide

73.95 g (0.839 mol) of 3-methylaminopropylamine were dissolved in a mixture of 1440 g of methanol and 160 g of water. The mixture was cooled to 0 ⁰ C and slowly added under stirring at 0 ⁰ C 149.46g (0.839 mol) of gluconolactone to. After complete addition, the mixture was stirred at 0 ° -5 ° C for 5h. The mixture was then stirred at 20 ⁰ C for 17 h. Then, 1.45 g of hydroquinone monomethyl ether were added and cooled to 5 ° C. Then, while stirring at 5 ° C., 129.40 g (0.90 mol) of methacrylic anhydride were added slowly. After complete addition, the mixture was allowed to warm for 1 h, the mixture to a temperature of 20 ⁰ C and stirred at 20 ° C for 3 h on. The water and methanol were distilled off in vacuo at 40 ° C. The residue obtained the desired product, which still contained a small amount of methacrylic acid. The chemical constitution of the product was determined by 1 H-NMR and 13 C-NMR spectroscopy.

Claims

claims

1. A process for the preparation of unsaturated acylamidoalkyl-polyhydroxy acid amides, characterized in that reacting the reaction product of polyhydroxysäurelacton and aliphatic diamine with the anhydride of a monounsaturated carboxylic acid.

A process for the preparation of unsaturated Acylamidoalkylpolyhydroxysäure- amides by reacting Polyhydroxysäurelacton with aliphatic diamine in an aqueous medium and reacting the reaction product with the anhydride of a monounsaturated carboxylic acid.

Process for the preparation of unsaturated acylamidoalkyl-polyhydroxyacids according to Claim 1 or 2, characterized in that the polyhydroxyacid lactone is the lactone of a saccharide oxidized only at the anomeric center.

4. A process for the preparation of unsaturated acylamidoalkyl polyhydroxysäure- amides according to any one of claims 1 to 3, characterized in that the Polyhydroxysäurelacton is a lactone of gluconic acid.

5. A process for the preparation of unsaturated acylamidoalkyl-polyhydroxysäure- amides according to claim 3, characterized in that the saccharide is an oligosaccharide.

6. A process for preparing unsaturated acylamidoalkyl-polyhydroxy-acid amides according to any one of claims 1 to 4, characterized in that the Polyhydroxysäurelacton is a compound of formula II,

in which n stands for the number 0, 1, 2, 3, 4, 5, 6, 7 or 8.

7. A process for the preparation of unsaturated acylamidoalkyl-polyhydroxy acid amides according to claim 3, characterized in that the saccharide Hydrolysis of a polysaccharide and subsequent oxidation of the hydrolysis product was obtained.

8. A process for the preparation of unsaturated acylamidoalkyl polyhydroxysäure- amides according to claim 3, characterized in that the saccharide

Hydrolysis of cellulose or starch and subsequent oxidation of the hydrolysis product was obtained.

9. A process for the preparation of unsaturated acylamidoalkyl polyhydroxysäure- amides according to any one of claims 1 to 8, characterized in that the

Anhydride of the monounsaturated carboxylic acid is selected from acrylic acid anhydride, methacrylic anhydride, itaconic anhydride or maleic anhydride.

10. Unsaturated Acylamidoalkyl polyhydroxysäureamide obtainable by reacting the reaction product of Polyhydroxysäurelacton and aliphatic diamine with the anhydride of a monounsaturated carboxylic acid.

1 1. Unsaturated acylamidoalkyl-polyhydroxysäureamide, which obey the general formula III,

Oz-N-Y-N- "- R

I ₁ I ₂

R R in the

Z is oxidized to the acid for the remainder of an anomeric carbon

Saccharide, whose bonding takes place via the carbonyl function, R ¹ and R ² independently of one another represent hydrogen or C 1 -C ₄ -alkyl or

C ¹ -C 4 -hydroxyalkyl, R ^{3 is} a vinyl radical which is optionally substituted by C 1 -C 6 -alkyl or

Is carboxyl or is an allyl radical which is optionally substituted by carboxyl and Y is C 2 -C 10 -alkylene which may optionally be interrupted by oxygen in ether function and / or by one or two carboxyls,

Hydroxyl and / or carboxamide groups may be substituted, or is a cycloaliphatic radical.

12. A process for the preparation of polymers containing copolymerized acylamidoalkyl polyhydroxysäure- amide groups, comprising providing an unsaturated Acylamidoalkyl-polyhydroxysäureamids by a process of claims 1 to 9 and the subsequent free radical polymerization of the unsaturated Acylamidoalkyl-polyhydroxysäureamid optionally together with them copolymerizable monomers.