EP1183298A1 - Polymeres reticules contenant des acides amines basiques condenses, et procede de preparation - Google Patents

Polymeres reticules contenant des acides amines basiques condenses, et procede de preparation

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Publication number
EP1183298A1
EP1183298A1 EP00931198A EP00931198A EP1183298A1 EP 1183298 A1 EP1183298 A1 EP 1183298A1 EP 00931198 A EP00931198 A EP 00931198A EP 00931198 A EP00931198 A EP 00931198A EP 1183298 A1 EP1183298 A1 EP 1183298A1
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EP
European Patent Office
Prior art keywords
acid
basic amino
amino acids
condensed
polymers
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Application number
EP00931198A
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German (de)
English (en)
Inventor
Bernhard Mohr
Dietrich Fehringer
Dieter Boeckh
Jürgen DECKER
Ralf NÖRENBERG
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BASF SE
Original Assignee
BASF SE
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Publication date
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Publication of EP1183298A1 publication Critical patent/EP1183298A1/fr
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3719—Polyamides or polyimides
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/26—Treatment of water, waste water, or sewage by extraction
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
    • C08G69/08—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino-carboxylic acids
    • C08G69/10—Alpha-amino-carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/48—Polymers modified by chemical after-treatment
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K47/00—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient
    • A61K47/30—Macromolecular organic or inorganic compounds, e.g. inorganic polyphosphates
    • A61K47/34—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polyesters, polyamino acids, polysiloxanes, polyphosphazines, copolymers of polyalkylene glycol or poloxamers
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/20—Heavy metals or heavy metal compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds

Definitions

  • the present invention relates to crosslinked, condensed basic amino acid-containing polymers and a process for their preparation.
  • US Pat. No. 5,028,689 relates to thermoplastic, easily branched aliphatic copolyamides of high molecular weight with increased melt viscosities.
  • the copolyamides are prepared by polycondensation of a monomer mixture of one or more actams, aminocarboxylic acids, diamine / dicarboxylic acid mixtures or mixtures thereof in the presence of small amounts of, for example, lysine or a lysine ester of a lower alcohol and one of the free amino groups of the lysine or lysine ester equivalent amount of a polycarboxylic acid.
  • the amount of lysine used leads to copolyamides which contain 0.1 to 1.0% by weight of lysine segments.
  • the combination of lysine and polycarboxylic acids added to the monomer mixture before the start of the reaction without prior salt formation drastically accelerates polyamide formation.
  • thermoplastically deformable, high molecular weight polyamides are produced by polycondensation of mixtures of polyamide-forming, aliphatic diamines and dicarboxylic acids in the presence of small amounts of ⁇ -amino- ⁇ -caprolactam
  • predominantly aliphatic polyamides are produced by hydrolytic polymerization at least one polyamide-forming lactam in the presence of 0.1 to 2 wt .-% ⁇ -amino- ⁇ -caprolactam and an equivalent amount of polycarboxylic acid.
  • These polyamides are used to make films and fibers.
  • US Pat. No. 3,651,023 relates to a polyamide composition which can be obtained by polymerizing caprolactam in the presence of, for example, lysine in an amount such that the polymer contains 0.5 to 5% by weight of lysine. Fibers and yarns are made from these polymers.
  • US Pat. No. 4,126,628 relates to a process for the monoacylation of diamino acids, such as, for example, lysine, ornithine and ⁇ , ⁇ -diaminobutyric acid, by reacting these acids with succinimidyl esters of carboxylic acids or substituted carbonic acids in approximately equimolar amounts at 25 to 50 ° C. in the presence of a basic catalyst which gives a pH of at least about 10.
  • the N-acylamino acid products are suitable for use as surfactants, pharmaceuticals or intermediates for pharmaceuticals.
  • U.S. Patent Application Serial No. 09 / 131,234 relates to an amino acid-based polymer, oligomer or copolymer with at least 5 mol units of a basic amino acid from the group consisting of lysine, arginine, ornithine, tryptophan and mixtures thereof and at least about 5 mol% of a polymerizable compound from the Group consisting of aliphatic or cycloaliphatic amines, alicyclic amines, diamines, triamines, tetraamines, aliphatic amino alcohols or mixtures thereof.
  • These polymers, oligomers or copolymers are produced by condensation of the basic amino acids at a temperature of at least 120 ° C. with at least one of the polymerizable compounds.
  • the condensation products can be used as additives for detergents and / or other detergent additives.
  • U.S. Patent Application Serial No. 09 / 131,282 relates to condensation products of basic amino acids with copolymerizable compounds which are obtained by condensation of
  • Carboxylic anhydrides diketenes, monohydroxycarboxylic acids, polyhydroxycarboxylic acids and their mixtures and optionally
  • Amines, lactams, non-proteinogenic amino acids, alcohols, alkoxylated alcohols, alkoxylated amines, amino sugars, carbohydrates and sugar carboxylic acids are available in a molar ratio of (a): (b) from 100: 1 to 1: 1 at a temperature of at least 120 ° C.
  • the condensation products can be used as an additive in detergents.
  • the invention has for its object to provide new condensation products of basic amino acids.
  • Cocondensates from basic amino acids and cocondensable compounds with
  • the object is also achieved with a process for the preparation of crosslinked polymers containing basic amino acids, in which
  • Cocondensates of mixtures of two or more basic amino acids are provided.
  • Polymers containing basic amino acids are preferably produced by thermal condensation of basic amino acids alone or together with cocondensable compounds.
  • Other methods of making basic amino acids containing polymers are based on chemical methods (eg via N-carboxylic acid anhydrides of the basic amino acids) or on microorganisms.
  • Basic amino acids which are referred to below as compounds of group (a), are, for example, lysine, arginine, ornithine, tryptophan and mixtures thereof. These compounds can be used in the form of their hydrates, their esters with lower alcohols or their salts, for example their sulfates, hydrochlorides or acetates.
  • esters of the basic amino acids are preferably derived from monohydric Cl to C4 alcohols, such as, for example, methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol or tert. -Butanol.
  • hydrochlorides the approach for neutralizing hydrogen chloride should be mixed with approximately equivalent amounts of a base.
  • Potassium hydroxide preferred.
  • a monohydrochloride of a basic amino acid one equivalent of a base is required, whereas in the case of dihydrochlorides two equivalents are required.
  • Lysine hydrate and aqueous lysine solutions are preferably used as the basic amino acid. Lysine can also be used in the form of its cyclic lactam, i.e. Use ⁇ -amino- ⁇ -caprolactam.
  • Compounds which can be co-condensed with basic amino acids and which are referred to below as compounds of group (b) are, for example, compounds having at least one carboxyl group, carboxylic anhydrides, diketenes, amines, lactams, alcohols, alkoxylated alcohols and alkoxylated amines.
  • Examples of compounds containing carboxyl groups are saturated monobasic carboxylic acids, unsaturated monobasic carboxylic acids, polybasic carboxylic acids, monohydroxycarboxylic acids, monobasic polyhydroxycarboxylic acids, non-proteinogenic amino acids and mixtures thereof.
  • saturated monobasic carboxylic acids are formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, octanoic acid, nonanoic acid, decanoic acid, lauric acid, palmitic acid, stearic acid, arachidic acid, behenic acid, myristic acid, undecanoic acid, 2-ethylhexanoic acid and all naturally occurring mixtures of these.
  • Acrylic acid methacrylic acid, crotonic acid, sorbic acid, oleic acid, linoleic acid and erucic acid.
  • polybasic carboxylic acids are oxalic acid, fumaric acid, maleic acid, malonic acid, succinic acid, itaconic acid, adipic acid, aconitic acid, suberic acid, azelaic acid, pyridinedicarboxylic acid, furanedicarboxylic acid, phthalic acid, Terephthalic acid, diglycolic acid, glutaric acid, substituted C4-dicarboxylic acid, sulfosuccinic acid, Cl to C26 alkyl succinic acids, C2 to C26 alkenyl succinic acids, 1,2, 3-propane tricarboxylic acids, 1,1,3, 3-propane tetracarboxylic acids, 1, 1, 2 , 2-ethanetetracarboxylic acid, 1, 2, 3, 4-butanetetracarboxylic acid, 1,2,2, 3-propanetetracarboxylic acid, 1,3,3, 5-pentanetetracarboxylic acid, 1, 2, 4-
  • Examples of monohydroxycarboxylic acids are malic acid, tartronic acid, citric acid and isocitric acid.
  • Examples of polyhydroxycarboxylic acids are tartaric acid, mucic acid, glyceric acid, bis (hydroxymethyl) propionic acid, gluconic acid and hydroxylated unsaturated fatty acids such as e.g. Dihydroxystearic acid.
  • Other compounds containing carboxyl groups are non-proteinogenic amino acids.
  • examples include anthranilic acid, N-methylamino-substituted acids such as N-methylglycine, dirnethylaminoacetic acid, ethanolaminoacetic acid, N-carboxymethylamino acids, nitrilotriacetic acid,
  • Ethylenediamine acetic acid ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid,
  • Hydroxyethylenediaminotriacetic acid diamino succinic acid, C4 to C26 aminoalkyl carboxylic acids, e.g. 4-aminobutyric acid, 6-aminocaproic acid and 11-aminoundecanoic acid.
  • carboxyl-containing compounds which differ from basic amino acids and ⁇ -amino acids and which can be condensed with basic amino acids are sugar carboxylic acids, such as e.g. Gluconic acid, glucaric acid, gluconolactone and glucuronic acid.
  • carboxylic anhydrides for example succinic anhydride, butane tetracarboxylic acid monoanhydride and dianhydride, phthalic anhydride, acetylci ronic acid anhydride, maleic anhydride, itaconic anhydride and aconitic acid anhydride.
  • diketenes which can be considered as a co-condensable compound are alkyldiketenes with 1 to 30
  • Compounds of the above formula are, for example, diketene, methyldiketene, hexyldiketene, cyclohexyldiketene, octyldiketene, decyldiketene, dodecyldiketene, palmityldiketene, stearyldiketene, oleyldiketene, octadecyldiketene, eicosyldiketene, docosyldiketene and behenyldiketene.
  • amines are: aliphatic and cycloaliphatic amines, preferably methyl amine, ethyl amine, propyl amine, butyl amine, pentyl amine, hexyl amine, heptyl amine, octyl amine, nonyl amine, decyl amine, undecyl amine, dodecyl amine, tridecyl amine, stearyl amine, palmityl amine, 2-ethyliminohexyl amine, isamonamino hexyl amine, isamonamylhexyl amine, isamonamylhexyl amine, isamonaminohexyl amine, isamonamylhexyl amine, isamonamyllaxin amine Dimethylamine, diethylamine, dipropylamine, dibutylamine,
  • Diamines, triamines and tetraamines preferably ethylenediamine, propylenediamine, butylenediamine, neopentyldiamin, hexamethylenediamine, octamethylenediamine, imidazole, 5-amino-1, 3-trimethylcyclohexylmethylamine, diethylenetriamine, dipropylenetriamine, tripropyltetraamine,
  • N- (aminopropyl) imidazole N- (aminoethyl) hexamethylene diamine
  • aliphatic amino alcohols preferably 2-aminoethanol
  • Aminosugars such as Chitosan or chitosamine and compounds which can be obtained by reducing carbohydrates by means of reductive amination, such as Aminosorbitol or glucose amine, and other amino group-containing compounds such as Melamine, urea, guanidine, polyguanides, piperidine, morpholine, 2, 6-dimethylmorpholine and tryptamine.
  • Preferred amines are selected from hexamethylene diamine, octylamine, monoethanolamine, octamethylene diamine, diaminododecane, decylamine, dodecylamine and mixtures thereof.
  • Lactams are further compounds that can be condensed with basic amino acids.
  • the lactams contain 5 to 13 atoms in the ring.
  • Suitable lactams include Butyrolactam, caprolactam and laurolactam.
  • Alcohols can be derived from monohydric alcohols, for example from primary, secondary or tertiary alcohols having 1 to 22 carbon atoms, for example methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, tert. -Butanol, pentanol, hexanol, 2-ethylhexanol, cyclohexanol, octanol, decanol, dodecanol, palmityl alcohol, stearyl alcohol and behenyl alcohol.
  • monohydric alcohols for example from primary, secondary or tertiary alcohols having 1 to 22 carbon atoms, for example methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, tert.
  • -Butanol pentanol, hexanol, 2-ethyl
  • alcohols are also suitable as alcohols, such as, for example, ethylene glycol, propylene glycol, glycerol, polyglycerols with 2 to 8 glycerol units, erythritol, pentaerythritol and sorbitol.
  • polyols such as, for example, ethylene glycol, propylene glycol, glycerol, polyglycerols with 2 to 8 glycerol units, erythritol, pentaerythritol and sorbitol.
  • co-condensable compounds are carbohydrates such as glucose, sucrose, dextrins, starch and degraded starch and maltose.
  • the alcohols can also be alkoxylated. Examples of such compounds are the addition products of 1 to 200 moles of a C - to C 4 -alkylene oxide to one mole of the alcohol mentioned. Examples of suitable alkylene oxides are ethylene oxide, propylene oxide and butylene oxides. Ethylene oxide and propylene oxide are preferably used or ethylene oxide and propylene oxide are added to the alcohol in this or the reverse order. Of particular interest are the addition products of 3 to 20 moles of ethylene oxide with 1 mole of a C 3 / Ci 5 oxo alcohol or with fatty alcohols.
  • the alcohols can optionally also contain a double bond, such as oleyl alcohol.
  • the basic amino acids can also be condensed with alkoxylated amines, for example with the addition products of 5 to 30 moles of ethylene oxide with 1 mole of stearylamine, oleylamine or palmitylamine.
  • the crosslinked, condensed, amino acid-containing polymers of the compounds of groups (a) and (b) contain them, for example, in a molar ratio of 100: 1 to 1:10 and preferably in a molar ratio of (a) to (b) of more than 1, for example more than 1.5 and preferably more than 2. If compounds (b) contain at least two different functional groups, a molar ratio (a): (b) of 1: 1 to 1:10 is preferably used. Examples of such compounds (b) are non-proteinogenic amino acids, lactams, amino alcohols, hydroxycarboxylic acids and amino sugars.
  • condensation products which are used as the starting material for the production of the crosslinked polymers containing condensed basic amino acids are homocondensates of basic amino acids and cocondensates which are obtained by condensation of
  • the condensation is advantageously carried out in water at a concentration of the compounds to be condensed of 10 to 98% by weight at a temperature of 120 ° to 300 ° C. According to a preferred embodiment of the
  • the condensation is carried out in water at a concentration of the compounds to be condensed of 20 to 70% by weight under pressure at a temperature of 140 ° to 250 ° C.
  • the condensation of these compounds can also be carried out in an organic solvent, e.g. Dimethylformamide,
  • dimethyl sulfoxide dimethylacetamide
  • glycol polyethylene glycol, propylene glycol, polypropylene glycol, monohydric alcohols, addition products of ethylene oxide and / or propylene oxide with monohydric alcohols, with amines or with carboxylic acids.
  • monohydric alcohols addition products of ethylene oxide and / or propylene oxide with monohydric alcohols, with amines or with carboxylic acids.
  • the condensation can be started, for example, in the presence of water either in an aqueous solution or in a water-containing organic solvent.
  • 35 compounds can then be continued in the presence of water.
  • the water can be distilled off before the compounds are condensed.
  • the condensation can also be carried out with removal of water which is formed during the condensation. This is preferably the case with condensation
  • the condensation time depends on the choice of reaction conditions and is generally in the range from 1 minute to 50 hours, preferably from 30 minutes to
  • Low molecular weight polycondensates can also be produced in a pressure-tightly closed container by at most partially removing the water formed in the course of the polycondensation.
  • condensation can also be carried out in the presence of a mineral acid as catalyst.
  • Mineral acid concentration can be 0.001 to 5, preferably 0.01 to 1.0% by weight.
  • suitable mineral acids are hypophosphorous acid, hypodiphosphoric acid, phosphorous acid, hydrochloric acid, sulfuric acid and mixtures thereof.
  • their alkali, ammonium and alkaline earth metal salts can also be used as catalysts.
  • condensation products from used as starting materials for the production of the crosslinked, condensed polymers containing basic amino acids are used as starting materials for the production of the crosslinked, condensed polymers containing basic amino acids
  • Cocondensates of basic amino acids and cocondensable compounds are cocondensates of basic amino acids and cocondensable compounds
  • the amino groups of the starting material can be present as free amine or in the form of their ammonium salts which can be obtained by partial or complete neutralization with a mineral acid, e.g. Hydrochloric acid, phosphoric acid or sulfuric acid, or with an organic acid such as e.g. Methanesulfonic acid, acetic acid, formic acid, propionic acid or citric acid are available.
  • a mineral acid e.g. Hydrochloric acid, phosphoric acid or sulfuric acid
  • an organic acid such as e.g. Methanesulfonic acid, acetic acid, formic acid, propionic acid or citric acid are available.
  • the condensed compounds (i) containing basic amino acids e.g.
  • Cocondensates of basic amino acids and cocondensable compounds are cocondensates of basic amino acids and cocondensable compounds
  • crosslinkers with at least two functional groups are modified by reaction with (ii) crosslinkers with at least two functional groups.
  • Suitable crosslinkers with at least two functional groups are, for example, ⁇ -, ⁇ -dichloroalkanes or vicinal dichloroalkanes, such as 1, 2-dichloroethane, 1, 2-dichloropropane, 1, 3-dichloropropane, 1, -dichlorobutane and 1, 6-dichlorohexane.
  • crosslinkers are glycidyl halides, such as epichlorohydrin, bischlorohydrin ethers of polyols, polychlorohydrin ethers of polyols, bischlorohydrin ethers of polyalkylene glycols, chloroformic acid esters, phosgene and in particular halogen-free crosslinkers.
  • glycidyl halides such as epichlorohydrin, bischlorohydrin ethers of polyols, polychlorohydrin ethers of polyols, bischlorohydrin ethers of polyalkylene glycols, chloroformic acid esters, phosgene and in particular halogen-free crosslinkers.
  • Epichlorohydrin is preferably used as the crosslinking agent
  • diepoxides such as e.g. Hexamethylene diisocyanate, and polyisocyanates
  • crosslinkers of group (1) propylene carbonate is preferably used.
  • suitable halogen-free crosslinkers of group (2) are monoethylenically unsaturated monocarboxylic acids, such as, for example, acrylic acid, methacrylic acid and crotonic acid, and the amides, esters and anhydrides derived therefrom.
  • the esters can be derived from alcohols having 1 to 22, preferably 1 to 18, carbon atoms.
  • the amides are preferably unsubstituted, but can carry a C 1 -C 22 -alkyl radical as a substituent.
  • Halogen-free crosslinkers of group (2) are furthermore at least dibasic saturated carboxylic acids, e.g.
  • Dicarboxylic acids and the salts, diesters and diamides derived therefrom. These compounds can be used, for example, using the formula
  • R Ci to C 22 alkyl
  • R 1 H
  • n 0 to 22.
  • dicarboxylic acids of the formula I monoethylenically unsaturated dicarboxylic acids such as, for example, maleic acid or itaconic acid are suitable.
  • the esters of the dicarboxylic acids in question are preferably derived from alcohols having 1 to 4 carbon atoms.
  • suitable dicarboxylic acid esters are dimethyl oxalate, diethyl oxalate, diisopropyl oxalate, dimethyl succinate, diethyl succinate, diisopropyl succinate, di-n-propyl succinate, diisobutyl ester and adipate adipate, adipate adipate.
  • Suitable ethers of ethylenically unsaturated dicarboxylic acids are dimethyl maleate, diethyl maleate, diisopropyl maleate, dimethyl itaconate and diisopropyl itaconate.
  • Substituted dicarboxylic acids and their esters such as tartaric acid (D-form, L-form and as a racemate) and tartaric acid esters, such as dimethyl tartaric acid and dietetic tartaric acid, are also suitable.
  • suitable dicarboxylic anhydrides are maleic anhydride, itaconic anhydride and
  • Aziridines are used with the halogen-free crosslinking agents mentioned above to form amide groups or in the case of amides, e.g. Adipic acid diamide, by means of
  • the at least dibasic saturated carboxylic acids include, for example, tricarboxylic acids and tetracarboxylic acids, e.g. Citric acid, propane tricarboxylic acid, ethylenediaminetetraacetic acid and butanetetracarboxylic acid.
  • tricarboxylic acids and tetracarboxylic acids e.g. Citric acid, propane tricarboxylic acid, ethylenediaminetetraacetic acid and butanetetracarboxylic acid.
  • crosslinkers of group (2) are the salts, esters, amides and anhydrides which are derived from the above-mentioned carboxylic acids.
  • crosslinkers of group (2) are polycarboxylic acids which are obtained by polymerizing monoethylenically unsaturated
  • Carboxylic acids or carboxylic anhydrides are available.
  • Suitable monoethylenically unsaturated carboxylic acids are acrylic acid, methacrylic acid, crotonic acid, maleic acid and / or itaconic acid.
  • polyacrylic acids are suitable for use as crosslinkers,
  • Acrylic acid-maleic acid copolymers are Acrylic acid-maleic acid copolymers.
  • crosslinkers (2) are obtained, for example, by polymerizing anhydrides, such as maleic anhydride, in an inert solvent, such as toluene, xylene, ethylbenzene or isopropylbenzene, or solvent mixtures in the presence of free-radical initiators.
  • Peroxyesters such as tert-per-2-ethylhexanoic acid, are preferably used as initiators.
  • -butyl ester are also suitable.
  • copolymers of maleic anhydride and isobutene or copolymers of maleic anhydride and diisobutene are preferred.
  • the copolymers containing anhydride groups can optionally be modified by reaction with C 1 -C 2 -alcohols, ammonia or amines and used in this form as crosslinking agents.
  • the molecular weight M w of the homopolymers and copolymers is, for example, up to 10,000, preferably 500 to 5,000.
  • Polymers of the above type are described, for example, in EP-A-0 276 464, US-A-3 810 834, GB-A-1 411 063 and US-A-4 818 795.
  • Carboxylic acids and the polycarboxylic acids can also be used as crosslinking agents in the form of their alkali metal or ammonium salts.
  • the sodium salts are preferably used here.
  • the polycarboxylic acids can be partially, e.g. up to 10 - 50 mol% or completely neutralized.
  • the compounds of group (2) used are preferably tartaric acid dimethyl ester, tartaric acid diethyl ester, adipic acid dimethyl ester, adipic acid diethyl ester, maleic acid dimethyl ester, maleic acid diethyl ester,
  • maleic anhydride maleic acid, acrylic acid, methyl acrylate, ethyl acrylate, acrylamide and methacrylamide.
  • halogen-free crosslinkers of group (3) are reaction products of polyether diamines, alkylene diamines,
  • the polyether diamines are produced, for example, by reacting polyalkylene glycols with ammonia.
  • the polyalkylene glycols can contain 2 to 50, preferably 2 to 40 alkylene oxide units. These can be, for example, polyethylene glycols, polypropylene glycols, polybutylene glycols or block copolymers of ethylene glycol and propylene glycol, block copolymers of ethylene glycol and butylene glycol or block copolymers of ethylene glycol, propylene glycol and butylene glycol.
  • random copolymers of ethylene oxide and propylene oxide and optionally butylene oxide are suitable for the preparation of the polyether diamines.
  • Polyether diamines are also derived from polytetrahydrofurans which have 2 to 75 tetrahydrofuran units.
  • the polytetrahydrofurans are also converted into the corresponding ⁇ , ⁇ -polyether diamines by reaction with ammonia converted.
  • Polyethylene glycols or block copolymers of ethylene glycol and propylene glycol are preferably used to prepare the polyether diamines.
  • alkylenediamines examples include ethylenediamine, propylenediamine, 1,4-diaminobutane and 1,6-diaminohexane.
  • Suitable polyalkylene polyamines are, for example, diethylenetriamine, triethylenetetramine, dipropylenetriamine, tripropylenetetramine, dihexamethylenetriamine, aminopropylethylenediamine, bis-aminopropylethylenediamine and polyethyleneimines with molar masses of up to 5000.
  • amines described above are reacted with monoethylenically unsaturated amides or the anides thereof or their esters products obtained as functional groups have at least two ethylenically unsaturated double bonds, carboxamide, carboxyl or ester groups.
  • monoethylenically unsaturated amides or the anides thereof or their esters products obtained as functional groups have at least two ethylenically unsaturated double bonds, carboxamide, carboxyl or ester groups.
  • maleic anhydride compounds are obtained which can be characterized, for example, using the formula II:
  • the compounds of formula (II) are obtainable, for example, by reacting alkylene glycols, polyethylene glycols, polyethyleneimines, polypropyleneimines, polytetrahydrofurans, ⁇ , ⁇ -diols or ⁇ , ⁇ -diamines with maleic anhydride or the other monoethylenically unsaturated carboxylic acids or carboxylic acid derivatives mentioned above.
  • the polyethylene glycols suitable for the preparation of the crosslinker II preferably have molar masses from 62 to 10,000, whereas the molar masses of
  • Polyethyleneimines are preferably 129 to 50,000 and the molecular weights of the polypropyleneimines are 171 to 50,000.
  • Suitable alkylene glycols are, for example, ethylene glycol, 1,2-propylene glycol, 1,4-butanediol and 1,6-hexanediol.
  • the ⁇ , ⁇ -diamines preferably used to prepare the crosslinkers of the formula II are ethylenediamine and ⁇ , ⁇ -diamines which are derived from polyethylene glycols or polytetrahydrofurans with molecular weights M w of about 400 to 5000 in each case.
  • crosslinkers of the formula II are reaction products of maleic anhydride with ⁇ , ⁇ -polyether diamines with a molecular weight of 400 to 5000, the reaction products of polyethyleneimines with a molecular weight of 129 to 50,000 with maleic anhydride and the reaction products of ethylenediamine or triethylenetetramine with maleic anhydride in one molar ratio of 1: at least 2.
  • crosslinking agents form
  • Polyether diamines, alkylene diamines and polyalkylene polyamines can also react with maleic anhydride or the ethylenically unsaturated carboxylic acids or their derivatives with addition to the double bond in the sense of a Michael addition.
  • Crosslinking agents of the formula III are then obtained
  • R 1 H or CH 3
  • R 2 H, COOMe, COOR or C0NH 2
  • R 3 OR, NH 2 , OH or OMe
  • crosslinkers of the formula III bring about crosslinking with the amino groups of the polymers formed in the polymerization via their terminal carboxyl or ester groups and with the formation of an amide function.
  • This class of crosslinker systems also includes the reaction products of monoethylenically unsaturated carboxylic acid esters with alkylenediamines and
  • Polyalkylene polyamines For example, the products of addition of ethylene diamine, diethylene triamine, triethylene tetramine, tetraethylene pentamine and polyethyleneimines with molecular weights of, for example, 129 to 50,000 of acrylic esters or methacrylic esters are suitable, with at least 2 moles of acrylic ester or methacrylic ester being used per mole of amine component.
  • the esters of monoethylenically unsaturated carboxylic acids are preferably the C 1 -C 8 -alkyl esters of acrylic acid or methacrylic acid. Methyl acrylate and ethyl acrylate are particularly preferred for the preparation of the crosslinkers.
  • the crosslinkers prepared by Michael addition of polyalkylene polyamines and ethylenically unsaturated carboxylic acids, esters, amides or anhydrides can contain more than two functional groups. The number of these groups depends on the molar ratio in which the reactants are used in the Michael addition. For example, 2 to 10, preferably 2 to 8, mol of ethylenically unsaturated carboxylic acids or their derivatives can be added to one mole of a polyalkylene polyamine having 10 nitrogen atoms using a Michael addition. At least 1 to at most 4 moles of the ethylenically unsaturated carboxylic acids or their derivatives can be added to 1 mole of polyethylenediamines and alkylenediamines using a Michael addition.
  • R 1 represents Ci to C 2 alkyl.
  • the secondary NH groups of the compounds of the formula IV can optionally react in the sense of a Michael addition with acrylic acid, acrylamide or acrylic esters.
  • the crosslinker of group (3) used is preferably the compounds of the formula II which contain at least two carboxylic acid groups and are obtainable by reacting polyether diamines, ethylenediamine or polyalkylene polyamines with maleic anhydride, or Michael addition products which contain at least 2 ester groups and which consist of polyether diamines, Polyalkylene polyamines or ethylenediamine and esters of acrylic or methacrylic acid, each with monohydric alcohols having 1 to 4 carbon atoms, are formed.
  • Reaction products which are prepared by reacting dicarboxylic acid esters which are completely esterified with monohydric alcohols having 1 to 5 carbon atoms with ethyleneimine are suitable for the use of halogen-free crosslinkers of group (4).
  • suitable dicarboxylic acid esters are dimethyl oxalate, diethyl oxalate, dimethyl succinate, diethyl succinate, dimethyl adipate, diethyl adipate and
  • Dimethyl glutarate Dimethyl glutarate.
  • the reaction of diethyl oxalate with ethyleneimine gives bis- [ß- (1-aziridino) ethyl] oxalic acid amide.
  • the dicarboxylic acid esters are reacted with ethyleneimine, for example in a molar ratio of 1 to at least 4.
  • the terminal aziridine groups are the reactive groups.
  • These crosslinkers can be characterized, for example, using the formula V. (V),
  • n 0 to 22.
  • Preferred group (5) compounds are bisglycidyl ethers of
  • Ethylene glycol polyethylene glycol with 2 to 40
  • Ethylene glycol units propylene glycol, polypropylene glycol ethers,
  • Copolymers of ethylene oxide and propylene oxide as well as diisocyanates e.g. Hexamethylene diisocyanate.
  • Crosslinked compounds containing condensed basic amino acids can be obtained by reacting at least one compound from group (i) with at least one compound from group (ii). The reaction can be carried out in bulk, in solution in an inert solvent or in dispersion in an aqueous medium or in an inert solvent. Depending on the degree of crosslinking, water-soluble or water-insoluble crosslinked polymers containing condensed basic amino acids are obtained.
  • a solution of the compounds (i) and (ii) is preferably first prepared in an inert solvent which does not react with the compounds (i) and (ii) under the reaction conditions and then combine the two solutions at once, in small portions, drop by drop or continuously.
  • Preferred inert solvents are ethers which are inert to the compounds of groups (i) and (ii) and are at least liquid under the reaction conditions.
  • ethers are dialkyl ethers with 1 to 6 carbon atoms in the alkyl group, for example diethyl ether, methyl n-propyl ether, methyl isopropyl ether, methyl n-butyl ether, methyl sec. -butyl ether, methyl tert. -butyl ether, ethyl hexyl ether and di-n-butyl ether.
  • end-capped polyalkylene glycols with, for example, 2 to 50 polymerized alkylene oxide units.
  • C 1 -C 4 -alkyl groups are suitable for use as end groups.
  • the end-capped polyalkylene glycols preferably have methyl groups or ethyl groups.
  • the end-capped polyalkylene glycols can be obtained, for example, by alkylating polyalkylene glycols.
  • Suitable polyalkylene glycols are, for example, polyethylene glycols, polypropylene glycols and polybutylene glycols, and block copolymers of ethylene oxide and propylene oxide, ethylene oxide and butylene oxide or ethylene oxide, propylene oxide and butylene oxide, or block copolymers of propylene oxide and butylene oxide.
  • Preferably used as end-capped polyalkylene glycols are glycols from the following group which are end-capped at both ends with methyl groups or ethyl groups: diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol and dibutylene glycol.
  • Suitable ethers are derived from polytetrahydrofuran, which contains 2 to 50 tetrahydrofuran units in the molecule and is end-capped at both ends with C 1 -C 4 -alkyl groups. From this group, preference is given to using ditetrahydrofuran ether or tritetrahydrofuran ether which are end-capped at both ends with methyl groups or ethyl groups.
  • organic solvents preferably used in the process according to the invention are methyl tert-butyl ether,
  • crosslinked compounds containing basic amino acids Tetrahydrofuran, dioxane or mixtures of these solvents.
  • water is the preferred for the crosslinking reaction Inert solvents.
  • compounds (i) can be dissolved or dispersed in water and an aqueous solution of the crosslinking agents (ii) added. Depending on the 5 reaction conditions, particulate, crosslinked polymers or gels containing basic amino acids are obtained.
  • the concentration of the compounds (i) and (ii) in the inert solvents is, for example, 1 to 80,
  • Reaction temperature can range from 15 to 200 ° C, preferably up to 100 ° C. If the reaction temperature is above the boiling point of the solvent used, the reaction is carried out under elevated pressure, for example at pressures up to
  • the response time depends on several different factors
  • the crosslinking reaction can be carried out over a period of between 1 minute and 20 hours, preferably between 10 minutes and 2 hours.
  • crosslinked polymers containing basic amino acids are used, for example, as additives for detergents and / or detergent additives.
  • the water-insoluble crosslinked polymers according to the invention can also be used for
  • compositions can be used.
  • the immobilized active ingredients are used correctly, the active ingredients are released in a controlled manner from combinations of crosslinked polymers containing basic amino acids and the active ingredient.
  • the finely divided, water-insoluble, crosslinked polymers are also suitable as absorbents for the extraction of formaldehyde or other aldehydes and ketones from waste water or waste air. 0 This results in numerous applications; for example, the cross-linked, finely divided polymers can be used in cigarette filters, filters for cleaning waste water or for absorbing formaldehyde in particle boards.
  • the finely divided, crosslinked polymers are also suitable for the absorption of acidic gases, such as sulfur dioxide, sulfur trioxide, hydrogen chloride and carbon dioxide. They also come to removal, for example acidic compounds, such as benzoic acid or p-toluenesulfonic acid, from aqueous solutions.
  • the finely divided, water-insoluble polymers are also suitable for removing heavy metal ions from waste water.
  • the solid / liquid extraction of heavy metals (main group metals, transition metals, lanthanides and actinides) from aqueous solutions or waste water is particularly preferred.
  • Iron ions, zinc ions, copper ions, lead ions, rhodium ions and mercury ions as well as chromium ions, manganese ions, nickel ions, silver ions and cadmium ions are particularly preferably extracted.
  • the weight average molecular weights (Mw) were determined using aqueous gel permeation chromatography (GPC) using a mixture of acetonitrile and water in a volume ratio of 20:80 as the mobile phase, columns with Waters Ultrahydrogel 500, 250, 250 and 120 and UV detection in a Wavelength of 230 nm determined. Pullulane standards with narrow molecular weight distributions were used for the calibration.
  • the amine functionality content of the non-crosslinked polymers was determined by potentiometric titration with a standard solution of alcoholic trifluoromethanesulfonic acid.
  • L-lysine monohydrate (821 g, 5.0 mol) and sodium hypophosphite (0.1 g) were introduced into a 2.5-1 pressure apparatus and blanketed with nitrogen.
  • the apparatus was then closed in a pressure-tight manner and heated to 200 ° C. for 6 hours, the internal pressure rising to 11.2 bar.
  • the pressure was then slowly released to atmospheric pressure to remove water from the reaction mixture.
  • the reaction temperature was held at 200 ° C for 0.5 hours to remove remaining solvent and volatile products.
  • the reaction mixture was then stirred at 200 ° C. under a pressure of 20 mbar for 25 minutes.
  • the viscous melt was cooled to 115 ° C., discharged from the apparatus and to room temperature cooled down.
  • the molecular weight Mw of the polymer was 4,300 g / mol.
  • L-lysine monohydrate (985.2 g, 6.0 mol) and sodium hypophosphite (0.1 g) were introduced into a 2.5-1 pressure apparatus and filled with
  • the apparatus was then closed in a pressure-tight manner and heated to 196 ° C. for 7 hours, the internal pressure rising to 11.0 bar. The pressure was then slowly released to atmospheric pressure to remove water from the reaction mixture. The reaction temperature was kept at 180 ° C for 2 hours to remove residual
  • the viscous melt obtained was discharged from the apparatus and then cooled to room temperature.
  • the molecular weight Mw of the polymer was 4,500 g / mol.
  • the reaction mixture is slowly released to atmospheric pressure.
  • the viscous melt obtained was discharged from the apparatus and then cooled to room temperature.
  • the molecular weight Mw of the polymer was 7,400 g / mol.
  • L-lysine monohydrate 492.6 g, 3.0 mol
  • hexamethylenediamine 69.6 c 0.6 mol
  • sodium hypophosphi 0.1 g
  • the apparatus was then closed in a pressure-tight manner and heated to 45 180 ° C. for 6 h, the internal pressure rising to 4.1 bar.
  • the pressure was then slowly released to atmospheric pressure to remove volatiles from the reaction mixture.
  • Then was the reaction continued for 30 minutes at 180 ° C. under normal pressure.
  • the viscous melt obtained was cooled to 90 ° C., discharged from the apparatus and then cooled to room temperature.
  • the molecular weight Mw of the polymer was 5,140 g / mol.
  • Crosslinker 1 bisglycidyl ether of polyethylene glycol with 14 ethylene glycol units
  • Crosslinker 2 mixture of hexamethylene diisocyanate and propylene carbonate in a weight ratio of 4
  • Crosslinker 4 ethylene glycol diglycidyl ether
  • crosslinker 3 2.5 g of crosslinker 3 were slowly added to 50 g of a 50% strength by weight aqueous solution of condensate 2 at 25 ° C. An insoluble gel was obtained.
  • crosslinker 3 2.5 g of crosslinker 3 were slowly added to 50 g of a 50% strength by weight aqueous solution of condensate 2 at 25 ° C. An insoluble gel was formed.

Abstract

Cette invention concerne des polymères réticulés contenant des acides aminés basiques condensés, pouvant être obtenus par transformation i) d'homocondensats d'acides aminés basiques, de condensats de mélanges d'au moins deux acides aminés basiques et/ou de cocondensats d'acides aminés basiques et de composés pouvant être cocondensés avec ii) au moins un agent de réticulation présentant au moins deux groupes fonctionnels. L'invention concerne également un procédé permettant leur préparation par transformation i) d'homocondensats d'acides aminés basiques, de cocondensats de mélanges d'au moins deux acides aminés basiques et de cocondensats d'acides aminés basiques et de composés pouvant être cocondensés avec ii) au moins un agent de réticulation présentant au moins deux groupes fonctionnels.
EP00931198A 1999-05-19 2000-05-12 Polymeres reticules contenant des acides amines basiques condenses, et procede de preparation Withdrawn EP1183298A1 (fr)

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TR201909167T4 (tr) 2011-01-04 2019-07-22 Gatt Tech B V Elektrofilik olarak aktive edilmiş polioksazolinden derive edilen çapraz bağlı polimerler ve implantlar.
JP6159973B2 (ja) 2012-01-02 2017-07-12 ユニヴェルシテイト ヘントＵｎｉｖｅｒｓｉｔｅｉｔ Ｇｅｎｔ ポリオキサゾリンポリマー及びそれらの製造方法、これらのポリマーのコンジュゲート並びにそれらの医学的使用
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