EP1518881A2 - Polymère modifié par un poyether utlisé comme adjuvant dans la fabrication du cuir - Google Patents

Polymère modifié par un poyether utlisé comme adjuvant dans la fabrication du cuir Download PDF

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Publication number
EP1518881A2
EP1518881A2 EP04021173A EP04021173A EP1518881A2 EP 1518881 A2 EP1518881 A2 EP 1518881A2 EP 04021173 A EP04021173 A EP 04021173A EP 04021173 A EP04021173 A EP 04021173A EP 1518881 A2 EP1518881 A2 EP 1518881A2
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Prior art keywords
mol
acid
formula
units
polyether
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German (de)
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EP1518881A3 (fr
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Jürgen Dr. Reiners
Martin Dr. Kleban
Nils Dr. Brinkmann
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Lanxess Deutschland GmbH
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Bayer Chemicals AG
Lanxess Deutschland GmbH
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Publication of EP1518881A2 publication Critical patent/EP1518881A2/fr
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    • C—CHEMISTRY; METALLURGY
    • C14—SKINS; HIDES; PELTS; LEATHER
    • C14C—CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
    • C14C9/00—Impregnating leather for preserving, waterproofing, making resistant to heat or similar purposes

Definitions

  • the invention relates to polyether-modified polymers, a process for their preparation, these containing dispersions and their use as leather auxiliaries.
  • Such aids are usually used in the leather manufacturing process during tanning or retanned used.
  • To increase the leather use value is at many leather articles, e.g. in footwear leather or furniture and automotive leather, a well-balanced Ratio of material properties asked. These include features such as a high abundance, a pleasantly soft grip, excellent grain and grain tightness and an optimal coloring result.
  • EP 0 959 091 A1 or EP-A-959 090 disclose hydrophobically modified polyaspartic ester amides derived copolymers containing aspartic acid aspartic acid ester, Aspartic acid amide units, other proteinogenic or non-proteinogenic amino acid units and iminodisuccinate units as structural units.
  • Such products are called Auxiliaries recommended for various applications, wherein the dispersing and complexing effect in cosmetic emulsions or foaming properties Surfactant preparations are in the foreground.
  • the mandatory ester groups in the product are not ideal for leather applications because of their sensitivity to hydrolysis.
  • the foaming Effect of the products described is a property that is suitable for use in Nachgerbflotten leather production is also undesirable.
  • aspartic acid-containing polymers are for other applications for example from DE-A-19 545 678, EP-A-884 344, US-A-5 292 858, DE-A-4 300 020, WO 94/01486, US-A-5 286 810, US-A-5 408 028, US-A-5 357 004, US-A-6 306 378 and WO 00/37023 known.
  • radicals W are derived, for example, from the hydrocarbon skeletons of the polycarboxylic acids from the following group or their anhydrides:
  • Dicarboxylic acids or dicarboxylic acid anhydrides such as maleic acid, maleic anhydride, fumaric acid, Itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, tricarboxylic acids or their Anhydrides such as 1,2,3-propanetricarboxylic acid, citric acid, 1,2,4-cyclohexanetricarboxylic acid, 1,2,3-cyclohexanetricarboxylic acid, 2,3,5-norbornane tricarboxylic acid, trimellitic acid, trimellitic anhydride, and tetracarboxylic acids or their anhydrides or bisanhydrides such as 1,2,3,4-butanetetracarboxylic acid, 1,2,4,5-cyclohexanetetracarboxylic acid, 2,3,5,6-norbornanetetracarboxylic acid, 2,3,5,6-norbornanetetracarboxylic anhydride, Derive pyrom
  • Suitable radicals M + are, for example, hydrogen (H + ), hydroxyethylammonium, bis (2-hydroxyethyl) ammonium, tris (2-hydroxyethyl) ammonium, triethylammonium, tetraethylammonium, ammonium, butylammonium, N-methyl-N-bis (2-hydroxyethyl) ammonium, N-dimethyl-N- (2-hydroxyethyl) -ammonium, N-diethyl-N- (2-hydroxyethyl) -ammonium, benzyltrimethylammonium, morpholinium, hexadecylammonium, oleylammonium, octadecylammonium, as well as alkali ions such as sodium, potassium, lithium. Preference is given to sodium, potassium, hydrogen, ammonium, 2-hydroxyethylammonium, triethylammonium, tetraeth
  • radicals -NR 1 R 2 are derived by abstraction of an H atom of monofunctional polyethers with primary amino groups based on oxirane, methyloxirane, tetrahydrofuran or mixtures thereof, wherein the polyether segments can be arranged randomly or in blocks. Particular preference is given to radicals derived from monofunctional aminopolyethers which have polyoxypropene and / or polyoxyethene units in any desired order.
  • Such products are known per se and are available, for example, under the name Jeffamine® M-600, Jeffamine® M-1000, Jeffamine® M-2070, Jeffamine® M-2005 (products of Huntsman).
  • radicals -NR 1 R 2 which are derived by abstraction of an H atom of monofunctional polyethers with primary amino groups, resulting from the reaction of polyisocyanates with monofunctional hydroxyl-terminated polyethers and subsequent hydrolysis. Instead of the hydrolysis, it is also possible to react the remaining isocyanate groups, for example with excess primary diamines, so that a free amino group remains.
  • polyisocyanates for the preparation of monofunctional polyethers with primary Amino groups may be mentioned: isophorone diisocyanate, bis (isocyanatocyclohexyl) methane, Xylylene diisocyanate, 1,4-bis (isocyanatomethyl) cyclohexane, hexamethylene diisocyanate, Toluylene diisocyanate, diphenylmethane-4,4'-diisocyanate, diphenylmethane-2,4'-diisocyanate, the Isocyanurate, biuret, allophanate, urea, uretdione group-containing oligomers of the aforementioned Diisocyanates.
  • monofunctional hydroxyl-functional polyethers are those of polyurethane chemistry per se known alkoxylation based on monofunctional starter alcohols by Polymerization of ethene oxide or propene oxide on e.g. Methanol, ethanol or butanol, etc. are accessible, called.
  • Suitable diamines which may be mentioned are: 1,2-ethylenediamine, 1,2-propylenediamine, 1,3-propylenediamine, 1,4-butylenediamine, 1,2-dimethyl-1,2-ethylenediamine, 1,6-hexamethylenediamine, isophoronediamine, Bis (aminocyclohexyl) methane, xylylenediamine.
  • the structural unit of the formula I corresponds to the formula II
  • the polymer according to the invention contains ester-containing units of the formula wherein W has the above meaning and R is any organic radical of less than 5 wt .-%, in particular less than 2 wt .-%, preferably less than 1 wt .-%, based on the copolymer.
  • Preferred units of the formula Ia in particular units of the formula Ib, contain, as the radical of the formula -NR 3 R 4, one which is derived from compounds of the formula HNR 3 R 4 , the following compounds being preferred as such: secondary, preferably primary Amines, such as 2-ethylhexylamine, 1-octylamine, 1-decylamine, 1-undecylamine, 1-dodecylamine, tetradecylamine, perfluorohexylethylamine, N-aminoethyl-N-methylperfluorooctylsulfonamide, hexadecylamine, octadecylamine, octadecenylamine, tallow fatty amine, hydrogenated tallow fatty amine, oleylamine, 12-hydroxyoctadec-9-enylamine, Eicosanylamin, dehydroabietylamine, Stearoyloxypropy
  • -NR 3 R 4 is C 8 - to C 30 -alkyl.
  • the polyether units may be in the main chain of the copolymer or in the side chain or in Main chain and side chain can be installed.
  • Suitable polyether units are derived from the side chain of monofunctional amino-polyethers or for the backbone of diamino-polyethers.
  • hydroxy-terminated building blocks such as polycarbonate diols, Polyesterdiols, Polyestercarbonatdiole and Polyethercarbonatdiole, for example, by Reaction of the aforementioned hydroxyl-functional polyethers and other conventional building blocks such Ethylene glycol, propylene glycol, butanediol, neopentyl glycol, hexanediol, caprolactone, by polycondensation with diphenyl carbonate or dimethyl carbonate (with elimination of Phenol or methanol) and / or by polycondensation with adipic acid, glutaric acid, terephthalic acid, Isophthalic acid (with elimination of water) or mixtures thereof derived, as Raw materials suitable for the preparation of diamino-polyethers, preferably those described in the Polymer chain incorporated built-in polyether units.
  • diisocyanates and diamines for the Implementation of these building blocks are the already mentioned diisocyanates and diamines.
  • Especially Preferred reactants for this synthesis are polyethers based on oxirane and Methyloxirane having two hydroxyl end groups, diisocyanates such as hexamethylene diisocyanate and Isophorone diisocyanate and diamines such as ethylenediamine, hexamethylenediamine and isophoronediamine.
  • diaminofunktioneller polyether Another possibility for the preparation of suitable diaminofunktioneller polyether is the Base-catalyzed addition of acrylonitrile to hydroxyl-terminated polyethers and subsequent Hydrogenation of the nitrile groups to amino groups.
  • Another possibility is the catalytic amination of the polyethers with ammonia.
  • these polyurethanes, polyureas or polyurethane ureas may also be any other polymer diols customary in polyurethane chemistry (C 4 polyethers, polyesters, polycarbonates, polyestercarbonates) , low molecular weight diols (butanediol, hexanediol, the adducts of ethylene oxide or propylene oxide with tallow fatty acid or hydrogenated tallow fatty amine), hydrophilicizing agents (dimethylolpropionic acid, the adduct of sodium bisulfite with a 1,4-butenediol-initiated propylene oxide polyether having a molecular weight between 300 and 1000 g / mol), diamines (hydrazine hydrate, ethylenediamine, hex
  • polyethene oxide and / or polypropene oxide units containing diamines with an average molecular weight of 200 to 6000 g / mol.
  • the prefix "poly" in the above-mentioned raw material designations preferably has one Value that the corresponding monoamines or diamines are a preferred number average certain molecular weight of 200 to 4000 g / mol, preferably from 400 to 2500 g / mol have.
  • Preferred copolymers according to the invention contain structural units of the formula (IIa) and (IIb)
  • copolymers according to the invention may contain further of the units a), b) and c) contain various bivalent bridge members V in the main chain.
  • Preferred copolymers contain 0 to 10 mol% of such divalent bridge members V in the Main chain, based on the sum of all units of formula I, wherein V is a bivalent Rest is derived from polycarboxylic acids, polyamines, lactams or aminocarboxylic acids derives.
  • the bridge members V are preferably derived from polyamines, in particular diamines, or polycarboxylic acids, in particular dicarboxylic acids, and of aminocarboxylic acids or their Lactams off.
  • These units may be contained in the main chain and then preferably serve for Linking the units of the formula I, Ia, II, IIa, IIb with one another in any order. she may also serve to link different polyether units that are in the backbone are installed. It can also be several divalent radicals from the above group of Polycarboxylic acids, polyamines, lactams and aminocarboxylic acids condensed and thus to longer Brückengliedem be installed.
  • Preferred bridge members V are derived from the following polyamines (V-1): ethylenediamine, 1,2- and 1,3-propylenediamine, 1,6-hexamethylenediamine, isophoronediamine, bisaminocyclohexylmethane, diethylenetriamine, triethylenetetramine, bishexamethylenetriamine, diaminocyclohexane, Xylylenediamine, bis-3-aminopropyl ether, bis-aminomethyltricyclo [5.2.1.0 2,6 ] decane.
  • Preference is given to diamines, in particular ethylenediamine and propylenediamine, isophoronediamine, hexamethylenediamine.
  • Preferred bridge members V are derived from the following polycarboxylic acids (V-2): oxalic acid, Malonic acid, succinic acid, glutaric acid, adipic acid, sebacic acid, tartaric acid, cyclohexane-1,2-dicarboxylic acid, Cyclohexane-1,3-dicarboxylic acid, cyclohexane-1,4-dicarboxylic acid, 1-cyclohexene-1,2-dicarboxylic acid anhydride, 4-cyclohexene-1,2-dicarboxylic acid, 4-cyclohexene-1,2-dicarboxylic anhydride, 3-cyclohexene-1,2-dicarboxylic anhydride, Norbornane-2,3-dicarboxylic acid, norbornane-2,3-dicarboxylic anhydride, 5-norbornene-2,3-dicarboxylic acid, phthalic acid, isophthalic acid, terephthalic acid, Na
  • Preferred bridge members V are derived from the following aminocarboxylic acids (V-3): glycine, Alanine, aspartic acid, glutamic acid, other naturally occurring amino acids, Aminopropionic acid, aminobutyric acid, aminohexanecarboxylic acid. Preference is given to glycine, Aspartic acid, glutamic acid.
  • Preferred bridge members V are derived from the following lactams (V-4): butyrolactam, Caprolactam, laurolactam. Preference is given to caprolactam.
  • Suitable longer bridge members V can also be obtained by condensation or cocondensation reaction be obtained from the aforementioned building blocks V-1 to V-4. These bridge members are due to the terminal amino groups and / or carboxyl groups in the preparation of (Co) polymers according to the invention are preferably incorporated in their main chain.
  • the (co) polymers according to the invention preferably have the following radicals which can be defined via the starting materials and preferably from the optionally used polycarboxylic acids, dicarboxylic acids, polyamines, diamines, lactams, ammonia, amines, polyethers and those for the preparation of monofunctional and difunctional Derive monomer used in polyether.
  • the end groups may be based on the following radicals: alkyl radicals, alkoxy radicals, alkylamino radicals, cycloalkylamino radicals or aliphatic amino-substituted aralkyl radicals, polyetheramino radicals, N-substituted maleimide radicals, OH, COOH, CONH 2 and NH 2 groups, and radicals, which are derived from aspartic acid and its derivatives.
  • Preferred end groups are, for example, hydroxyl, amino, carboxyl and its salts, carboxamide, N-substituted maleimide, N-substituted aspartic acid amide, methyl, ethyl, butyl, methyloxy, ethoxy, butoxy, butylamino, hexylamino, decylamino, dodecylamino, tetradecylamino, hexadecylamino, octadecylamino , Eicosanylamino, N-methyl-N-octadecylamino, bis (octadecyl) amino, benzylamino and 2-hydroxyethylamino.
  • Particularly preferred polyether-modified copolymers according to the invention having a number average molecular weight of 500 to 50,000, preferably 1 500 to 30 000 g / mol, in particular those which 5 to 35 mol% of structural units of the formula IIa and Contain from 15 to 90 mol% of structural units of the formula IIb, in each case based on the sum of the structural units of the formula I.
  • copolymers of the invention which contain from 10 to 90% by weight, in particular from 30 to 80 wt .-% of structural units of the formula I, each based on the copolymer.
  • the copolymer according to the invention preferably consists of more than 95% by weight, in particular to more than 98 wt .-% of the structural units of the formula I, Ia, the polyether units and optionally divalent bridge members.
  • the radical -NR 3 R 4 in formula Ia in particular Ib, represents radicals which are derived from the following amines HNR 3 R 4 : dodecylamine, tetradecylamine, hexadecylamine, octadecylamine, hexadecenylamine, octadecenylamine, tallow fatty amine, hydrogenated Tallow fatty amine, N-methyl-octadecylamine, branched aliphatic amines derived from the corresponding Guerbet alcohols, such as 2-butyl-1-octylamine, 2-hexyl-1-octylamine, 2-butyl-1-decylamine, 2- Hexyl-1-decylamine, 2-octyl-1-decylamine, 2-hexyldodecylamine, 2-octyldodecylamine
  • radical -NR 3 R 4 in formula Ia, in particular Ib has the same meaning as stated for the embodiment A1 above.
  • the radical -NR 5 R 6 is derived from amines of the formula HNR 5 R 6 which correspond to the abovementioned monofunctional amino-polyethers, in particular primary amino-polyethers.
  • Suitable polycarboxylic acids of component A-2 are: oxalic acid, Malonic acid, succinic acid, glutaric acid, adipic acid, sebacic acid, tartaric acid, cyclohexane-1,2-dicarboxylic acid, Cyclohexane-1,3-dicarboxylic acid, cyclohexane-1,4-dicarboxylic acid, 1-cyclohexene-1,2-dicarboxylic acid anhydride, 4-cyclohexene-1,2-dicarboxylic acid, 4-cyclohexene-1,2-dicarboxylic anhydride, 3-cyclohexene-1,2-dicarboxylic anhydride, Norbornane-2,3-dicarboxylic acid, norbornane-2,3-dicarboxylic anhydride, 5-norbornene-2,3-dicarboxylic acid, phthalic acid, phthalic anhydride, isophthalic acid, Terephthalic acid, na
  • Suitable polyamines of component B-2) are: ethylenediamine, 1,2-propylenediamine, 1,3-propylenediamine, 1,4-butylenediamine, 1,6-hexamethylenediamine, isophoronediamine, bis (aminocyclohexyl) methane, diethylenetriamine, triethylenetetramine , Bishexamethylenetriamine, the various isomers of diaminocyclohexane, xylylenediamine, bis-3-aminopropyl ether, bis-aminomethyltricyclo [5.2.1.0 2,6 ] decane.
  • Suitable aminocarboxylic acids of component A-3 are, for example: alanine, glycine, Glutamic acid, aspartic acid, or other naturally occurring amino acids, aminopropionic acid, Aminobutyric acid, aminohexanoic acid.
  • reaction of components A-1) (optionally in the presence of A-2) and / or A-3)) with ammonia B-1), preferably aqueous ammonia solution, and optionally the Polyether diamines B-2) and optionally polyamines B-3) to the polycarboxylic acid amide ammonium salts takes place in the temperature range between 5 ° C and 100 ° C, preferably 20 to 80 ° C.
  • ammonia B-1 preferably aqueous ammonia solution
  • the metering of component B-2) takes place before, during or after the reaction with Ammonia, preferably in the presence of solvents.
  • Suitable solvents are N-methylpyrrolidone, pyrrolidone, ethylene glycol, dimethylacetamide, dimethylformamide, diethylene glycol, Triethylene glycol, ethanol, butanol, n-propanol, isopropanol, ethoxy-propanol, Butoxy propanol.
  • Particularly preferred solvents are ethylene glycol and diethylene glycol, Pyrrolidone and N-methylpyrrolidone. Especially preferred is diethylene glycol.
  • the condensation C) is preferably carried out with heating of the after the reaction of A-1) (optionally in the presence of A-2) and / or A-3)) with B-1) (and optionally B-2) as well as if appropriate B-3)), the reaction mixture is heated to between 70 and 200 ° C, preferably 90 to 170 ° C, wherein the water from the added in the previous step Ammonia solution and the reaction water formed in the polycondensation is distilled off.
  • the polycondensation is preferably carried out under reduced pressure in the range between 0.1 mbar and 800 mbar.
  • the reaction of the resulting polycondensate with amines of the formula HNR 3 R 4 D-1) and optionally with polyether-containing amines of the formula HNR 5 R 6 D-2) takes place at temperatures above 120 ° C., preferably 120 to 170 ° C.
  • the reaction is carried out in the presence of a solvent.
  • the above-mentioned solvents are suitable.
  • the reaction E) with a ring-opening base takes place during or after the dispersion in Water.
  • the dissolved melt of the reaction mixture which after the Reaction with D-1) and optionally D-2) is obtained, dispersed in water at 70 to 140 ° C and simultaneously carrying out the reaction with the ring-opening base, wherein a dispersion of the Copolymers is obtained.
  • the amount of the base is preferably chosen so that a homogeneous, readily stirrable dispersion is obtained. Preference is given to so much ring-opening base added that after the reaction with D-1) and optionally D-2) in the copolymer still existing Imid Quiltmaschineen be hydrolyzed.
  • the reaction E) is preferably carried out in the presence of derivatives of C 1 -C 18 monocarboxylic acids.
  • Particularly preferred for the production of the products of the invention more than 95 wt .-%, in particular more than 98 wt .-% of building blocks used from the group of maleic anhydride, maleic acid, fumaric acid, ammonia, polyether-containing diamines having an average molecular weight of 200 to 6 000 g / mol, amines of the formula HNR 3 R 4 and polyether-containing amines of the formula HNR 5 R 6 are selected.
  • polyether-containing diamines in step B-2), it is preferably a polymer structure in which one or more units of formula I on Polyether units are interconnected, or in a block-like structure, wherein the Linkage both on both sides via a carboxylic acid amide bond (head-to-head linkage) or on both sides in the sense of a Michael addition to still existing double bonds in Maleic acid units (tail-tail linkage) or via a mixture of both Binding types (head-tail linkage) can be done.
  • the groups I can do the Change orientation in the main chain of the copolymer.
  • additional Components in A-2) and / or A-3) and / or B-3)
  • bivalent Bridge members V within the polymer chain.
  • Preferred polyether-modified polymers according to embodiment A1 have as weight average by gel permeation chromatography (calibrated with polystyrene) certain molecular weights of 500 to 30,000, preferably 1,000 to 20,000, in particular 1,000 to 10,000 g / mol.
  • the Structural units are preferably arranged alternately, block-wise or statistically distributed.
  • the polymers may also contain branching points which, for example, in the case of Maleic anhydride by incorporation of iminodisuccinate residues or incorporation of nitrilotrisuccinate residues or with concomitant use of tri- or tetracarboxylic acids or by Michael addition of polyamines to the double bond of maleimide end groups and others Reaction of the resulting secondary amine can arise.
  • branching points which, for example, in the case of Maleic anhydride by incorporation of iminodisuccinate residues or incorporation of nitrilotrisuccinate residues or with concomitant use of tri- or tetracarboxylic acids or by Michael addition of polyamines to the double bond of maleimide end groups and others Reaction of the resulting secondary amine can arise.
  • branching points which, for example, in the case of Maleic anhydride by incorporation of iminodisuccinate residues or incorporation of nitrilotrisuccinate residues or with concomit
  • branched structures are those copolymers which account for ⁇ 5 mol% (based on structural units I) are preferred have branched structures to have sufficient solubility or miscibility with water to ensure.
  • monofunctional Compounds in the condensation reaction it may be possible through the use of monofunctional Compounds in the condensation reaction to reduce the molecular weights so that a higher proportion of branching becomes available.
  • Suitable monofunctional compounds for controlling the molecular weights are monocarboxylic acids such as formic acid, Acetic acid, propionic acid, benzoic acid, cyclohexanecarboxylic acid, stearic acid, or monoamines, such as for example, butylamine, dibutylamine, aminoethanol, hexylamine, dodecylamine, hexadecylamine, Octadecylamine, octadecenylamine, and the above-mentioned monofunctional polyetheramines.
  • monocarboxylic acids such as formic acid, Acetic acid, propionic acid, benzoic acid, cyclohexanecarboxylic acid, stearic acid
  • monoamines such as for example, butylamine, dibutylamine, aminoethanol, hexylamine, dodecylamine, hexadecylamine, Octadecylamine, octadecenyl
  • a 1 is a method for producing the polyether-modified Polymers particularly preferred, which is characterized in that maleic acid or maleic anhydride A-1) - or optionally mixtures thereof with other dicarboxylic acids, Tricarboxylic acid (anhydrides) n and / or tetracarboxylic acid (bisanhydrides) n from the group of Building blocks leading to the trivalent radicals W in formula (also process component A-1) in the presence of a solvent such as diethylene glycol, ethylene glycol, propylene glycol, N-methylpyrrolidone, Pyrrolidone with ammonia and a diaminofunctional polyether B-2) with a average molecular weight of 200 to 6,000 g / mol simultaneously or sequentially in the temperature range between 5 ° C and 100 ° C, the resulting reaction mixture with elimination of water in a vacuum at temperatures between 80 ° C and 200 ° C, preferably 80 ° C to 160 ° C, condensed and the
  • maleic acid or maleic anhydride are reacted with ammonia and the polyether-containing diamines B-2) (hereinafter referred to as "polyetherdiamine” for short) and the reaction mixture is subsequently condensed with elimination of water.
  • polyetherdiamine polyether-containing diamines
  • the copolymer contains predominantly succinimide structural units, amide groups and optionally also free carboxyl groups, which may be present in the form of the ammonium salts or the polyetheramine salts.
  • the resulting polysuccinimide-containing polycondensate is preferably with a C 1 -C 60 -alkylamine D-1), in particular a C 8 -C 60 -alkylamine, particularly preferably a C 12 -C 30 -alkylamine, if appropriate in the presence of a monofunctional polyetheramine D -2), and then dispersed in water in the presence of a base. Subsequently, after pH adjustment to a pH between 6 and 10 bleached with hydrogen peroxide and excess oxidant removed by means of a reducing agent.
  • the reaction of polysuccinimide with amines is known in principle; see. eg DE-OS 2 253 190, EP-A 274 127, EP-A 406 623 and EP-A 519 119, US-A 3 846 380, US-A 3 927 204 and US-A 4 363 797; P. Neri et al., Macromol. Syntheses 8 , 25.
  • the reaction of the polyether-modified polysuccinimides is preferably carried out in organic solvents.
  • Suitable such are, for example, lactams such as caprolactam, N-methylpyrrolidone, N-methylcaprolactam, polyalkylenediols and their mono- and diethers, such as ethylene glycol, diethylene glycol, triethylene glycol, ethylene glycol dimethyl and diethyl ether and diethylene glycol monoethyl ether, and also pyrrolidinone, N-methyl-pyrrolidinone, dimethylformamide and dimethyl sulfoxide.
  • Preferred solvents are diethylene glycol, ethylene glycol and pyrrolidinone. The solvent content will usually not exceed 30 wt .-%, based on the total reaction mixture.
  • the reaction with amines HNR 3 R 4 and optionally with monofunctional amino-polyethers HNR 5 R 6 is carried out in a temperature range from 100 ° C to 180 ° C, preferably from 120 to 150 ° C, the reaction times being generally from 3 to 24 Hours, preferably 4 to 8 hours.
  • the inventive polyether-modified (co) polymers by opening the remaining incorporated Succinimidringe using bases and water.
  • the ring-opening bases are preferably alkali metal hydroxides, carbonates and bicarbonates, in particular sodium and potassium hydroxide and Sodium carbonate, as well as ammonia and amines, including those used as reactants Amines - in question.
  • the concomitant use of an organic solvent, so that the mixture remains stirrable.
  • the polyether-modified copolymers according to the invention are obtained.
  • the ring opening by simultaneous addition of water and base to the melt or the solution of the polymer at 70 ° C to 140 ° C.
  • pH adjustment to a pH between 6 and 10 bleached with hydrogen peroxide and excess oxidant removed by means of a reducing agent.
  • the invention furthermore relates to those obtainable by the processes according to the invention (Co) polymers.
  • polyether-modified polymers according to the invention are preferably self-dispersing. But it can also be used external dispersants become; As such, in principle cationic, anionic and nonionic dispersants come in Question, as they e.g. in "Methods of Organic Chemistry” (Houben-Weyl), 4th Edition, Volume XIV / 1, Georg Thieme Verlag, Stuttgart 1961, p. 190 f. are described.
  • Preferred dispersants include, for example, C 8 -C 18 -n-alkyl sulfates, C 8 -C 18 -n-alkylbenzenesulfonates, C 8 -C 18 -n-alkyl-trimethylammonium salts, n-di-C 8 -C 18 -alkyl- dimethylammonium salts, C 8 -C 18 -n-alkyl-carboxylates, C 8 -C 18 -n-alkyl-dimethylamine oxides, C 8 -C 18 -n-alkyldimethylphosphine oxides and - preferably - oligoethyleneglycol-mono-C 6 -C 18 -alkyl ethers with an average of 2 to 30 ethoxy groups per molecule.
  • n-alkyl radicals may also be replaced by partially unsaturated linear aliphatic radicals.
  • Particularly preferred dispersants are oligoethylene glycol mono-C 10 -C 14 -alkyl ethers having on average 4 to 12 ethoxy groups per molecule, in particular oligoethylene glycol mono-C 12 -alkyl ethers having an average of 8 ethoxy groups per molecule.
  • Preferred dispersants further include oleic acid, oleic acid sarcosides, ricinoleic acid, stearic acid, Fatty acid partial esters of polyols such as glycerol, trimethylolpropane or pentaerythritol and their Acylation, ethoxylation and propoxylation products, e.g.
  • Glycerol monostearate and monooleate, sorbitan monostearate and monooleate, sorbitan tristearate and trioleate and their reaction products with dicarboxylic acid anhydrides such as succinic anhydride, maleic anhydride, Phthalic anhydride or tetrahydrophthalic anhydride, reaction products of bis (hydroxymethyl) tricyclodecane and maleic anhydride or succinic anhydride and their derivatives, preferably in the form of their alkali or ammonium salts.
  • Particularly preferred dispersants are salts of long-chain fatty acids, preferably from Oleic acid and an aminoalcohol, preferably hydroxyethylamine, bishydroxyethylamine or Trishydroxyethylamine.
  • aqueous dispersant For the preparation of an aqueous dispersion, it is generally advisable to prepare the dispersant, during or after the dispersion to the reaction mixture with stirring at temperatures of 70 ° C to 140 ° C to dose. It is also possible, the reaction mixture in an aqueous Disperse dispersant solution.
  • the dispersant content is generally not more than 30, preferably 3 to 15 wt .-%, based on finished dispersion.
  • the solids content of the dispersions is preferably 5 to 60 wt .-%, particularly preferably 10 bis 40% by weight.
  • the mean particle size of the dispersed polyaspartic acid amides is Generally 50 to 1000, preferably 50 to 700 and in particular 80 to 400 nm.
  • the pH during the dispersion is preferably between 5 and 11, particularly preferably 6 to 10, set.
  • the Reduce the particle size of the disperse phase In order to facilitate the penetration of the aids into the leather, it may be desirable to use the Reduce the particle size of the disperse phase.
  • This can be a pre-emulsion already obtained under high shear rate in known dispersing machines such as jet dispersers with suitable Nozzles, high-pressure emulsifying machines or mixers with rotor-stator principle aftertreated become. It is also possible the dispersion in situ in the chambers or nozzles of the mentioned devices to create.
  • the dispersion time can be between a few minutes and up to 4 hours.
  • the Dispersion is preferably carried out in a temperature range between 20 and 75 ° C.
  • the invention therefore further relates to aqueous dispersions containing the inventive Polymer, preferably with solids contents of 10 to 60 wt .-%.
  • the dispersions with a Solids content below 35 wt .-% are usually in the form of low-viscosity emulsions.
  • the pH of the dispersions is preferably 4.5 to 12, preferably in the pH range of 4.5 to 10, especially at 5 to 8.
  • the bleaching can be carried out oxidatively or reductively.
  • the oxidative bleaching Suitable oxidizing agents are hydrogen peroxide or alkali or Ammonium persulfate in aqueous solution.
  • the bleach can be in the temperature range between 20 and 90 ° C, preferably between 30 and 60 ° C are performed. Unused bleach will subsequently destroyed with a reducing agent.
  • Suitable reducing agents are, for example Sodium hydrogen sulfite solution, or peroxide-decomposing enzyme formulations such as BAYLASE® EPK (product of BAYER AG).
  • the decomposition of residues of the oxidizing agent is advantageous in Temperatures between 20 and 45 ° C in the pH range between 5 and 8 performed.
  • the invention further relates to the use of the polymer according to the invention Treatment of leather and its precursors from the leather manufacturing processes.
  • Precursors off the leather manufacturing processes are, for example, raw hides, Pollen mateiral, wet white, wet blue, and all substrates during retanning, staining and greasing in the trough to the finished crust.
  • Preferred substrates are wet blue or Wet white.
  • Especially during or after a Tanning with mineral tanning agents, vegetable tanning agents and syntans are the inventive (Co) polymers used advantageously.
  • tanning agents are in this case called: titanium, zirconium, iron, aluminum tannins, aldehydes, isocyanates, blocked Isocyanates, epoxides, oxazolidines, etc.
  • the leather is preferably with an aqueous liquor containing these compounds by application by rolling or in a Container, preferably in a tannery, brought into contact. After the treatment becomes the leather generally acidified and dried.
  • Aids are used. These include, for example: polymeric retanning agents based on of known polyacrylate dispersions, leather dyes, vegetable tanning agents, Syntans, Fatliquoring agents, neutral oils, water repellents. Only such combinations can be used be with the dispersions of the polyether-modified polymers of the invention are compatible.
  • the use of additives with an anionic charge is usually unproblematic at a liquor pH of 6 to 4.5. These additives can be particularly beneficial though also used before or after the application of the polymers to be used according to the invention become.
  • Suitable vegetable tanning agents are e.g. Chestnut extracts, Mimosa, Quebracho etc.
  • Suitable syntans are, for example, synthetic organic tanning agents known to the person skilled in the art (cf. K. Faber, "Tanning, Tanning and Retanning", Frankfurt 1984).
  • Suitable fatliquoring agents are, for example, oxidized and / or sulfoxidized, preferably halogen-free C 16-30 hydrocarbons and / or C 32-100 waxes, with C 8-30 alcohols partially esterified C 2-54 polycarboxylic acids, such as octadecyl citric acid, glutaric acid monooleate, with C 12- 24- fatty acids at least partially esterified C 2-54 polyols such as sorbitan, glycerol, trimethylolpropane, pentaerythritol monostearate, monooleate, distearate, dioleate, monolaurate, etc.
  • C 2-54 polycarboxylic acids such as octadecyl citric acid, glutaric acid monooleate
  • C 12- 24- fatty acids at least partially esterified C 2-54 polyols such as sorbitan, glycerol, trimethylolpropane, pentaeryth
  • Suitable neutral oils are, for example, animal and / or vegetable fats and oils, such as claw oil, Fish oil, sunflower oil, rapeseed oil, coconut oil, palm kernel oil, soybean oil, preferably non-halogenated Fatty acid ester, oleic acid methyl ester, paraffin oil, tallow.
  • Suitable water repellents are silicone emulsions containing perfluoroalkyl groups
  • Polymer dispersions including polyurethanes containing perfluoroalkyl groups are silicone emulsions containing perfluoroalkyl groups.
  • the polymers according to the invention also give the above without further aids Categories a pleasantly soft grip. Moreover, it is surprising that the dyeing Properties and the levelness are improved and the leather at the same time a very high abundance have.
  • a reduction is sufficient the pH by addition of a carboxylic acid.
  • the fleet attrition is usually so good that it is also possible to add the acid into the keg without draining the liquor.
  • Preferred pH values should be less than 4.5 to achieve sufficient fixation in the leather. Especially preferred is the range of 3.0 to 4.5.
  • a fixation with a carboxylic acid can also by addition of polyvalent Metal compounds, such as aluminum, titanium, zirconium or chromium salts or carboxylates, or Alkoxides are fixed in the liquor.
  • polyvalent Metal compounds such as aluminum, titanium, zirconium or chromium salts or carboxylates, or Alkoxides are fixed in the liquor.
  • the pH the liquor is preferably from 5 to 7 at the beginning of the treatment.
  • the pH may optionally be be corrected by addition of bases such as ammonia.
  • the treatment is preferably carried out at a temperature between 20 and 80 ° C, preferably at 35 to 60 ° C. After the treatment presents In general, the pH of the liquor is about 4 to 6.
  • the pH can be reduced to 3 to 4.5.
  • Preferred carboxylic acid for Acidification is formic acid.
  • Fatliquoring agents for example, fat-modified aminocarboxylic acid derivatives (for example LEVOTAN® L, commercial product of Bayer AG) or hydrophobically modified polyacrylate dispersions (for example, Lubritan® WP, commercial product of Rohm and Haas) become.
  • a preferred polyacrylate-based fatliquoring agent is also XERODERM® P-AF (Commercial product of BAYER AG).
  • silicone agents or fluorocarbon resins For higher demands on the hydrophobic effect it is possible to have a final one Hydrophobing with silicone agents or fluorocarbon resins perform. These agents are known in the art and can after a running time of the fleet of preferably 30 minutes be dosed into the same barrel. Usually anionic agents are preferred because they are with the dispersions of the polyether-modified polyaspartic acid amides to be used according to the invention are well tolerated. Particularly good results in terms of Hydrophobic effect are achieved, for example, with silicone emulsions (for example XERODERM® S-AF, product of BAYER AG). It is also possible to use other commercial ones To combine silicone emulsions with the products of the invention.
  • silicone emulsions for example XERODERM® S-AF, product of BAYER AG. It is also possible to use other commercial ones To combine silicone emulsions with the products of the invention.
  • the invention further relates to leather containing the polymers of the invention.
  • TANIGAN® WLF Condensation product of aromatic sulfonic acids Synthetic tanning agent, Bayer AG
  • TANIGAN® BN Condensation product of aromatic sulfonic acids Synthetic tanning agent, Bayer AG
  • BAYKANOL® SL Condensation product of aromatic sulfonic acids Synthetic dyeing auxiliaries, Bayer AG
  • RETINGAN® RD fl Synthetic dyeing auxiliaries
  • Formaldehyde condensation product Resin tanning agent, Bayer AG; Lubritan® GX Polymer retanning agent with softening properties, Rohm and Haas; BAYKANOL® Licker CAR Synthetic fatliquoring agent; Product of Bayer AG; BAYGENAL® Gray L-NG Dye; Bayer AG TANIGAN® AN Condensation product of aromatic sulfonic acids and lignosulfonate; Synthetic tanning agent, Bayer AG; TANIGAN® PAK-S Condensation product of aromatic sulfonic acids; Synthetic Tannery Aid, Bayer AG; RETINGAN® R 7 Formaldehyde condensation product with dicyandiamide; Resin tanning agent, Bayer AG; LEVOTAN® C Polymeric retanning agent, Bayer AG; BAYKANOL® Licker PAN Softening oil based on marine oils; Bayer AG; BAYKANOL® Licker NB Synthetic fatliquoring agent; Bayer AG
  • the reactor is then gradually evacuated to 200 mbar and with simultaneous Distillation of water is further heated until a bottom temperature of 130-140 ° C is reached and no more reaction water passes.
  • RESPUMIT S a defoamer
  • hydrogen peroxide 35% within 20 minutes at 60-70 ° C are added. It is stirred for 4 hours at 65 ° C and then cooled to 30-38 ° C.
  • 30-38 ° C add 1.0 g of RESPUMIT S followed by 3.0 g of BAYLASE EPK in 2 portions. The mixture is stirred for 3 hours at 35 ° C, cooled below 30 ° C and filled through a 100 micron filter.
  • 109.45 g of the precursor A described above (0.5 mol) are initially charged at 140.degree. Then 175 g (0.175 mol) of a heated to 80 ° C melt of polyether 2 are added. The mixture is stirred for a further 4 hours at 140 ° C and then cooled to 115 ° C. Then 14.25 g of oleic acid are added, stirred for 5 minutes, and starting at 115 ° C and the highest stirrer speed, a solution of 465 g of water and 6.1 g of ethanolamine dosed within 60 minutes, the batch is cooled to 65 ° C. After addition of 0.5 g of RESPUMIT S, 20.0 g of 35% hydrogen peroxide are added at 65 ° C. within 10 minutes.
  • Example 2 Analogously to Example 2, 109.45 g of precursor A (0.5 mol) are reacted with 45 g (0.075 mol) of polyether 3 at 140 ° C. for 4 hours. After cooling to 65 ° C., 8.4 g of oleic acid are added and a solution of 280 g of water and 3.6 g of ethanolamine are metered in over the course of 60 minutes. It is stirred for 10 minutes. Then at 65 ° C 20.0 g of hydrogen peroxide 35% are added within 10 minutes. The mixture is stirred for 3 hours at 65.degree. At 35 ° C, 0.2 g RESPUMIT S and then 1.5 g BAYLASE EPK are added in 2 portions within 30 minutes.
  • the precursor B is produced, with the change that 337.0 g (1.25 mol) Armeen HT, which was previously melted at 80 ° C, can be used.
  • the Reaction time is 3 hours at 140 ° C. 1229.3 g reddish brown melt are discharged and crushed after cooling.
  • 125 g (0.125 mol) of polyether 2 and 12.8 g (0.125 mol) of 3-aminopropyl-dimethylamine are metered into 122.9 g of precursor B (0.5 mol) analogously to Example 4, and the mixture is stirred at 140 ° C. for 6 hours , Then 8.4 g of oleic acid are added at 125 ° C, stirred for 5 minutes and starting at 125 ° C and the highest stirrer speed, a solution of 465 g of water and 3.63 g of ethanolamine dosed within 60 minutes and stirred for another 30 minutes, the Approach cooled to 65 ° C. At 65 ° C 20.0 g of hydrogen peroxide 35% are added within 10 minutes.
  • the products with polyether 1 and polyether 2 should be emphasized.
  • the installation the polyether in the main chain surprisingly gives the products with the most favorable allround properties.
  • the product properties can be determined by a suitable choice of Proportions of the components to the requirements for the desired leather articles to adjust.
  • the leathers with a test product according to example 1 (leather A), a test product according to example 1 of DE-A 195 28 782 (leather B) and without test product (leather C) were evaluated for their properties as follows: Grain / Millkom: A / B comparably good, C is significantly worse than A / B. Softness: A is almost as soft as B. C is significantly harder than A / B. A is significantly fuller than B, followed by C with significantly less fullness. Color accuracy / depth: A / B have a comparable color depth and levelness, C is much brighter. Overall rating: A / B get the best score in terms of softness, fullness, and Millkom, with A being fuller and more compact than B, but B softer than A. C is far worse than the other leathers.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Polyethers (AREA)
EP04021173A 2003-09-17 2004-09-07 Polymère modifié par un poyether utlisé comme adjuvant dans la fabrication du cuir Withdrawn EP1518881A3 (fr)

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DE10342926A DE10342926A1 (de) 2003-09-17 2003-09-17 Polyethermodifizierte Polymere als Lederhilfsmittel

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WO2007003264A2 (fr) * 2005-07-02 2007-01-11 Lanxess Deutschland Gmbh Derives d'acide polyaspartique dans des produits de revetement contenant du polysiloxane
CN104099433A (zh) * 2014-07-14 2014-10-15 陕西科技大学 一种树枝状-线性聚酰胺加脂复鞣剂的制备方法

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BRPI0919300A2 (pt) * 2008-09-26 2015-12-22 3M Innovative Properties Co materiais poliméricos, método de preparo dos mesmos, artigo e composições
US10324747B1 (en) * 2016-12-13 2019-06-18 EMC IP Holding Company LLC Distributed configuration checking and troubleshooting in data center using best practices rules
CN111777738B (zh) * 2020-07-28 2021-10-15 陕西科技大学 一种植物油衍生物改性的两性聚氨酯复鞣剂及其制备方法

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