JP2003500500A - Crosslinked condensed basic amino acid-containing polymer and method for producing the same - Google Patents

Abstract

  (57) [Summary] (I) a homocondensate of a basic amino acid, a condensate of a mixture of two or more basic amino acids and / or a cocondensate of a compound cocondensable with a basic amino acid, and (ii) at least one functional group. And (i) a homocondensate of a basic amino acid, a condensate of a mixture of two or more basic amino acids, and / or A process for producing the polymer, comprising reacting a co-condensate of a basic amino acid with a compound capable of co-condensation with (ii) at least one crosslinking agent having at least one functional group.

Description

Detailed Description of the Invention

TECHNICAL FIELD The present invention relates to a crosslinked condensed basic amino acid-containing polymer and a method for producing the same.

BACKGROUND OF THE INVENTION US Pat. No. 5,028,689 relates to high molecular weight slightly branched aliphatic thermoplastic copolyamides with improved melt viscosity. One or more lactams, aminocarboxylic acids, diamine / dicarboxylic acid mixtures or mixtures thereof in the presence of small amounts of lysine or lysine esters of low alcohols and polycarboxylic acids in approximately the same amount as the free amino groups of lysine or lysine esters. A copolyamide is produced by polycondensing a monomer mixture consisting of a mixture. Depending on the amount of lysine used, 0.1 to 1.0% by weight of copolyamide with lysine moieties results.
The conventional addition of salt and the combined addition of lysine and polycarboxylic acid to the monomer reaction mixture before the start of the reaction dramatically increases the polyamide formation rate.

US Pat. No. 4,892,927 describes thermoplastic, deformable high molecular weight polyamides in the presence of small amounts of α-amino-ε-caprolactam, a polyamide forming agent, an aliphatic diamine / dicarboxylic acid mixture. Production by polycondensation is described, whereas in US Pat. No. 4,959,452, the presence of 0.1 to 2% by weight of α-amino-ε-caprolactam and an equivalent amount of polycarboxylic acid. Under,
At least one polyamide-forming lactam is hydrolytically polymerized to produce predominantly aliphatic polyamides. These polyamides are used to make films and fibers.

US Pat. No. 3,651,023 describes producing a polyamide composition, for example by polymerizing caprolactam in the presence of lysine, the lysine being present in the polymer at 0.5-5% by weight. It may be present in the amount of lysine. Fibers and threads are made from this polymer.

US Pat. No. 4,126,628 relates to a process for monoacylation of diamino acids such as lysine, ornithine and α, γ-diaminobutyric acid, wherein the pH is at least about 10 in the presence of a basic catalyst, The acid and a succinimidyl ester of a carboxylic acid or a substituted carboxylic acid are reacted in approximately the same amount at 25 to 50 ° C. N-
Acyl amino acid products are useful as surfactants, pharmaceuticals or intermediates for pharmaceuticals.

US Pat. No. 09/131234 describes at least 5 mol% of basic amino acid units selected from the group consisting of lysine, arginine, ornithine, tryptophan and mixtures thereof and aliphatic or cycloaliphatic amines, lipids. Cyclic amine,
It relates to amino acid-based polymers, oligomers or copolymers containing at least about 5 mol% of a polymerizable compound selected from the group consisting of diamines, triamines, tetraamines, aliphatic amino alcohols or mixtures thereof. The polymer, oligomer or copolymer is prepared by condensing the basic amino acid with at least one polymerizable compound at a temperature of at least 120 ° C. The condensation products may be used as detergent additives and / or other laundry additives.

US Pat. No. 09/131282 relates to condensation products of basic amino acids with compounds copolymerizable with said condensation products consisting of (a) lysine, arginine, ornithine, tryptophan and mixtures thereof. A basic amino acid selected from the group: (b) saturated monobasic carboxylic acid, unsaturated monobasic carboxylic acid, polybasic carboxylic acid,
Copolymerizable compounds selected from the group consisting of carboxylic anhydrides, diketene, monohydroxycarboxylic acids, polyhydroxycarboxylic acids and mixtures thereof, and optionally (c) amines, lactams, non-protein amino acids, alcohols, alkoxylations At least one compound selected from the group consisting of alcohols, alkoxylated amines, amino sugars, carbohydrates and sugar carboxylic acids in a molar ratio of (a) :( b) of 100: 1 to 1: 1. By condensing at a temperature of at least 120 ° C. This condensation product can be used as an additive in detergents.

[0008]   An object of the present invention is to provide a novel condensation product of basic amino acids.

SUMMARY OF THE INVENTION The above problems are (i) a homocondensate of a basic amino acid, a condensate of a mixture of two or more basic amino acids, and / or a cocondensate of a compound capable of cocondensing with a basic amino acid. And (ii) a crosslinked condensed basic amino acid-containing polymer obtained by reacting at least one crosslinking agent having at least two functional groups.

This problem is (i) a homocondensate of a basic amino acid, a cocondensate of a mixture of two or more basic amino acids, and a cocondensate of a compound capable of cocondensing with a basic amino acid, and (ii) at least It is also solved by a process for preparing crosslinked basic amino acid-containing polymers, which consists of reaction with at least one crosslinker having two functional groups.

[0011]   Detailed Description of the Invention   The basic amino acid-containing polymer advantageously comprises basic amino acids either alone or together.
It is obtained by thermal condensation with a condensable compound. Basic amino
Another method for producing acid-containing polymers is by chemical methods (eg basic amines).
No acid via N-carboxyanhydride) or microbial methods. Salt here
A basic amino acid is understood as a compound belonging to group (a), for example lysine,
Luginine, ornithine, tryptophan and mixtures thereof. A combination of these
The product is a hydrate, an ester with a low alcohol or a salt thereof, for example, a sulfate thereof.
, Hydrochloride or acetate. Esters of basic amino acids are preferably monovalent C ₁ ~ C_Four-Alcohols such as methanol, ethanol, n-propanol, a
Sopropanol, n-butanol, sec-butanol or tert-butano
It is derived from When using the hydrochloride salt, add approximately equal amounts of base to the reaction mixture.
Hydrogen chloride must be neutralized. Sodium hydroxide and potassium hydroxide
Is the preferred base. Because it uses the basic amino acid monohydrochloride
If so, 1 equivalent of base is required, whereas dihydrochloride is 2 equivalent.
You need the amount. Use of lysine hydrate and aqueous solution of lysine as basic amino acid
Is advantageous. Lysine is converted into its cyclic lactam, namely α-amino-ε-carcinoma.
It can also be used in the form of prolactam.

Compounds which can be co-condensed with basic amino acids are understood here as compounds of group (b), for example compounds having at least one carboxyl group, carboxylic anhydrides, diketene, amines, lactams, alcohols, alkoxyls. Alcohols and alkoxylated amines. Carboxyl group-containing compounds are, for example, saturated monobasic carboxylic acids, unsaturated monobasic carboxylic acids, polybasic carboxylic acids, monohydroxycarboxylic acids, monobasic polyhydroxycarboxylic acids, non-protein amino acids and mixtures thereof. Examples of saturated monobasic carboxylic acids are formic acid, acetic acid, propionic acid, butyric acid, valeric acid, capric 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 natural fatty acids and mixtures thereof.

Examples of unsaturated monobasic carboxylic acids are acrylic acid, methacrylic acid, crotonic acid, sorbic acid, oleic acid, linoleic acid, and erucic acid.

Examples of polybasic carboxylic acids are oxalic acid, fumaric acid, maleic acid, malonic acid, succinic acid, itaconic acid, adipic acid, aconitic acid, suberic acid, azelaic acid, pyricindicarboxylic acid, furandicarboxylic acid, phthalic acid, terephthalic acid, diglycolic acid, glutaric acid, substituted _{C 4} - dicarboxylic acid, sulfosuccinic _acid, C 1 _{-C 26} - alkyl succinic _acids, C 2 _{-C 26} - alkenyl succinic acid, 1,2,3 propane Tricarboxylic acid, 1,1,3,3-propanetetracarboxylic acid, 1,1,2,2-ethanetetracarboxylic acid, 1,2,3,4-butanetetracarboxylic acid, 1,2,2,3- Propane tetracarboxylic acid, 1,3,3,5-pentane tetracarboxylic acid, 1,2,4
Benzenetricarboxylic acid and 1,2,4,5-benzenetetracarboxylic acid.

Examples of monohydroxycarboxylic acids are malic acid, tartronic acid, citric acid, and isocitric acid. Polyhydroxycarboxylic acids include, for example, tartaric acid, mucus acid,
Glyceric acid, bis (hydroxymethyl) propionic acid, gluconic acid, and hydroxylated unsaturated fatty acids such as dihydroxystearic acid.

Other carboxylic acid group-containing compounds are non-protein amino acids. Examples of such acids include anthranilic acid, N-methylamino substituted acids such as N-methylglycine, dimethylaminoacetic acid, ethanolaminoacetic acid, N-carboxymethylamino acid, nitrilotriacetic acid, ethylenediamineacetic acid, ethylenediaminotetraacetic acid,
Diethylenetriaminepentaacetic acid, hydroxyethylene diamino triacetic acid, diaminosuccinic _acid, C 4 _{-C 26} - aminoalkyl carboxylic acids, such as 4-aminobutyric acid, 6-aminocaproic acid, and 11-aminoundecanoic acid.

Unlike basic amino acids and α-amino acids, other carboxyl-containing compounds that can be condensed with basic amino acids are sugar carboxylic acids, such as gluconic acid, glutaric acid, gluconolactone, and glucuronic acid.

Carboxylic anhydrides are also suitable as co-condensable compounds, for example, succinic anhydride, butantetracarboxylic acid monoanhydrides and dianhydrides, phthalic anhydride, acetylcitric anhydride, maleic anhydride, anhydrous. There are itaconic acid and aconitic acid anhydride.

Examples of diketones which can be used as co-condensable compounds are alkyl diketene having 1 to 30 carbon atoms in the alkyl radical. Such diketene is characterized by the following formula:

[0020]

[Chemical 1]

Wherein the substituents R ¹ and R ² have the same meaning or are different,
H, C ₁ -C _30- , preferably C ₆ -C ₂₂ -saturated or ethylenically unsaturated alkyl. Compounds of the above formula are, for example, diketene, methyldiketene, hexyldiketene, cyclohexyldiketene, octyldiketene, decyldiketene, dodecyldiketene, palmityldiketene, stearyldiketene, oleyldiketene, octadecyldiketene, eicosyldiketene, docosyldiketene, and behenyldiketene.

Examples of amines: Aliphatic and cycloaliphatic amines, preferably methylamine, ethylamine, propylamine, butylamine, pentylamine, hexylamine, heptylamine,
Octylamine, nonylamine, decylamine, undecylamine, dodecylamine, tridecylamine, stearylamine, palmitylamine, 2-ethylhexylamine, isononylamine, hexamethyleneimine, dimethylamine, diethylamine, dipropylamine, dibutylamine, Dihexylamine, ditridecylamine, N-methylbutylamine, N-ethylbutylamine; cycloaliphatic amines, preferably cyclopentylamine, cyclohexylamine, N-methylcyclohexylamine, N-ethylcyclohexylamine, dicyclohexylamine;
Diamines, triamines and tetraamines, preferably ethylenediamine, propylenediamine, butylenediamine, neopentyldiamine, hexamethylenediamine, octamethylenediamine, imidazole, 5-amino-1,3-trimethylcyclohexylmethylamine, diethylenetriamine, dipropylenetriamine, Tripropyltetraamine, 4,4'-methylenebiscyclohexylamine, 4,4'-methylenebis (2-methylcyclohexylamine), 4,7-dioxadecyl-1,10-diamine, 4
, 9-Dioxadodecyl-1,12-diamine, 4,7,10-trioxatridecyl-1,13-diamine, 2- (ethylamino) ethylamine, 3- (ethylamino) propylamine, 3- ( Cyclohexylamino) propylamine, 3- (
2-aminoethyl) aminopropylamine, 2- (diethylamino) ethylamine, 3- (dimethylamino) propylamine, dimethyldipropylenetriamine, 4-aminomethyloctane-1,8-diamine, 3- (diethylamino) propylamine, N, N-diethyl-1,4-pentanediamine, diethylenetriamine, dipropylenetriamine, bis (hexamethylene) triamine, aminoethylpiperazine, aminopropylpiperazine, N, N-bis (aminopropyl) methylamine, N, N- Bis (aminopropyl) ethylamine, N, N-bis (aminopropyl) hexylamine, N, N-bis (aminopropyl) octylamine, N, N-dimethyldipropylenetriamine, N, N-bis (3-dimethylamino) Propyl) amine, N, N ' 1,2-ethanediylbis (1,3-propanediamine), N- (aminoethyl) piperazine, N- (2-imidazole) piperazine, N-ethylpiperazine, N- (hydroxyethyl) piperazine, N- (aminoethyl) Piperazine, N- (aminopropyl) piperazine, N- (aminoethyl) morpholine, N- (aminopropyl) morpholine, N- (aminoethyl) imidazole, N- (aminopropyl) imidazole, N- (aminoethyl) hexamethylene Diamine, N- (aminopropyl) hexamethylenediamine, N- (
Aminoethyl) ethylenediamine, N- (aminopropyl) ethylenediamine,
N- (aminoethyl) butylenediamine, N- (aminopropyl) butylenediamine, bis (aminoethyl) piperazine, bis (aminopropyl) piperazine,
Bis (aminoethyl) hexamethylenediamine, bis (aminopropyl) hexamethylenediamine, bis (aminoethyl) ethylenediamine, bis (aminopropyl) ethylenediamine, bis (aminoethyl) butylenediamine, bis (aminopropyl) butylenediamine, aliphatic Amino alcohols, preferably 2-aminoethanol, 3-amino-1-propanol, 1-amino-2-propanol, 2- (2-aminoethoxy) ethanol, 2- [2-aminoethyl) amino] ethanol, 2 -Methylaminoethanol, 2- (ethyl-amino) ethanol, 2-butylaminoethanol, diethanolamine, 3-[(hydroxyethyl) amino] -1-propanol, diisopropanolamine, bis (hydroxyethyl) aminoethylamine Down, bis (
Hydroxypropyl) aminoethylamine, bis (hydroxyethyl) aminopropylamine, bis (hydroxypropyl) aminopropylamine; amino sugars such as chitosan or chitosamine, and compounds obtained by reducing carbohydrates by reductive amination, and other aminos Group-containing compounds such as melamine, urea, guanidine, polyguanide, pipericin, morpholine, 2,6-dimethylmorpholine and tryptamine.

Preferred amines are selected from hexamethylenediamine, octylamine, monoethanolamine, octamethylenediamine, diaminododecane, decylamine, dodecylamine and mixtures thereof.

Another compound that can be co-condensed with basic amino acids is the lactam. Lactams have, for example, 5 to 13 atoms in the ring. Suitable lactams include butyrolactam, caprolactam and laurolactam.

Other compounds that can be co-condensed with basic amino acids are alcohols. Alcohols are monohydric alcohols, for example primary, secondary or tertiary alcohols having 1 to 22 carbon atoms, for example methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, tert-butanol, It may be derived from pentanol, hexanol, 2-ethylhexanol, cyclohexanol, octanol, decanol, dodecanol, palmityl alcohol, stearyl alcohol, and behenyl alcohol. Other suitable alcohols are polyols such as ethylene glycol, propylene glycol, glycerol,
Polyglycerols having 2-8 glycerol units, erythritol, pentaerythritol and sorbitol.

Other co-condensable compounds are carbohydrates such as glucose, sucrose, dextrins, starch and degraded starch, and maltose.

[0027]   Alcohols may also be alkoxylated. Examples of such compounds are C_Two~ C _Four -Addition product of 1 to 200 mol of alkylene oxide and 1 mol of the alcohol.
Is. Suitable alkylene oxides are, for example, ethylene oxide, propylene oxide and
And butylene oxide. Preference is given to using ethylene oxide and propylene oxide
At this time, propylene oxide may be added to the alcohol after ethylene oxide,
The reverse is also possible. Surprisingly, 3 to 20 mol of ethylene oxide and C_Thirteen/ C₁₅−
Addition products of 1 mol of oxo-process alcohols or aliphatic alcohols are particularly preferred
It If desired, the alcohol may have double bonds, for example oleyl alcohol.
It may be rucor.

The basic amino acid may be condensed with an alkoxylated amine, for example 5 to 30 mol of ethylene oxide and stearylamine, oleylamine or palmitylamine 1
Addition product with moles.

The cross-linked condensed amino acid-containing polymer consisting of the compounds of groups (a) and (b) comprises compounds of groups (a) and (b) in a molar ratio of, for example, 100: 1 to 1:10, preferably It is contained such that the molar ratio of (a) to (b) is greater than 1, for example 1.5 or preferably greater than 2. If compound (b) has at least two different functional groups, a molar ratio of (a) :( b) of 1: 1 to 1:10 is advantageously used. Examples of such compounds (b) are non-protein amino acids, lactams, amino alcohols, hydroxycarboxylic acids and amino sugars.

Preferred condensation products used as starting materials for preparing crosslinked condensed basic amino acid-containing polymers are homocondensates of basic amino acids and (a) lysine and (b) palmitic acid, stearic acid. , Lauric acid, octanoic acid, propionic acid,
A cocondensate obtained by condensing at least one compound selected from the group consisting of acetic acid, 2-ethylhexanoic acid, adipic acid, succinic acid, citric acid and mixtures thereof, and (a) lysine (b) 1,6-hexamethylene Chi diamine, octylamine, aminocaproic acid, aminolauric acid, .epsilon.-caprolactam, laurolactam, and _C 14 - _{/ C 2 2} - at least one selected from the group consisting of alkyl diketene It is a condensate obtained by condensing a compound.

To obtain the starting material for producing the crosslinked condensed basic amino acid-containing polymer, the basic amino acids alone, a mixture thereof or at least one basic amino acid and at least one co-condensable compound The condensation with can be carried out in the substance, in an organic solvent or in an aqueous medium. With a concentration of the compound to be condensed of 10 to 98% by mass,
Condensation in water at temperatures of 120 to 300 ° C. is advantageous. In a preferred embodiment of the process, the condensation is carried out in water at a concentration of the compound to be condensed of from 20 to 70% by weight and under pressure at a temperature of from 140 to 250 ° C. Condensation of these compounds can be accomplished by organic solvents such as dimethylformamide, dimethylsulfoxide, dimethylacetamide, glycols, polyethylene glycol, propylene glycol, polypropylene glycol, monohydric alcohols, ethylene oxide and / or propylene oxide to monohydric alcohols. , To the amine or to the carboxylic acid. Some of these solvents react with basic amino acids.

For example, the condensation may be initiated in an aqueous solution or an organic solvent containing water. The condensation of the compounds may be carried out in the presence of water. Also, the water may be distilled off before the compound is condensed. The condensation may be carried out while removing water produced during the condensation. The water produced during the condensation is advantageously removed from the reaction mixture. Under this,
It may be carried out under normal pressure or reduced pressure. The condensation time depends on the reaction conditions selected.
Generally, it may be carried out for 1 minute to 50 hours, preferably for 30 minutes to 16 hours. Low molecular weight polycondensates can also be prepared in pressure-sealed vessels, where water is removed if water is formed during polycondensation.

If desired, the condensation can be carried out in the presence of a mineral acid as catalyst. The concentration of mineral acid is 0.001 to 5, preferably 0.01 to 1.0% by weight. Examples of suitable mineral acids are hypophosphorous acid, hypodiphosphoric acid, phosphoric acid, hydrochloric acid, sulfuric acid and mixtures thereof. In addition to acids, their alkali, ammonium and alkaline earth metal salts can be used as catalysts.

Used as a starting material for the production of crosslinked condensed basic amino acid-containing polymers-homocondensates of basic amino acids-condensates of mixtures of two or more basic amino acids-co-condensable with salt-isomeric amino acids Condensation products which are co-condensates with such compounds are, for example, 300 to 1,000,000, preferably 300 to 200.
00 and particularly preferably a weight average molecular weight Mw of 300 to 2000. They are generally soluble in water and readily disperse therein. The amino groups of the starting materials may be present as preferred amines or partly with mineral acids such as hydrochloric acid, phosphoric acid or sulfuric acid or with organic acids such as methanesulfonic acid, acetic acid, formic acid, propionic acid or citric acid. Alternatively, it may be present in the form of an ammonium salt obtained by complete neutralization.

Condensed basic amino acid-containing compound (i), for example: -a homocondensate of a basic amino acid-a condensate of a mixture of two or more basic amino acids and-a co-condensation of a compound capable of co-condensing with a basic amino acid The condensate is modified by reacting it with a crosslinker (ii) having at least two functional groups. Suitable crosslinkers having at least two functional groups are, for example, α-, ω- or vicinal-dichloroalkanes such as 1,2-dichloroethane, 1,2-dichloropropane, 1,3-dichloropropane, 1,4 -Dichlorobutane and 1,6
-Dichlorohexane. Further suitable crosslinking agents are glycidyl halides,
Examples are epichlorohydrin, bischlorohydrin ethers of polyols, polychlorohydrin ethers of polyols, bischlorohydrin ethers of polyalkylene glycols, chloroformates, phosgene and especially halogen-free crosslinkers.

Crosslinking agents preferably used are epichlorohydrin, bischlorohydrin ethers of ethylene glycol, polyethylene glycols having 2 to 100, preferably 2 to 40 ethylene glycol units, propylene glycol, polypropylene. Glycol, copolymers of ethylene oxide and propylene oxide, glycerol,
Diglycerols, polyglycerols having up to 8 glycerol units, pentaerythritol and sorbitol, and halogen-free crosslinkers which are at least difunctional, preferably (1) ethylene carbonate, propylene carbonate and / or urea, (2) Monoethylenically unsaturated carboxylic acid and its ester, amide and anhydride, at least dibasic saturated carboxylic acid or polycarboxylic acid and its ester, amide and anhydride, (3) Polyetherdiamine, alkylenediamine, A reaction product of a polyalkylene polyamine, an alkylene glycol or an alkylene glycol, or a mixture thereof with an ester, amide or anhydride of a monoethylenically unsaturated carboxylic acid or a monoethylenically unsaturated carboxylic acid. Wherein the reaction product has at least two ethylenically unsaturated double bonds or a carboxamide, carboxyl or ester group as a functional group, and (4) a dicarboxylic acid ester having at least two aziridino groups. Selected from the group consisting of reaction products with ethyleneimine, (5) diepoxides, polyepoxides, α, ω-diisocyanates such as hexamethylene diisocyanate and polyisocyanates, and mixtures of said crosslinkers.

[0037]   Of the crosslinking agents of group (1), propylene carbonate is preferably used.

Examples of suitable halogen-free crosslinker groups (2) are monoethylenically unsaturated monocarboxylic acids, such as acrylic acid, methacrylic acid and crotonic acid, and their amides, esters and anhydrides. The esters may be derived from alcohols having 1 to 22 carbon atoms, preferably 1 to 18 carbon atoms. The amide is preferably unsubstituted, but it may also carry one C ₁ -C ₂₂ -alkyl group as a substituent.

Another halogen-free group (2) crosslinkers are at least dibasic saturated carboxylic acids, such as dicarboxylic acids, their salts, diesters and diamines. These compounds are characterized, for example, by the formula:

[0040]

[Chemical 2]

R = C ₁ -C ₂₂ -alkyl, R ¹ = H, C ₁ -C ₂₂ -alkyl, and n = 0-22.

Monoethylenically unsaturated carboxylic acids, such as maleic acid or itaconic acid, are preferred in addition to the dicarboxylic acids of the formula I. The ester of the dicarboxylic acid in question is preferably derived from an alcohol having 1 to 4 carbon atoms. Examples of suitable dicarboxylic acid esters are dimethyl oxalate, diethyl oxalate, diisopropyl oxalate, dimethyl succinate, diethyl succinate, diisopropyl succinate, di-n-propyl succinate, diisobutyl succinate, dimethyl adipate. , Diethyl adipate and diisopropyl adipate. Examples of suitable ethylenically unsaturated dicarboxylic acid esters are dimethyl maleate, diethyl maleate, diisopropyl maleate, dimethyl itaconate and diisopropyl itaconate. Also suitable are substituted dicarboxylic acids and their esters such as tartaric acid (D, L and racemic forms) and tartaric acid esters such as dimethyl tartaric acid and diethyl tartaric acid.

Examples of suitable dicarboxylic acid anhydrides are maleic anhydride, itaconic anhydride, citric anhydride. Aziricin crosslinks with said halogen-free crosslinkers either under the formation of amide groups or, in the case of amides such as adipic acid diamide, by transamidation. Maleic acid esters, and monoethylenically unsaturated dicarboxylic acids, and their anhydrides can be crosslinked by both forming carboxamide groups and introducing NH groups by Michael addition.

At least dibasic saturated carboxylic acids include, for example, tricarboxylic acids and tetracarboxylic acids, such as citric acid, propanetricarboxylic acid, ethylenediaminetetraacetic acid and butanetetracarboxylic acid. Salts, esters, amides and anhydrides derived from the carboxylic acids are also suitable crosslinkers of group (2).

A polycarboxylic acid obtained by polymerizing a monoethylenically unsaturated carboxylic acid or an anhydride is also a preferable crosslinking agent of the group (2). Examples of suitable monoethylenically unsaturated carboxylic acids are acrylic acid, methacrylic acid, crotonic acid, maleic acid and / or itaconic acid. Thus, for example, polyacrylic acid, copolymers of acrylic acid and methacrylic acid or copolymers of acrylic acid and maleic acid are also suitable for use as crosslinkers.

Another suitable (2) crosslinker is, for example, an anhydride such as maleic anhydride in the presence of a free radical forming initiator in an inert solvent such as toluene, xylene, ethylbenzene or isopropylbenzene or a solvent mixture. It can be produced by polymerizing below. Peroxyesters such as tert-butylper-2-ethylhexanoate are preferably used as initiators. In addition to homopolymers, copolymers of maleic anhydride, such as copolymers or maleic anhydride with C ₂ -C 30 acrylic acid and maleic acid _- copolymers of olefins are also suitable. Preference is given, for example, to a copolymer of maleic anhydride and isobutene or a copolymer of maleic anhydride and diisobutene. Anhydride group-containing copolymers can also optionally be modified by reaction with C ₁ -C ₂₀ -alcohols or ammonia or amines and used as crosslinkers.

The molar amount Mw of the homopolymer or copolymer is, for example, up to 10,000, preferably 500 to 5000. Polymers of said type are for example EP-A-0276.
464, US-A-3810834, GB-A-1411063 and US-A.
No. 4,818,795. At least dibasic saturated carboxylic acids and polycarboxylic acids can also be used as crosslinking agents in the form of their alkali metal or ammonium salts. The sodium salt is preferably used here. The polycarboxylic acid may be partially neutralized, for example up to 10 to 50 mol%, or it may be completely neutralized.

Compounds of group (2) which are advantageously used are dimethyl tartrate, diethyl tartrate, dimethyl adipate, diethyl adipate, dimethyl maleate, diethyl maleate, maleic anhydride, maleic acid, acrylic acid, methyl acrylate. , Ethyl acrylate, acrylamide and methacrylamide.

Examples of halogen-free group (3) crosslinkers are polyetherdiamines, alkylenediamines, polyalkylenepolyamines, alkyleneglycols and polyalkyleneglycols, or monoethylenically unsaturated carboxylic acids, monoethylenically unsaturated Saturated carboxylic acid esters, monoethylenically unsaturated carboxylic acid amides, or mixtures with monoethylenically unsaturated carboxylic acid anhydrides.

The polyether diamine is produced, for example, by reacting polyalkylene glycol with ammonia. The polyalkylene glycol may contain 2 to 50, preferably 2 to 40, alkylene oxide units. The polyalkylene glycol may be, for example, polyethylene glycol, polypropylene glycol or polybutylene glycol, or a block copolymer of ethylene glycol and propylene glycol, a block copolymer of ethylene glycol and butylene glycol or ethylene glycol, propylene glycol and butylene glycol. Block copolymer of Copolymers containing randomly ethylene oxide and propylene oxide and optionally butylene oxide, if not block copolymers, are also suitable for the preparation of polyetherdiamines. Furthermore, the polyether diamine is derived from polytetrahydrofuran having 2 to 75 tetrahydrofuran units. Polytetratrahydrofuran likewise reacts with ammonia to give the corresponding α-, ω-polyether diamines. Polyethylene glycol or block copolymers of ethylene glycol and propylene glycol are preferably used for preparing the polyetherdiamine.

Examples of suitable alkylenediamines are ethylenediamine, propylenediamine,
1,4-diaminobutane and 1,6-diaminohexane. Examples of suitable polyalkylenepolyamines are diethylenetriamine, triethylenetetramine, dipropylenetriamine, tripropylenetetramine, dihexamethylenetriamine, aminopropylethylenediamine, bis-amino-propylethylenetriamine and polyethyleneimines of molecular weight up to 5000. The amine is reacted with a monoethylenically unsaturated carboxylic acid, or an ester, amide or anhydride of a monoethylenically unsaturated carboxylic acid to give at least two ethylenically unsaturated double bonds, carboxamide, carboxyl or A product with ester groups is obtained. Thus, for example, when an amine or glycol is reacted with maleic anhydride, a compound as characterized by Formula II below is obtained.

[0052]

[Chemical 3]

Where X, Y and Z = O or NH, Y may be CH ₂ , m and n are 0-4, and p and q are 0-45000.

The compound of formula (II) is, for example, alkylene glycol, polyethylene glycol, polyethyleneimine, polypropyleneimine, polytetrahydrofuran, α
, Ω-diol or α, ω-diamine can be prepared by reacting with maleic anhydride or the other monoethylenically unsaturated carboxylic acid or carboxylic acid derivative. Suitable polyethylene glycols for producing the crosslinker II are preferably 6
It has a molecular weight of 2 to 10,000, while the molecular weight of polyethyleneimine is preferably 1
29 to 50,000, and the molecular weight of polypropyleneimine is 171 to 50,000.
Is. Examples of suitable alkylene glycols are ethylene glycol, 1,2-propylene glycol, 1,4-butanediol and 1,6-hexanediol.

The α, ω-diamines which are advantageously used for preparing the crosslinkers of the formula II are ethylenediamine and α, ω-diamines derived from polyethylene glycol or polytetrahydrofuran having a molecular weight Mw of about 400 to 5000, respectively. Is.

Particularly preferred suitable crosslinkers of the formula II are the reaction products of maleic anhydride and α, ω-polyetherdiamines having a molecular weight of 400 to 5000, 129 to 5000.
A reaction product of polyethyleneimine having a molecular weight of 0 with maleic anhydride and a reaction product of ethylenediamine or triethylenetetramine with maleic anhydride in a molar ratio of 1: at least 2. When polyalkylene glycol or diol is reacted with monoethylenically unsaturated carboxylic acid or its ester, amide or anhydride, a cross-linking agent is formed while retaining the double bond of monoethylenically unsaturated carboxylic acid or its derivative. Here, the monoethylenically unsaturated carboxylic acid or a derivative thereof is bonded to polyethylenediamine, alkylenediamine or polyalkylenepolyamine through an amide group, and is bonded to alkyleneglycol or polyalkyleneglycol through an ester group. These reaction products have at least two ethylenically unsaturated double bonds. This type of crosslinker reacts with the amino group of the polymer formed by Michael addition of azilysine or polymer amino groups, at the terminal double bond of the crosslinker, optionally with the formation of additional amide groups.

By being added to the double bond by Michael addition, the polyetherdiamines, alkylenediamines and polyalkylenepolyamines can react with maleic anhydride, or ethylenically unsaturated carboxylic acids or their derivatives. Thus formula III
The cross-linking agent of is obtained.

[0058]

[Chemical 4]

Where X, Y and Z = O or NH, Y may be CH ₂ , R ¹ = H or CH ₃ , and R ² = H, COOMe, COOR or CONH ₂ . R ³ = OR, NH ₂ , OH or OMe, R = C ₁ -C ₂₂ -alkyl, Me = H, Na, K, Mg or Ca, m and n = 0-4 Yes, p and q = 0-45000.

The cross-linking agent of formula (III) achieves cross-linking with the amino groups of the polymer formed during polymerization by way of its terminal carboxyl or ester groups and by forming amide groups. This class of cross-linking dosage forms also includes the reaction products of monoethylenically unsaturated carboxylic acids with alkylenediamines and polyalkylenepolyamines;
A reaction product obtained by adding ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine and polyethyleneimine having a molecular weight of, for example, 129 to 50,000 to at least 2 moles of acrylic or methacrylic ester per mole of amine content. The thing is suitable. The C ₁ -C ₆ -alkyl esters of acrylic acid or methacrylic acid are preferably used as monoethylenically unsaturated carboxylic acid esters. Methyl acrylate and ethyl acrylate are particularly advantageous for making crosslinkers. Crosslinking agents prepared by Michael addition of polyalkylene polyamines and ethylenically unsaturated carboxylic acids, their esters, amides or anhydrides have two or more functional groups. The number of these groups will vary depending on the molar ratio of the reactants used in the Michael addition. Therefore, for example, ethylenically unsaturated carboxylic acid, or its derivative is 2 to
10 moles, preferably 2-8 moles, may be added by Michael addition to 1 mole of a polyalkylene polyamine containing 10 nitrogen atoms. At least 2 mol, at most 4
In moles, the ethylenically unsaturated carboxylic acid or its derivative is added by Michael addition to 1 mole of polyalkylenediamine and alkylenediamine, respectively.

[0061]   Diethylenetriamine and formula:

[0062]

[Chemical 5]

A cross-linking agent having the following structure by reacting with a compound of the formula: X = OH, NH ₂ or OR ¹ and R ¹ ═C ₁ -C ₂₂ -alkyl.

[0064]

[Chemical 6]

Embedded image where X = NH ₂ , OH or OR ¹ and R ¹ = C ₁ -C ₂₂ -alkyl are prepared, for example by Michael addition.

The secondary NH group in the compound of formula IV is optionally reacted with acrylic acid, acrylamide or an acrylic ester by Michael addition.

A compound of formula II having at least two carboxyl groups, which can be prepared by reacting a polyetherdiamine, ethylenediamine or polyalkylenepolyamine with maleic anhydride, or polyetherdiamine, polyalkylenepolyamine or ethylenediamine and carbon respectively 1 with 1 to 4 atoms
It is advantageous to use crosslinkers of group (3), which are Michael addition products having at least two ester groups, prepared from acrylic or methacrylic acid esters of polyhydric alcohols.

The reaction product produced by reacting a dicarboxylic acid ester completely esterified with a monohydric alcohol having 1 to 5 carbon atoms with ethyleneimine is a halogen-free (4) group crosslinker. It is suitable for use as. Examples of suitable dicarboxylic acid esters include dimethyl oxalate, diethyl oxalate, dimethyl succinate,
Diethyl succinate, dimethyl adipate, diethyl adipate and dimethyl glutarate. Thus, for example, the reaction of diethyl oxaloate with ethyleneimine gives bis [β- (1-aziridino) -ethyl] oxalamide. The dicarboxylic acid ester reacts with ethyleneimine in a molar ratio of, for example, 1: at least 4. The terminal azilysin group is the reactive group of these crosslinkers. Such crosslinkers are characterized by Formula V:

[0069]

[Chemical 7]

[0070] [In the formula, n = 0 to 22].

Preferred compounds of group (5) are bisglycidyl ethers of ethylene glycol,
Polyethylene glycols having 2 to 40 ethylene glycol units, propylene glycol, polypropylene glycol ethers, copolymers of ethylene oxide and propylene oxide, and diisocyanates such as hexamethylene diisocyanate.

Crosslinker mixture, for example: a mixture of ethylene glycol diglycidyl ether and ethylene glycol bischlorohydrin ether, polyethylene glycol diglycidyl ether having 2 to 40 ethylene glycol units and 2 to 40 It is also advantageous to use mixtures of polyethylene glycols having ethylene glycol units with bischlorohydrin ether, or of hexamethylene diisocyanate with propylene carbonate.

The crosslinked condensed basic amino acid-containing compound can be produced by reacting at least one compound of group (i) with at least one compound of group (ii). The reaction can be carried out in a substance, a solution of an inert solvent or a dispersion of an aqueous medium or an inert solvent. Depending on the degree of crosslinking, water soluble or water insoluble crosslinked condensed basic amino acid-containing polymers are produced.

In producing the fine particle crosslinked condensed basic amino acid-containing polymer, first, the compound (i) is reacted in an inert solvent which does not react with the compounds (i) and (ii) under the reaction conditions.
It is advantageous to prepare the solutions of)) and (ii) and then to add the two solutions dropwise or continuously in one portion or in small portions.

Preferred inert solvents are ethers which are inert towards the compounds of groups (i) and (ii) and which are liquid at least under the reaction conditions. Examples of ethers are dialkyl ethers having 1 to 6 carbon atoms in the alkyl group, such as diethyl ether, methyl n-propyl ether, methyl isopropyl ether, methyl n-butyl ether, methyl sec-butyl ether, methyl tert-butyl ether, ethers. Hexyl ether and di-n-butyl ether.

More preferred ethers are end-group capped polyalkylene glycols having, for example, 2 to 50 polymerized alkylene oxide units. It is preferred to use C ₁ -C ₄ -alkyl groups for capping the end groups. The end-group-capped polyalkylene glycol preferably has methyl or ethyl groups. The end group-capped polyalkylene glycol is obtained, for example, by alkylation of polyalkylene glycol. Examples of suitable polyalkylene glycols are polyethylene glycol, polypropylene glycol and polybutylene glycol, block copolymers of ethylene oxide and propylene oxide or of ethylene oxide and butylene oxide or of ethylene oxide, propylene oxide and butylene oxide. Or a block copolymer of propylene oxide and butylene oxide. These end group-capped polyalkylene glycols which are advantageously used are
Glycols derived from the following groups end-capped with methyl or ethyl groups at both ends: diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol and dibutylene glycol.

Further preferred ethers used are those derived from polytetrahydrofuran having 2 to 50 tetrahydrofuran units in the molecule and endcapped with C ₁ -C ₄ -alkyl groups at both ends. Is. Among them, ditetrahydrofuran ether or tritetrahydrofuran ether whose both ends are end-capped with a methyl group or an ethyl group is advantageously used.

Further preferred ethers for use in the present invention are C ₁ -C ₄ − at each end.
Derived from ethylene glycol, propylene glycol and butylene glycol end-capped with alkyl. Of these, dimethyl ethers of ethylene glycol, propylene glycol and butylene glycol are advantageously used. Another suitable solvent is tetrahydrofuran and dioxane.

Methyl-tert-butyl ether, tetrahydrofuran, dioxane or mixtures of said solvents are organic solvents which are advantageously used according to the invention. However, water is a suitable inert solvent for the crosslinking reaction. The compound (i) is dissolved or dispersed in water, and the crosslinking agent (ii) solution is added to produce a crosslinked basic amino acid-containing compound. Depending on the reaction conditions, a granulated and crosslinked basic amino acid-containing polymer or gel is produced.

The concentration of compounds (i) and (ii) in the inert solvent is, for example, 1-80, preferably 25-50% by weight, based on the mixture. The reaction mixture ranges from 15 to 200 ° C, preferably up to 100 ° C. If the reaction temperature exceeds the boiling point of the solvent used, 40 ba in a pressure-sealed device such as an autoclave equipped with a stirrer.
The reaction is carried out under high pressure up to r, preferably 2 to 40 bar.

The reaction time depends on various factors such as the reactivity of the compounds (i) and (ii) and the temperature at which the reaction is carried out. The crosslinking reaction is carried out for 1 minute to 20 hours, preferably 10 minutes.
It is carried out in minutes to 2 hours.

The crosslinked basic amino acid-containing polymers are used, for example, as detergent additives and / or laundry additives. The water-insoluble crosslinked polymer of the present invention is an active compound,
For example, it is also used for non-fluidization of insecticides, pharmaceuticals, cosmetics and plant protection agents. If non-fluidised active compounds are used, it is advantageous to release the active compounds from the combination of active compound with crosslinked basic amino acid-containing compound polymers by defined methods.

It is also suitable to use the particulate, water-insoluble crosslinked polymers as absorbents of formaldehyde or other aldehydes and ketones from waste water or exhaust gases. It has a variety of applications; for example, crosslinked particulate polymers can be used as cigarette filters, as filters for purifying wastewater, or as absorbents of formaldehyde in pressboard sheets. Particulate cross-linked polymers are also useful for absorbing acidic gases such as sulfur dioxide, sulfur trioxide, hydrogen chloride and carbon dioxide. They can also be used, for example, for the removal of acidic compounds such as benzoic acid or p-toluenesulfonic acid derived from aqueous solutions.

The particulate, water-insoluble polymer is also useful for removing heavy metal ions from wastewater. Here, it is particularly advantageous to carry out solid / liquid extraction of heavy metals (main group metals, transition metals, lanthanides and actinides) from aqueous solutions or waste water. It is particularly advantageous to extract iron, zinc, copper, lead, rhodium and mercury ions, as well as chromium, manganese, nickel, silver and cadmium ions.

Weight average molecular weight (Mw) was determined by aqueous gel filtration chromatography (GPC) using a 20/80 v / v mixture of acetonitrile and water as the mobile phase, Water Ultra Hydrogel 500, 250, 250, 120 columns and 230 nm. Measured by wavelength UV detector. A pullulan standard that can distinguish a narrow range of molecular weights was used as a calibration curve.

The content of amine functional groups in the uncrosslinked polymer was determined by potentiometric titration with a standard solution of alcoholic trifluoromethanesulfonic acid.

Examples Synthesis of Condensates 1 to 4 Condensate 1 Condensation product of L-lysine L-lysine monohydrate (821 g, 5.0 mol) and sodium hypophosphite (0.1 g) were pressurized. It was introduced into a possible 2.5 l reaction vessel and blanketed with nitrogen.
The reaction vessel is then pressure-sealed and its contents are heated at 200 ° C. for 6 hours, during which the internal pressure is raised to 11.2 bar. Slowly reduce the pressure to atmospheric pressure,
Water was removed from the reaction mixture. The reaction temperature was maintained at 200 ° C for 0.5 hours to remove residual solvent and volatile products. The reaction mixture was subsequently stirred for 25 minutes at 200 ° C. under a pressure of 20 mbar. The viscous melt was cooled to 115 ° C., removed from the reaction vessel and cooled to ambient temperature. The molecular weight of the polymer is Mw = 4300 g / mo.
It was l.

Condensate 2 Condensation product of L-lysine L-lysine monohydrate (985.2 g, 6.0 mol) and sodium hypophosphite (0.1 g) in a 2.5 l reaction vessel capable of pressurization It was introduced into the inside and gas-sealed with nitrogen. The reaction vessel was then pressure sealed and heated at 196 ° C. for 7 hours, while maintaining an internal pressure of 11
Increase to 0.0 bar. The pressure was slowly reduced to atmospheric pressure and water was removed from the reaction mixture. The reaction temperature was maintained at 180 ° C. for 2 hours to remove residual solvent and volatile products. The resulting viscous melt was removed from the reaction vessel and cooled to ambient temperature. The molecular weight of the polymer was Mw = 4500 g / mol.

Condensate 3 Condensation product of L-lysine and aminocaproic acid in a molar ratio of 1: 1 L-lysine monohydrate (656.8 g, 4.0 mol), aminocaproic acid (52
4.7 g (4.0 mol) and sodium hypophosphite (0.1 g) were introduced into a pressurizable 2.5 l reaction vessel and blanketed with nitrogen. The reaction vessel is then pressure-sealed and heated at 196 ° C. for 7 hours, during which the internal pressure is raised to 8.2 bar.
The pressure was slowly reduced to atmospheric pressure to remove volatile materials from the reaction mixture.
The resulting viscous melt was removed from the reaction vessel and cooled to room temperature. The molecular weight of the polymer was Mw = 7400 g / mol.

Condensate 4 Condensation product of L-lysine and hexamethylenediamine in a molar ratio of 5: 1 L-lysine monohydrate (492.6 g, 3.0 mol), hexamethylenediamine (69.6 g, 0) 0.6 mol) and sodium hypophosphite (0.1 g) were introduced into a pressurizable 2.5 l reaction vessel and blanketed with nitrogen. The reaction vessel is then pressure-sealed and heated at 180 ° C. for 6 hours, during which the internal pressure is raised to 4.1 bar. The pressure was slowly reduced to atmospheric pressure to remove volatile materials from the reaction mixture. The reaction was continued under atmospheric pressure at 180 ° C. for 30 minutes. 90% of the viscous melt obtained
It was cooled to 0 ° C., removed from the reaction vessel and further cooled to ambient temperature. The molecular weight of the polymer was Mw = 5140 g / mol.

Crosslinking agent 1: Bisglycidyl ether crosslinking agent of polyethylene glycol having 14 ethylene glycol units 2: Mixture of hexamethylene diisocyanate and propylene carbonate in a mass ratio of 4: 1 Crosslinking agent 3: Lysine ethyl ester diisocyanate crosslinking agent 4: Ethylene glycol diglycidyl ether Example 1 12 g of an aqueous solution of crosslinking agent 1 having a concentration of 25% by mass was slowly added to 40 g of an aqueous solution of condensate 3 having a concentration of 25% by mass at 25 ° C. The reaction mixture was then heated to 65 ° C. and stirred at that temperature for 1 hour. The viscous solution obtained is cooled to ambient temperature and treated with sulfuric acid 1
The pH was adjusted to 7.5 by the addition of g to give a highly viscous orange solution.

Example 2 16 g of a 25% strength by weight aqueous solution of the crosslinking agent 1 were slowly added at 25 ° C. to 40 g of a 25% strength by weight aqueous solution of the condensate 3. The reaction mixture was then heated to 65 ° C. and stirred at that temperature for 1 hour. An insoluble gel was formed.

Example 3 6 g of a 50% strength by weight aqueous solution of crosslinking agent 1 were slowly added at 25 ° C. to 25 g of a 25% strength by weight aqueous solution of condensate 1. The reaction mixture is then heated to 65 ° C,
The mixture was stirred at this temperature for 2 hours. The resulting viscous solution was cooled to ambient temperature and sulfuric acid was added to adjust the pH to 7.5 to give a highly viscous orange solution.

Example 4 6 g of a 50% strength by weight aqueous solution of crosslinking agent 1 were slowly added at 25 ° C. to 20 g of a 50% strength by weight aqueous solution of condensate 1. The reaction mixture is then heated to 65 ° C,
The mixture was stirred at this temperature for 2 hours. An insoluble gel was formed.

Example 5 3.13 g of an aqueous solution of crosslinking agent 2 having a concentration of 80% by mass was slowly added at 25 ° C. to 50 g of an aqueous solution of condensate 2 having a concentration of 50% by mass. An insoluble gel was formed.

Example 6 2.5 g of Crosslinker 3 were slowly added at 25 ° C. to 50 g of a 50% strength by weight aqueous solution of Condensate 2. An insoluble gel was formed.

Example 7 2.5 g of Crosslinking Agent 3 were slowly added to 50 g of a 50% strength by weight aqueous solution of Condensate 2. An insoluble gel was formed.

[Procedure for Amendment] Submission for translation of Article 34 Amendment of Patent Cooperation Treaty

[Submission date] April 19, 2001 (2001.4.19)

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be amended] Claims

[Correction method] Change

[Contents of correction]

[Claims]

23. A halogen-free cross-linking agent (ii) comprises: (1) ethylene carbonate, propylene carbonate and urea, (2) monoethylenically unsaturated carboxylic acid and its ester, amide and anhydride, at least dibasic Saturated carboxylic acid or polycarboxylic acid and its ester, amide and anhydride, (3) Polyether diamine, alkylene diamine, polyalkylene polyamine, alkylene glycol or polyalkylene glycol, or a mixture thereof and monoethylenically unsaturated carboxylic acid or mono A reaction product of an ester, amide or anhydride of an ethylenically unsaturated carboxylic acid, the functional product being at least 2
Reaction product having one ethylenically unsaturated double bond, or carboxamide, carboxyl or ester group, (4) Reaction product of dicarboxylic acid ester having at least two aziridino groups with ethyleneimine, (5) 15. The method of claim 14 selected from the group consisting of diepoxides, polyepoxides, diisocyanates and polyisocyanates, and mixtures of said crosslinkers.

[Procedure amendment]

[Submission date] January 7, 2002 (2002.1.7)

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be amended] Claims

[Correction method] Change

[Contents of correction]

[Claims]

─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Dieter Beck             Limburger Hof, Federal Republic of Germany             Zeppelin Strasse 3 (72) Inventor Jürgen Decker             Federal Republic of Germany Speyer Mate             In Luther-Strasse 8 (72) Inventor Ralph Nellenberg             Butterbornma, Federal Republic of Germany             Intour Strasse 28 F term (reference) 4J001 DA01 DB02 EA15 EA33 EA37                       GE11 JB01

Claims (23)

[Claims] 1. (i) a homocondensate of a basic amino acid, a condensate of a mixture of two or more basic amino acids and / or a cocondensate of a compound capable of cocondensing with a basic amino acid, and (ii) at least 2 A crosslinked condensed basic amino acid-containing polymer obtained by reacting with at least one crosslinker having one functional group. 2. The crosslinked condensed basic amino acid-containing polymer according to claim 1, wherein the basic amino acid is selected from the group consisting of lysine, arginine, ornithine and tryptophan. 3. The crosslinked condensed basic amino acid-containing polymer according to claim 1, wherein the basic amino acid is lysine. 4. The co-condensable compound is selected from the group consisting of carboxylic acid group-containing compounds, carboxylic acid anhydrides, diketene, amines, lactams, alcohols, alkoxylated alcohols and alkoxylated amines. A crosslinked condensed basic amino acid-containing polymer of. 5. The condensed basic amino acid-containing polymer is (a) lysine alone or (b) palmitic acid, stearic acid, lauric acid, octanoic acid, propionic acid,
A crosslinked condensation according to claim 1, obtained by combining and condensing with at least one compound selected from the group consisting of acetic acid, 2-ethylhexanoic acid, adipic acid, succinic acid, citric acid and mixtures thereof. Basic amino acid-containing polymer. 6. The condensed basic amino acid-containing polymer is (a) lysine and (b) 1,6-hexamethylenediamine, octylamine, aminocaproic acid,
Aminolauric acid, .epsilon.-caprolactam, laurolactam, and _{C 14 /} C ₂ 2 _- obtained by condensing in combination with at least one compound selected from the group consisting of alkyl diketenes, crosslinking of claim 1, wherein Condensed basic amino acid-containing polymer. 7. The condensed basic amino acid-containing polymer is 300 to 1,000,000.
The crosslinked condensed basic amino acid-containing polymer according to claim 1, having a weight average molecular weight of. 8. The crosslinked condensed amino acid-containing polymer according to claim 5, wherein the molar ratio of (a) to (b) is 100: 1 to 1:10. 9. The crosslinked condensed amino acid-containing polymer according to claim 5, wherein the molar ratio of (a) to (b) is greater than 1. 10. The cross-linking agent (ii) is α, ω-dichloroalkane, vicinal dichloroalkane, epihalohydrin, bischlorohydrin ether of polyol, bischlorohydrin ether of polyalkylene glycol, chloroformate, phosgene, The crosslinked condensed amino acid-containing polymer of claim 1, selected from the group consisting of halogen-free crosslinkers and mixtures thereof. 11. A halogen-free cross-linking agent (ii) is (1) ethylene carbonate, propylene carbonate and urea, (2) monoethylenically unsaturated carboxylic acid and its ester, amide and anhydride, at least dibasic Saturated carboxylic acid or polycarboxylic acid and its ester, amide and anhydride, (3) Polyether diamine, alkylene diamine, polyalkylene polyamine, alkylene glycol or polyalkylene glycol, or a mixture thereof and monoethylenically unsaturated carboxylic acid or mono A reaction product of an ester, amide or anhydride of an ethylenically unsaturated carboxylic acid, the functional product being at least 2
Reaction product having one ethylenically unsaturated double bond, or carboxamide, carboxyl or ester group, (4) Reaction product of dicarboxylic acid ester having at least two aziridino groups with ethyleneimine, (5) 11. The crosslinked condensed amino acid-containing polymer of claim 10, selected from the group consisting of diepoxides, polyepoxides, diisocyanates and polyisocyanates, and mixtures of said crosslinkers. 12. The crosslinker (ii) is selected from the group consisting of epichlorohydrin, bischlorohydrin ethers of polyethylene glycol having 2 to 40 ethylene glycol units and mixtures thereof. A crosslinked condensed basic amino acid-containing polymer of. 13. The crosslinked product according to claim 1, wherein at least one crosslinking agent (ii) is used in an amount of 0.001 to 100 mol% relative to 1 mol of the amino group in the condensed basic amino acid-containing polymer. Polymer containing condensed basic amino acid. 14. (i) a homo-condensate of a basic amino acid, a co-condensate of a mixture of two or more amino acids and a co-condensate of a compound capable of co-condensing with a basic amino acid, and (ii) at least two A process for producing a crosslinked basic amino acid-containing polymer, which comprises reacting with at least one crosslinker containing a functional group. 15. The method according to claim 14, wherein the basic amino acid is lysine. 16. The co-condensable compound is selected from the group consisting of carboxylic acid group-containing compounds, carboxylic acid anhydrides, diketene, amines, lactams, alcohols, alkoxylated alcohols and alkoxylated amines. Manufacturing method. 17. The condensed basic amino acid-containing polymer is (a) lysine alone or (b) palmitic acid, stearic acid, lauric acid, octanoic acid, propionic acid,
15. The process according to claim 14, obtained by combining with at least one compound selected from the group consisting of acetic acid, 2-ethylhexanoic acid, adipic acid, succinic acid, citric acid and mixtures thereof, and condensing. 18. The condensed basic amino acid-containing polymer comprises: (a) lysine; (b) 1,6-hexamethylenediamine, octylamine, aminocaproic acid;
Aminolauric acid, .epsilon.-caprolactam, laurolactam, and _{C 14 /} C ₂ 2 _- obtained by condensing in combination with at least one compound selected from the group consisting of alkyl diketene claim 14 A process according. 19. The condensed basic amino acid-containing polymer is 300 to 10,000.
15. The method of claim 14, having a weight average molecular weight of 00. 20. The process according to claim 17, wherein the molar ratio of (a) to (b) is 100: 1 to 1:10. 21. The process according to claim 18, wherein the molar ratio of (a) to (b) is greater than 1. 22. The crosslinking agent (ii) is α, ω-dichloroalkane or vicinal dichloroalkane, epihalohydrin, bischlorohydrin ether of polyol, bischlorohydrin ether of polyalkylene glycol, chloroformate, phosgene, 15. A method according to claim 14 selected from the group consisting of halogen-free crosslinkers and mixtures thereof. 23. A halogen-free cross-linking agent (ii) comprises: (1) ethylene carbonate, propylene carbonate and urea, (2) monoethylenically unsaturated carboxylic acid and its ester, amide and anhydride, at least dibasic Saturated carboxylic acid or polycarboxylic acid and its ester, amide and anhydride, (3) Polyether diamine, alkylene diamine, polyalkylene polyamine, alkylene glycol or polyalkylene glycol, or a mixture thereof and monoethylenically unsaturated carboxylic acid or mono A reaction product of an ester, amide or anhydride of an ethylenically unsaturated carboxylic acid, the functional product being at least 2
Reaction product having one ethylenically unsaturated double bond, or carboxamide, carboxyl or ester group, (4) Reaction product of dicarboxylic acid ester having at least two aziridino groups with ethyleneimine, (5) 15. The method of claim 14 selected from the group consisting of diepoxides, polyepoxides, diisocyanates and polyisocyanates, and mixtures of said crosslinkers.