EP2726522A1 - Composition à base de composés contenant des groupes sulfonate de carbamoyle - Google Patents

Composition à base de composés contenant des groupes sulfonate de carbamoyle

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Publication number
EP2726522A1
EP2726522A1 EP12733655.0A EP12733655A EP2726522A1 EP 2726522 A1 EP2726522 A1 EP 2726522A1 EP 12733655 A EP12733655 A EP 12733655A EP 2726522 A1 EP2726522 A1 EP 2726522A1
Authority
EP
European Patent Office
Prior art keywords
acid
water
composition according
reaction
bisulfite
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP12733655.0A
Other languages
German (de)
English (en)
Inventor
Jürgen REINERS
Christopher Tysoe
Holger Lütjens
Dietrich Tegtmeyer
Nils Brinkmann
Claus Dreisbach
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Lanxess Deutschland GmbH
Original Assignee
Lanxess Deutschland GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from EP11171954A external-priority patent/EP2540753A1/fr
Application filed by Lanxess Deutschland GmbH filed Critical Lanxess Deutschland GmbH
Priority to EP12733655.0A priority Critical patent/EP2726522A1/fr
Publication of EP2726522A1 publication Critical patent/EP2726522A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
    • C08G18/0819—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups
    • C08G18/0828—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups containing sulfonate groups or groups forming them
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/089—Reaction retarding agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/80—Masked polyisocyanates
    • C08G18/8061—Masked polyisocyanates masked with compounds having only one group containing active hydrogen
    • C08G18/8083—Masked polyisocyanates masked with compounds having only one group containing active hydrogen with compounds containing at least one heteroatom other than oxygen or nitrogen
    • 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
    • C14C3/00—Tanning; Compositions for tanning
    • C14C3/02—Chemical tanning
    • C14C3/08—Chemical tanning by organic agents

Definitions

  • the invention relates to a composition based on carbamoylsulfonate-containing compounds, a process for their preparation and their use as a reaction component for amino-containing compounds, for example as leather auxiliaries, there in particular as Vorgerbstoff, tanning, retanning
  • Polyisocyanates having a functionality greater than 2 are useful as crosslinkers for polymeric materials and have been used successfully for example for a long time in the coating of, for example, metallic surfaces. Polyisocyanates can be used according to the field of application in unmodified form for purely organic coating compositions. Due to the great demand for solvent-free systems, coating agents have been developed which are solvent-free or low-solvent systems. For the crosslinking of the polymeric binders contained in such coating compositions, polyisocyanates are desired which can be dispersed in water. However, the crosslinkers must be dispersed in water directly before use, since the NCO groups are not stable in water and thus have a limited pot life.
  • polyisocyanates can be used for crosslinking polymers containing amino groups, for example copolymers based on monomers such as isobutene, butadiene, acrylonitrile, isoprene, styrene and acrylic monomers, where the amino groups can be introduced by subsequent reaction of a copolymer or by copolymerization.
  • Suitable amino-containing polymers are also polycondensates or polyaddition products. For certain applications, it is advantageous or even essential to use crosslinkers which are used in
  • DE-B 10 2006 056 479 discloses bisulfite-blocked polyisocyanates which can be prepared in the presence of solvents. Also known from US4413997 blocked isocyanates. The use of internal or external emulsifiers as auxiliaries for the synthesis of aqueous bisulfite-blocked polyisocyanates is also known from EP-A 0 690 135, EP-A 0 814 168 and EP-A-1647563.
  • composition which comprises a) at least one carbamoylsulfonate-containing compound and b) at least one carboxylic acid containing less than 0.001% by weight, based on the composition of emulsifier, wherein the compounds containing carbamoylsulfonate groups of component a) a reaction product of at least one organic polyisocyanate and at least one bisulfite and / or disulfite, characterized in that the organic polyisocyanate has a molecular weight of less than 400 g / mol and NCO groups bound to aliphatics or cycloaliphatic, in particular 1, 4-diisocyanatobutane , 1, 6-diisocyanatohexane (HDI), l, 5-diisocyanato-2,2-dimethylpentane, 2,2,4- and 2,4,4-trimethyl-l, 6-diisocyanatohexane (TMHI), 1, 3 -
  • Carbamoylsulfonate-containing compounds are understood as meaning those having the following structural unit:
  • K + is a cation equivalent
  • diisocyanates Preference is given to using the above diisocyanates.
  • monofunctional aliphatic isocyanates such as, for example, butyl isocyanate, hexyl isocyanate, cyclohexyl isocyanate, stearyl isocyanate or dodecyl isocyanate and / or polyisocyanates having an average NCO functionality of 2.2 to 4.2.
  • the higher-functionality polyisocyanates are preferably trimeric 1,6-diisocyanatohexane, trimeric 1,2-, 1,3- or 1,4-bis (isocyanatomethyl) cyclohexane, trimeric 1, 2-, 1, 3.
  • the use of monofunctional and of more than difunctional isocyanates in both cases is preferably limited to amounts of not more than 10 mol%, based on all polyisocyanates. However, very particular preference is given to the abovementioned aliphatic, cycloaliphatic and araliphatic diisocyanates.
  • hexamethylene diisocyanate (HDI), Diisocyanato-cyclohexane, 1,2-, 1, 3- and 1,4-bis (isocyanatomethyl) -cyclohexane and any mixtures of isomers, 1, 2-, 1, 3- and 1,4-bis (isocyanatoethyl) cyclohexane and any mixtures of these isomers, 1,2-, 1, 3- and 1,4-bis (isocyanato-n-propyl) -cyclohexane and any mixtures of these isomers, 2,4'- and 4,4'-diisocyanato-dicyclohexylmethane , 1-isocyanatopropyl-4-isocyanatomethylcyclohexane and 1-somere and 1-isocyanato-3,3,5-trimethyl-5-
  • HDI hexamethylene diisocyanate
  • Diisocyanato-cyclohexane 1,2-, 1, 3- and 1,4-bis (
  • IPDI Isocyanatomethylcyclohexane
  • Preferred bisulphites and / or disulphites are their alkali metal or ammonium salts, in particular the sodium salts of sulphurous or disulphurous acid, i. Sodium hydrogen sulfite (NaHSC> 3) or sodium disulfite (Na2S2Ü5) in question.
  • the other alkali and ammonium salts of these acids namely potassium bisulfite, potassium bisulfite, lithium bisulfite, lithium disulfite, ammonium bisulfite, Ammoniumdisulf t and simple tetraalkylammonium salts of these acids such as tetramethylammonium bisulfite, tetraethylammonium bisulfite, etc.
  • Salts are preferably used as aqueous solutions with solids contents of 5 to 40% by weight.
  • the compounds containing carbamoyl groups are based on aliphatic polyisocyanates such as hexamethylene diisocyanate, isophorone diisocyanate, bis (isocyanato) cyclohexane, 1,2,2,1,3- and 1,4-bis (isocyanatomethyl) cyclohexane and also any desired mixtures of isomers, 1, 2-, 1, 3- and 1,4-bis (isocyanatoethyl) cyclohexane and any mixtures of these isomers, 1,2-, 1, 3- and 1,4-bis (isocyanato-n-propyl cyclohexane and any desired mixtures of these isomers, isocyanatopropyl-4-isocyanatomethylcyclohexane and isomers, 2,4 'and 4,4'-diisocyanato-dicyclohexylmethane or nonyltriisocyanate, and mixtures thereof,
  • the carbamoyl-containing compounds are particularly preferably based on hexamethylene diisocyanate (HDI), 1, 2-, 1, 3- and 1, 4-bis (isocyanatomethyl) cyclohexane and mixtures of these isomers.
  • Component a) preferably has the following structural units in the case of diisocyanates as raw materials:
  • Alkali metal cation such as sodium, potassium or lithium.
  • radicals Q are, for example, tetramethylene, pentamethylene, hexamethylene, trimethylhexamethylene, octamethylene, decamethylene or dodecamethylene, which may be by one or more identical or different heteroatoms or 1,2-, 1, 3 or 1,4-cyclohexylene, and 1, 2, 1, 3, and 1, 4-cyclohexylene dimethylene or 3,3,5-trimethyl-1, 5-cyclohexylene-5-methylene.
  • n has the meaning of 1 to 5, very particularly preferably n has the value 1.
  • component a) can also have as raw materials the following structural units:
  • X is a group of the formula -NH-CO-SO 3 K or a bivalent, optionally, preferably carboxyl-substituted bridge member which is different from Q, and
  • K + , Q, and n have the meaning given above.
  • Atoms of the hydroxyl group of the hydroxycarboxylic acid results.
  • Suitable compounds of component b) are in particular mono- or polycarboxylic acids, preferably hydroxypolycarboxylic acids. Examples which may be mentioned are: formic acid, acetic acid, oxalic acid, glyoxylic acid, malonic acid, lactic acid, tartaric acid, maleic acid, glutaric acid,
  • Phthalic acid, adipic acid, malic acid, succinic acid, citric acid, or polycarboxylic acids such as (co) polymers of (meth) acrylic acid, maleic acid, crotonic acid or itaconic acid or derivatives thereof with optionally further monomers such as ethene, propene, styrene, hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxyethyl acrylate, Hydroxypropyl acry l at, 4-hydroxybutyl vinyl ether, in particular those having an average molecular weight (weight average MW) of 500 to 100000 g / mol, in particular 500 to 30,000 g / mol.
  • weight average MW average molecular weight
  • component b) at least one carboxylic acid, preferably oxalic acid, succinic acid, glutaric acid, or adipic acid, in particular at least one hydroxy-polycarboxylic acid, preferably citric acid, tartaric acid or lactic acid or mixtures thereof.
  • Suitable components b) are also aminocarboxylic acids such as glycine, alanine, lysine,
  • Aspartic acid glutamic acid, leucine, isoleucine, tyrosine, proline, tryptophan, etc. but also peptides, proteins or protein hydrolysates based on vegetable and animal proteins or collagen-containing materials such as soy protein hydrolysates, hydrolyzates of skin, hair and pumice Waste, white waste, leather waste, hydrolyzates of keratinous materials, polyaspartic acid, polyglutamic acid, and products obtained by polycondensation of
  • component b) are derivatives of cellulose, oligosaccharides or monosaccharides which contain a carboxyl group, for example carboxymethylcellulose, oxidized starch, preferably having a molecular weight of less than 100,000 g / mol, in particular less than 20,000 g / mol, gluconic acid, glucuronic acid, oxidatively degraded anionic starch, alginates, pectins, etc.
  • Preferred component b) is also a carboxylic acid group-containing reaction product of a hydroxypolycarboxylic acid and a polyisocyanate.
  • Suitable hydroxypolycarboxylic acids are, in particular, those mentioned above, in particular citric acid.
  • Suitable polyisocyanates are in particular the abovementioned, in particular the preferred diisocyanates, in particular hexamethylene diisocyanate.
  • a preferred component b) preferably contains 0 to 5 wt .-%, preferably 0 to 2 wt .-%, based on the composition, of a reaction product of a carboxylic acid and the polyisocyanate used.
  • composition according to the invention is preferably essentially free of emulsifiers, ie compounds which reduce the interfacial tension between an organic and an aqueous phase, so that an oil-in-water emulsion can form, in particular it is emulsifier-free.
  • emulsifiers ie compounds which reduce the interfacial tension between an organic and an aqueous phase, so that an oil-in-water emulsion can form, in particular it is emulsifier-free.
  • Preferred further additives of component c) may preferably comprise or not contain fatliquoring agents, dedusting agents, buffers and / or fillers.
  • Emulsifiers are for the purposes of this invention preferably no additives.
  • Fatliquoring agents are preferably substances based on biological, mineral or synthetic oils which can be provided with hydrophilic groups in order to improve the usability in water, eg. B. by complete or partial sulfation, sulfitation, carboxylation or phosphating.
  • Suitable fillers are preferably inert inorganic salts and organic polymers, for.
  • sulfates such as sodium sulfate or calcium sulfate, talc, silica compounds, starch or lignosulfonates into consideration.
  • Suitable buffers are those which can be adjusted and stabilized by addition in a sufficient amount of a pH range, in particular a pH range of 1 to 5, preferably 2.0 to 3.5.
  • Suitable buffers for this are preferably mixtures of compounds of component c) and their salts in question.
  • Preferred salts are in particular alkali metal salts, preferably sodium or potassium salts.
  • Examples of preferred dedusting agents are alkoxylates of aromatic compounds or polyethers or certain diesters. Examples which may be mentioned specifically: ethoxylates, propoxylates or mixed polyethers based on EO / PO, hydroquinone or phenol-styrene being mentioned as aromatic compounds, polyethylene glycol having an average molecular weight of from 100 to 800, polypropylene glycol having an average molar mass of from 100 to 800, EO / PO mixed polyether having an average molecular weight of 100 to 800, monoalkyl ethers or dialkyl ethers of the abovementioned polyethers, where the alkyl radical may have 1 to 4 carbon atoms. Dustproofing agents based on mineral oil are also suitable.
  • Dedusting agents are preferably used in an amount of 0 to 5.0, preferably 0.1 to 2.0%, based on inventive solid material.
  • the composition according to the invention may also contain or not contain further additives, the amount of these additives including that of component c) preferably being up to 30% by weight.
  • the inventive solid composition preferably contains
  • component b From 65 to 99.9% by weight, in particular from 78 to 99.9% by weight, of component a), from 0.1 to 15% by weight, in particular from 0.1 to 10% by weight, of component b),
  • the solid composition contains 0 to 5 wt .-%, in particular 0 to 2 wt .-% water (residual moisture).
  • the weight ratio of component a) to b) is preferably 1: 1 to 10: 1, in particular 1: 1 to 1000: 1.
  • the aqueous composition according to the invention preferably contains
  • the aqueous composition according to the invention preferably contains from 35 to 90% by weight, in particular from 50 to 80% by weight, of water.
  • compositions of the invention may be present as a solid, particulate material or as a liquid, in particular aqueous composition.
  • composition of the invention is preferably in the form of a solid, particulate material having a melting point of greater than 20 ° C., preferably greater than 60 ° C., in particular greater than 100 ° C.
  • "Particulate” is in particular a material having an average particle size of 0.1 ⁇ m to 1000 ⁇ m, preferably 1 to 800 ⁇ m, in particular 50 to 300 ⁇ m, the mean being based on the mass (weight average) of all particles. Volume average) can be calculated therefrom by analytical methods and vice versa The average particle size can be determined, for example, microscopically.
  • the particulate solid material according to the invention has a residual moisture content of 0 to 10 wt .-%, in particular 0 to 5 wt .-%, particularly preferably 0 to 2 wt .-%, based on the material.
  • the particulate solid material according to the invention is based on any, preferably a spherical or spherical shape-like or derived particle structure. There are also agglomerates of particles from the mentioned forms in the range specified
  • the material may be present as a powder, granules or as so-called.
  • Micro granules, as it is z. B. is obtained in the one-fluid nozzle spray drying.
  • composition of the invention as an aqueous composition, in particular aqueous solution, preferably having a solids content of 10 to 49.9 wt .-%, preferably from 20 to 49.9 wt .-%.
  • the composition according to the invention contains less than 1% by weight of organic or inorganic tannins, preferably less than 0.1% by weight, in particular the composition is essentially free of organic or inorganic tannins, with very particular preference it is free of organic or inorganic tannins.
  • the solid composition according to the invention additionally contains 0 to 15% by weight, in particular 0 to 10% by weight, very particularly preferably 0.01 to 5% of component c), in each case based on the solid composition.
  • the aqueous composition according to the invention additionally contains 0 to 7.5 wt .-%, in particular 0 to 5 wt .-%, most preferably 0.005 to 2.5% of component c), each based on the aqueous composition.
  • the formulation contains a percentage of components a) to c) which has been reduced by the proportion of water.
  • the material according to the invention also contains reaction products of polyisocyanates or polyisocyanate bisulphite adducts and citric acid.
  • reaction products containing urethane groups and carbamoylsulfonate groups are obtainable by reaction of an excess of polyisocyanate with component b) and subsequent reaction with a bisulfite and / or disulfite.
  • Examples of compounds of this type are bisurethanes of 1 mol of hexamethylene diisocyanate and 2 mol of citric acid or, for example, the monourethane of 1 mol of hexamethylene diisocyanate and 1 mol of citric acid, with residual NCO groups reacting in situ with bisulfite and / or disulfite to give the carbamoylsulfonate group.
  • compositions are those containing compounds containing Carbamoylsulfonat phenomenon- by reacting at least one organic isocyanate with at least one bisulfite and / or disulfite and at least one hydroxy-polycarboxylic acid (component b), in particular citric acid, preferably in an amount of 0.05 to 3, preferably 0.1 to 2% wt .-%, based on the composition were obtained.
  • the preferred materials of the present invention contain less than 5%, especially less than 1% of urea group-containing dimeric, trimeric or polymeric carbamoylsulfonates which may be by-produced by hydrolysis of the polyisocyanates in the synthesis.
  • composition according to the invention preferably contains
  • the invention further relates to a process for the preparation of the invention
  • Composition characterized in that the component a) with component b), if appropriate, mixed with further additives.
  • the invention further relates to a process for the preparation of the composition according to the invention which is characterized in that at least one organic polyisocyanate having a molecular weight of less than 400 g / mol with aliphatics or
  • Cycloaliphaten bonded NCO groups with at least one bisulfite and / or disulfite in the presence of water and with simultaneous action of shear forces, wherein the carboxylic acid of component b) and optionally further additives before, during or after the bisulfite and / or disulfite Reaction is added and the resulting reaction mixture is then optionally dried.
  • the invention further relates to a process for the preparation of a solid, particulate composition according to the invention, which comprises reacting at least one organic polyisocyanate with at least one bisulfite and / or disulfite in the presence of water and with the simultaneous action of shear forces, and the resulting aqueous solution then dried, wherein the carboxylic acid of component b) is added before, during or after the bisulfite reaction or only after drying.
  • the sonotrode is immersed in the reaction medium, or high-pressure homogenizers which can be designed, for example, for high pressures (eg 10 to 1000 bar) or jet dispersers using nozzles which are operated, for example, in a pressure range in the middle range (eg 10 to 100 bar).
  • high pressures eg 10 to 1000 bar
  • jet dispersers using nozzles which are operated, for example, in a pressure range in the middle range (eg 10 to 100 bar).
  • reaction components are fed continuously into a plant part, which allows an intimate mixture of the components, and the reaction mixture at elevated temperatures, preferably from 20 to 100 ° C and at the Temperature-adapted short residence time, for example, is reacted in a microreactor to the final product, the resulting reaction mixture, optionally after adjusting the temperature, pH, concentration and addition of further components is fed into a drying apparatus, and after evaporation of the water, the solid, particulate material is discharged from the plant and filled in appropriate containers.
  • Suitable microreaction systems are, for example, those from Ehrfeld BTS GmbH or GEA / Niro.
  • reaction temperature 20 to 100 ° C.
  • the residence time in the reaction system can be shortened by increasing the reaction temperature to a few minutes.
  • a solution of alkali bisulfite or disulfite is prepared in water.
  • This aqueous solution and the polyisocyanate are now separated and in a stoichiometric ratio of bisulfite groups (HSO 3 -) to NCO groups of 1.0: 1.0 to
  • a mixer which is integrated into a microreaction system.
  • microreaction plants with a modular structure from Ehrfeld BTS GmbH can be used for the continuous production.
  • the two liquid streams are preferably metered with pulsation-free working high-pressure pumps via inlet modules in the microreaction system.
  • the liquid streams supplied to the mixer are intimately mixed by the microstructure of the mixer, passed through a heat exchanger and then in a microreactor at a temperature between 20 and 120 ° C, preferably with a residence time of a few seconds to 15 minutes, reacted to give complete conversion of the NCO groups.
  • the aqueous product solution is cooled by a heat exchanger and pumped via an outlet module from the microreaction system into a separate container.
  • the solution may now be mixed continuously in this container with further additives of component b) and optionally c) and passed directly into a spray dryer.
  • the metering rate of the raw materials in the microreaction plant is thereby advantageously adapted to the speed of discharge of the spray-dried material from the spray dryer.
  • the inlet temperature is preferably set at 120 to 200 ° C, preferably at 130 ° C to 180 ° C.
  • the solid material has a residual moisture content of more than 2%, it may be advantageous to reduce the residual moisture to a value below 2% in a downstream, likewise continuously operated drying step, for example in a fluidized-bed dryer or paddle dryer.
  • the material obtained is then filled continuously into corresponding containers. It may be advantageous in the continuous process, for example, before, during or after spray drying to add a dedusting agent to obtain a dust-free product that is free-flowing and can be easily dosed by the user.
  • the resulting solid material is very soluble in water (at 20-25 ° C) and is characterized as a solid material by excellent storage stability even at high temperatures (60 ° C).
  • the per se known apparatuses such as spray dryers, thin film evaporators, evaporation screws, apparatus for cooling crystallization or vacuum dryers such as apparatuses for freeze drying or vacuum dryers with forced conveying.
  • spray dryers optionally also spray dryers with integrated fluidized bed drying.
  • a drying of the predried material may be required, so that the maximum residual moisture content is kept as low as possible.
  • the residual moisture is usually in the range of 0 to 5%, preferably between 0 and 2%, particularly preferably between 0 and 1%, based on solid material.
  • a suitable process for the drying is in particular the spray-drying, preferably single-substance spray drying by means of high-pressure or swirl chamber nozzles or spray drying by means of sputtering disks, freeze-drying with upstream or downstream granulation or dry work-up, built-up granulation, for example after the plate or drum granulation process optionally with partly pre-dried product, Fluidized bed drying and granulation, mixed agglomeration and drying optionally in combination with fluidized bed or fluidized bed drying. Furthermore, processes such as mixed agglomeration in suspension with optionally downstream fluidized bed or fluid bed drying, granulation by means of paste deformation and subsequent post-drying and come Comminution or pelletizing and steam jet agglomeration in question.
  • Combinations of said methods are also possible. It is also possible to dry the aqueous solution by evaporating the water by depressurizing a solution subjected to high pressure with carbon dioxide, whereby fine powders are also obtained. Particularly preferred are the methods of spray drying by means of high-pressure or swirl chamber nozzles, spray drying with integrated and / or downstream fluidized-bed agglomeration and / or drying, built-up granulation by the plate method and fluidized-bed granulation and drying.
  • the solid carbamoylsulfonate group-containing compounds can be prepared by various methods. Three methods are briefly described below.
  • a process according to the invention for the preparation of the solid composition according to the invention is preferably characterized in that a precipitating agent such as acetone, ethanol, isopropanol, methyl ethyl ketone is added to the liquid reaction mixture obtained by one of the processes described above and the precipitate is dried.
  • a precipitating agent such as acetone, ethanol, isopropanol, methyl ethyl ketone
  • Method 1 Precipitation of the Carbamoylsulfonat phenomenon-containing compound from aqueous solution.
  • the precipitation is carried out by mixing the aqueous solution with an excess of an at least partially water-immiscible non-solvent for component a), preferably ethanol, methanol, n-propanol, isopropanol, methoxypropanol, acetone, methyl ethyl ketone, ethyl acetate. Most preferred is acetone.
  • the aqueous solution to be used preferably has a concentration of from 10 to 50%, particularly preferably from 25 to 45%.
  • aqueous solutions which are prepared by reacting the polyisocyanate with the alkali salt of bisulfite / disulfite, wherein 1.00 to 1, 10 mol of bisulfite equivalents are preferably used per 1.00 NCO equivalent.
  • aqueous solutions which are prepared by reacting the polyisocyanate with the bisulfite / disulfite alkali salt, with 1.00 to 1.05 mol of bisulfite equivalents being preferably used per 1.00 NCO equivalent.
  • aqueous solutions prepared by reacting the polyisocyanate with the bisulfite / disulfite alkali salt are used, wherein per 1, 00 NCO equivalent, preferably 1, 00 to 1, 10 moles of bisulfite equivalents, wherein a proportion of component b) of at least 10% based on component b), already added during the reaction and the Rest after the implementation.
  • the aqueous solutions are particularly preferably prepared by reacting the polyisocyanate with the bisulfite / disulfite alkali salt, 1.00 mol of bisulfite being present per 1.00 NCO equivalent.
  • the organic solvent for precipitating the solid carbamoylsulfonate group-containing compound is preferably used in excess.
  • the weight ratio of water to solvent is 1: 1 to 1:10, more preferably 1: 1 to 1: 5. It is possible to add the organic solvent to the aqueous solution containing the carbamoylsulfonate group-containing compound or the aqueous solution inversely to add to the submitted organic solvent. In general, the mixture is stirred during the precipitation.
  • the precipitated product is then separated by decantation, centrifugation or filtration, preferably by suction using filter media, for example by means of a vacuum chute, a pressure filter or a chamber press, then optionally washed with fresh solvent and then dried.
  • the separation process can also be continuous if a combination with the above-described continuous preparation of the aqueous solution is provided.
  • the drying of the solid material is preferably carried out in vacuo at a temperature of -20 to + 40 ° C.
  • the aqueous solution to be used preferably has a concentration of between 10% and 60%, more preferably from 25 to 45%, based on the sum of component a) and b) and optionally c).
  • the aqueous solution to be used preferably has a pH of 2.0 to 6.0, more preferably a pH of 2.3 to 4.0, most preferably a pH of 2.5 to 3.5.
  • the precipitation with organic solvent is preferably carried out below the boiling point of the organic solvent, more preferably below 50 ° C, most preferably in the temperature range of 0 ° C and 40 ° C.
  • the temperature at the beginning of the drying is kept as low as possible and increased towards the end of the drying to the final temperature. This gentle procedure ensures that hydrolysis of the carbamoylsulfonate group-containing compound during work-up is avoided.
  • the yield is almost quantitative when using acetone in most cases.
  • the filtrate can then be replenished.
  • the combined filtrates can then be worked up in a suitable form, for example by a vacuum distillation, to recover the organic solvent.
  • the aqueous solution to be used preferably has a concentration of 10 to 60%, particularly preferably 35 to 50%.
  • the aqueous solution to be used preferably has a pH of 2.0 to 6.0, more preferably a pH of 2.3 to 4.0, most preferably a pH of 2.5 to 3.5.
  • the aqueous solution fed to the dryer is preferably adjusted to a temperature below 90 ° C., very particularly preferred is a temperature range from 10 ° C. to 80 ° C., in particular from 20 to 60 ° C.
  • the temperature setting of the solution supplied to the spray dryer is preferably carried out shortly before the inlet nozzle of the spray dryer. It is particularly advantageous to pass the solution for heating through a separate heat exchanger in order to achieve a brief heating of the material.
  • Suitable for drying are the technical apparatuses customary in drying technology. Particularly preferred are methods in which spray dryers are used. All known process variants are suitable.
  • spray drying towers are suitable with single-fluid nozzles, in which the aqueous solution is injected into the head of the spray dryer by means of overpressure, wherein the particle size is adjustable, inter alia, on the nozzle diameter used.
  • spray dryers with a disc atomizer in which the aqueous solution is applied to an externally driven rotating plate and finely distributed by centrifugal forces.
  • the inlet temperature in the spray dryer is for example 100 ° C to 250 ° C, but preferably 110 ° C to 200 ° C, more preferably 1 10 ° C to 180 ° C.
  • the outlet temperature is for example 20 to 130 ° C, preferably 50 ° C to 1 10 ° C, more preferably 70 to 100 ° C.
  • the residual moisture of the powder obtained is preferably below 20%, preferably below 10%, more preferably below 5% and most preferably below 1.5%.
  • the obtained carbamoylsulfonate-containing compounds are preferably obtained as colorless powders which only slightly dust. If appropriate, it may be advantageous to add a dedusting agent to the material to be dried before, during or after the spray drying. It is preferred to add the dedusting agent to the aqueous solution. Furthermore, it is possible to introduce the dedusting agent into the dryer during the spray-drying process. Furthermore, it is possible to cover the resulting powder on the surface with a dedusting agent.
  • Method 3 Isolation of the solid material by cryogenic techniques
  • the workup is carried out in a known manner by a mechanical separation of the solid or by evaporation of the water from the frozen aqueous solution.
  • Very particularly preferred for drying the aqueous reaction mixtures are the spray-drying processes according to Method 2.
  • the invention further relates to the use of the composition according to the invention as a reaction component for amino group-containing compounds.
  • a l s amino-containing compound A l s amino-containing compound
  • suitable compounds are polymers such as gelatin, polysaccharides containing amino groups, diamines such as ethylenediamine, propylenediamine, butylenediamine, hexamethylenediamine, diaminocyclohexane, 1,1-diaminododecane, amino-containing polyethers, polyamines such as diethyltriamine, triethylentetramine, tetraethylenepentamine, aminoethylpiperazine, pentaethylenehexamine, Polyethyleneimine, polyvinylamine, polyamidoamine-based resins, which are used, for example, in the paper industry for increasing the wet strength and as retention aids, amino-containing (co) polymers based on monomers from the group of dienes, such as butadiene, isoprene, isobutene, olefins, such as ethylene, Propylene, styrene, acrylic acid esters, methacrylic acid esters, (
  • Suitable amino group-containing compounds can furthermore be biological material, such as, for example, tissue in association with other materials, such as skin material, connective tissue, bones, organs, muscle fibers or wall material of blood vessels, optionally in isolated or purified form.
  • biological material such as, for example, tissue in association with other materials, such as skin material, connective tissue, bones, organs, muscle fibers or wall material of blood vessels, optionally in isolated or purified form.
  • the end products used with the biological material according to the invention are advantageously suitable for the production of surgical sutures, for the production of implantological preparations, for the production of bone substitutes and for the production of body-compatible replacement materials for surgery.
  • the end product used according to the invention is then a tanned leather with advantageous properties.
  • the invention therefore also relates to reaction products obtainable by reaction of amino-containing compounds with the compositions according to the invention.
  • the invention further relates to the use of the composition of the invention as a crosslinker for water-soluble protein-based polymers, preferably gelatin.
  • An advantageous application is the stabilization of monomer suspensions in water through a sheath of stabilizing material, wherein the stabilizing material contains gelatin.
  • the gelatin can be crosslinked with the composition according to the invention. This prevents stabilization of the capsules and coalescence of the monomer droplets.
  • the polymerization of the monomers can be initiated inside the capsules, for example by increasing the temperature.
  • oil-soluble initiators which are introduced in the monomer phase before the encapsulation of the monomers with the gelatin, is advantageous.
  • the process is particularly advantageous for the preparation of crosslinked styrene copolymers and for the preparation of ion exchangers which must have a very narrow average particle size distribution, being used for the polymerization and preparation of the monodisperse monomer droplets per se known methods and technologies.
  • composition according to the invention thus represents an alternative to the previous formaldehyde crosslinking.
  • reaction of the compositions according to the invention with amino-containing reaction components can be carried out in an aqueous medium or in the presence of organic
  • Solvents take place. Particular preference is given to solvents in which the products according to the invention are partially soluble and which are partially miscible with water, for example. Examples include: polar solvents such as pyrrolines, dimethylsulfoxide, Dimethylformamide, N-methylpyrrolidinone, N-ethylpyrrolidinone, ethanol, methanol, ethylene glycol, diethylene glycol, dipropylene glycol, methoxypropyl acetate, tetrahydrofuran.
  • polar solvents such as pyrrolines, dimethylsulfoxide, Dimethylformamide, N-methylpyrrolidinone, N-ethylpyrrolidinone, ethanol, methanol, ethylene glycol, diethylene glycol, dipropylene glycol, methoxypropyl acetate, tetrahydrofuran.
  • the invention further relates to the use of the composition according to the invention as auxiliaries for papermaking, in particular for the production of wet strength agents or retention aids.
  • the compositions according to the invention are suitable as
  • Polyamidoamine resins are, for example, polycondensates of adipic acid with one or more polyamines, for example, a group of diethylenetriamine, ethylenediamine, caprolactam, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine and their homologs or polyamines with piperazine-
  • Units such as aminoethylpiperazine.
  • the reaction is advantageously carried out in aqueous solution in a stoichiometric ratio of 0.1 to 2 mol of component a) based on the amine equivalents of the polyamidoamine resin. If the desired molecular weight increase, which can be monitored, for example, by measuring the solution viscosity, is reached, the condensation can be interrupted by acidification of the reaction mixture to pH 2.5 to 4 and the resulting
  • Reaction product to be stabilized may then be fed to a high dilute cellulose slurry in papermaking at a dosage of 0.1 to 8% by weight.
  • a paper is obtained with an increased tear strength in the dry state and with rewetting with water.
  • the composition according to the invention can advantageously be used for the production of filter paper, photo paper, kitchen towels, handkerchiefs, tissue papers, banknotes, wallpapers, etc.
  • the cationic polyamidoamine and polyamine resins obtained by using the compositions of the present invention can be used as a retention agent in papermaking. These aids accelerate dewatering in sheet formation on a paper machine and thus contribute significantly to increasing the running speed of the paper machine.
  • the compositions according to the invention are added directly to the cellulose slurry in situ in papermaking as flocculant and dewatering accelerator.
  • the invention further relates to the use of the composition according to the invention, in particular a solid, particulate composition, for example as Vorgerbstoffe, tannins or as retanning of hides and skins.
  • compositions according to the invention with the amino-containing compounds in an aqueous system at a pH of 6 to 10.
  • pretanning agent is understood to mean a product with which a skin or a coat can be converted into a state which permits commercial mechanical treatments such as wilting or wrinkling, but requires further treatment steps with tanning substances to complete the leather or fur.
  • the invention further relates to a process for the tanning of hides and skins, which is characterized in that treated after washing, liming, possibly depilation and deliming pretreated hides or skins with the composition of the invention.
  • the invention also relates to the wet white leather obtained by the tanning process according to the invention, including a chromium-free tanned leather intermediate for mechanical
  • the appropriately prepared skins are preferably in a commercial Gerbank in aqueous liquor at a temperature of 10 ° C to 60 ° C and a pH of 5 to 10, preferably 7 to 9, with 0.5 to 10%, preferably 1 to 4% (based on the proportion of pure component a)) of the composition according to the invention treated in such a way that a tanned intermediate having a shrink temperature of at least 65 ° C, preferably at least 68 ° C, particularly preferably at least 70 ° C. receives.
  • the shrinkage temperature is determined by methods known to those skilled in the art, for example by heating the tanned intermediate by immersion in a water bath whose temperature matches a certain temperature
  • the product is preferably left to be from 0.1 to 8 h, preferably from 0.2 to 2 h, at a pH in the section of 8 to 10 and penetrate a liquor pH of 7 to 8 and then add a fixative.
  • Suitable fixing agents in the tannery are known bases or mixtures thereof, for example sodium hydroxide, alkali metal carbonates, alkali hydrogen carbonates, magnesium oxide, dolomite, tertiary amines, etc., but especially dolomite, magnesium oxide, sodium carbonate and sodium hydroxide solution.
  • the fixation is preferably carried out over a period of 2 to 24 h, preferably 4 to 12 h at a
  • suitable amino compounds are ethanolamine, diethanolamine, propylamine, butylamine, hydroxypropylamine, dihydroxypropylamine, 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxy si 1, N- (2-aminoethyl) -3-aminopropyltriethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, bis (3-triethoxysilylpropyl) amine, bis (3-trimethoxysilylpropyl) amine,
  • silanes are suitable for addition during the tanning process within the substrate by hydrolysis to silanol groups and self-condensation of the silanol groups
  • Polysiloxanyl phenomenon additionally build a three-dimensional secondary network and can therefore contribute advantageously to further stabilization of the skin material.
  • the presence of mineral fillers can also enhance the stabilizing effect.
  • Suitable mineral fillers are, for example, silica-containing materials such as hydrolytically produced or pyrolytically produced silicas, ground glasses, sheet silicates, aluminum silicates, zirconium dioxide, titanium dioxide. Such mineral fillers may also form an over-surface specially treated by organofunctional silanes and chemically modified. Such materials are commercially available.
  • the stabilization of the skin is a desirable effect, especially when used as a pretanning agent, in order, for example, to positively influence the mechanical processing during the folding process. Also, this can be favorably influenced the shrinkage temperature.
  • These silanes can also be used in the retanning in combination with the composition according to the invention can be used to influence the haptic properties (fullness, softness) and the dyeing properties (levelness, colouration).
  • the obtained, tanned intermediates are suitable for mechanical processing by z. B. Wilting, folding or splitting.
  • these intermediates are characterized by a very white, clear and light-fast intrinsic color, which is a clear advantage over glutardialdehyde tanned leathers.
  • the pre-tanned intermediates can be retanned by methods known to those skilled in the art and finished to give soft and airy crust leathers.
  • the invention further relates to a process for the production of leather and furs, characterized in that in an aqueous liquor at a temperature of 10 ° C to 60 ° C and a pH of 5 to 10, preferably 7 to 9 prepared plow material (ie for the tanning conditioned skins or delimbed and / or pickled bloom material) with 0.5 to 10%, preferably 1 to 4% (based on active ingredient of component a)) of the material according to the invention until a tanned intermediate having a shrinkage temperature of at least 65 ° C, preferably at least 68 ° C, particularly preferably at least 70 ° C receives.
  • a aqueous liquor at a temperature of 10 ° C to 60 ° C and a pH of 5 to 10, preferably 7 to 9 prepared plow material (ie for the tanning conditioned skins or delimbed and / or pickled bloom material) with 0.5 to 10%, preferably 1 to 4% (based on active ingredient of component a)) of the material according to the invention
  • the mechanical processing of the tanned intermediates, the so-called wet white material, on e.g. Folding machines problematic because the wet white material sticks too much to the knife rollers and can be poorly processed.
  • the tanning is allowed to run for longer, if more tannin is metered or fixated at higher pH values, considerably higher shrinkage temperatures can be achieved. But these are not required for the mechanical processing of the arms.
  • Further processing and the final leather properties can be adapted to the requirements of the customer by before, during or after the addition of the composition according to the invention further in the tannery typical substances of the tannery are added.
  • these agents include the commercially known organic organic tanning agents known to those skilled in the art, such as syntans, resin tanning agents, vegetable tanning agents, filling and softening polymer (post) tanning agents, fatliquoring agents and water repellents.
  • these agents used in the subsequent Nachgerbönen in the usual quantities for wet white.
  • pro rata lignosulfonates can be used.
  • Advantage of the tanning process according to the invention is that leather can be obtained with a wide range of properties and which can be used versatile as raw materials in the mechanical processing shavings, u.a. also for the production of valuable products that can be used in the leather manufacturing process. This provides a significant contribution to further reducing waste in leather production.
  • compositions according to the invention do not foam when used in aqueous solution and have very good stability to hydrolysis under application conditions.
  • the mixture still looks milky at this time, but the isocyanate has already been converted to such an extent that no organic phase is observed after stopping the dispersing machine and waiting for 120 seconds. It is then further dispersed for 1 hour at 20,000-24,000 revolutions per minute, with the temperature rising to 56 ° C. After a reaction time of a total of 3 hours, a clear solution has emerged. The pH is 3.66. The batch is then cooled to 25 ° C in 30 minutes and it will be
  • a solution of 1.75 g of powder in 5 ml of water is clear and has a pH of 2.20.
  • the solid is then homogeneously mixed with 31.1 g of citric acid monohydrate by means of a grinder.
  • a solution of 1.75 g of powder in 5 ml of water is clear and has a pH of 2.00.
  • a solution of 1.75 g of powder in 5 ml of water is clear and has a pH of 2.20.
  • the temperature of the reaction mixture is 3 hours after addition of the isocyanate 60 ° C. After a reaction time of 3.5 hours, the organic phase has disappeared. It is then cooled in 1, 5 hours at 40 ° C, while further dispersed at 15000 revolutions per minute. After a total reaction time of 5 hours, the mixture is filtered and mixed with a solution of 28.3 g of citric acid monohydrate in 23.4 g of water, resulting in a pH of 2.58. A 35.0% solution with a pH of 2.58 is obtained.
  • a solution of 1.75 g of powder in 5 ml of water is clear and has a pH of 2.60.
  • a solution of 1.75 g of powder in 5 ml of water is clear and has a pH of 2.4.
  • Adduct prepared and applied in a 30% aqueous solution according to the specifications of US4413997.
  • Nips (3, 3-3, 5mm) are pretreated with 300% water (20 ° C) and 2% calcium hydroxide overnight (reliming) and the liquor is drained off. Subsequently, the arms are washed with 200% water (based on weight of the body) and the liquor is drained off. The pod material is then destined for deliming in 100% fresh water with 0.1% sodium bisulfite and 1.2% of an N-free decalcifying agent for 30 minutes. Annually (pH 8.4) 0.2% of a fatty alcohol ethoxylate-based degreaser, 150% water and 0.15% of a beeignem (Novobate® 1547, product of Novozyme) are added and agitated for 1 hour.
  • a fatty alcohol ethoxylate-based degreaser 150% water and 0.15% of a beeignem (Novobate® 1547, product of Novozyme) are added and agitated for 1 hour.
  • the keg is moved overnight (pH 2.1). The next morning, the fleet is drained and the
  • the shrinkage temperature was 66 ° C.
  • the retanning by addition of 24.9 g of anhydrous citric acid to 950 g of the above 30% aqueous solution by the same procedure a shrinkage temperature of 68 ° C were measured.
  • 33% of the isophorone diisocyanate-bisulphite adduct solution was used in relation to pum weight.
  • the leather treated without citric acid was not so good foldable and shows an undesirable scar pull.
  • the quantities of the respective products used are based on the weight of the raw materials or intermediates used.
  • the buff is conditioned for 1 hour with 0.25% magnesium oxide to pH 9.5 and mixed with 6% of the product according to the invention from Example 1 (as powder or diluted with water 1: 1) (pH 8.3 ). After 3 hours, the pH of the liquor is raised to 9.0 to 9.5 by adding 0.3% of magnesium oxide, and the shrinkage temperature is measured. After a period of 1 hour, 0.2% of magnesium oxide and 0.1% of an aqueous ammonia solution (diluted with water 1: 5) are added (after 1 hour, the pH is 9.1) and the barrel at 35 ° C over Night moves (pH 9.2).
  • the pH is reduced to 5.3 in 3 portions with 0.6% of formic acid (diluted with water 1: 5) in 3 portions. After 90 minutes, the fleet is drained.
  • the wet white leather chrome-free tanned leather intermediate for mechanical treatment and further (subsequent) tanning
  • the shrinking temperature is measured again (77 ° C) and the leathers folded to 1, 0 mm.
  • a leather having a shrinking temperature of 77 ° C., a smooth grain texture, a dry, firm feel, and a very good wiping and folding properties were obtained.
  • Salted cowhides are washed commercially, limed, depilated, fleshed, and split.
  • the pod material (2.7 mm) is washed with 200% water and drained the liquor.
  • the bins are agitated in 30% fresh water with 0.4% sodium bisulfite and 1.4% of an N-free decalcifying agent (Decaltal AN, product of BASF) for 10 minutes.
  • 0.15% of a fatty alcohol ethoxylate-based degreaser is added and for 1 h at 25 ° C (pH 8.4).
  • 50% water and 1% of a Beeignym (Novobate® 1547, product of Novozyme) are added and agitated for 1 hour.
  • the liquor is then drained and the buff washed again.
  • the buff is conditioned for 1 hour with 0.25% magnesium oxide to pH 9.5 and mixed with 6% of the product of Example 1 according to the invention (as powder or diluted with water 1: 1) (pH 8.7 ).
  • a 4,4'-dihydroxydiphenylsulfone / naphthalenesulfonic acid / formaldehyde condensate eg TANIGAN® BN, product of LANXE SS
  • 1% of the formaldehyde condensate of aromatic sulfonic acids eg TANIGAN® PR, Product of Lanxess.
  • the pH is reduced to 5.3 with 0.6% formic acid (diluted with water 1: 5) in 3 portions. After 90 minutes, the fleet is drained. The wet white leathers are washed and wiped off. The shrink temperature is measured again (76 ° C) and the leather folded to 1.0 mm.
  • Salted cowhides are washed commercially, limed, depilated, fleshed, and split.
  • the pod material (2.7 mm) is washed with 200% water and drained the liquor.
  • the bins are agitated in 30% fresh water with 0.4% sodium bisulfite and 1.5% of an N-free decalcifying agent (Decaltal® A-N, product of BASF) for 10 minutes.
  • 0.15% of a fatty alcohol ethoxylate-based degreaser is added and agitated for 90 minutes at 25 ° C (pH 8.5).
  • 50% water and 1% of a Beeignym (Novobate® 1547, product of Novozyme) are added and agitated for 45 minutes.
  • the liquor is then drained and the buff washed again.
  • the prepared fin is conditioned in 50% liquor with 1% sodium acetate and 1% sodium carbonate to pH 9.9 and then admixed with 6% of the product according to the invention from Example 1 (as powder or diluted with water 1: 1) (pH 8, 6). After a 30 minute penetration time, 4% of a 4,4'-dihydroxydiphenylsulfone / naphthalenesulfonic acid / formaldehyde condensate (e.g.
  • TANIGAN® BN product of LANXESS
  • 2% of a formaldehyde condensate of aromatic sulfonic acids eg TANIGAN® PR, product of LANXESS
  • pH 7 50% solutions, pH 7
  • TANIGAN® PR formaldehyde condensate of aromatic sulfonic acids
  • the prepared boshes are conditioned for 1 hour with 1% sodium acetate to pH 8.0 and mixed with 1.7% of the product according to the invention from Example 1 (as a powder or diluted with water 1: 1). After 20 minutes of penetration time, 0.2% sodium carbonate (diluted 1:10 with water) is added and agitated for 30 minutes. Then another 3.4% of the product according to the invention from example 1 (diluted as powder or with water 1: 1) is added. After 1.5 hours, the pH is raised to 8.2 and the shrinkage temperature is measured by adding in portions a total of 0.4% sodium carbonate (diluted 1:10 with water) within 2 hours. Then the barrel is moved at 35 ° C overnight. The pH is then reduced to 7.0 with formic acid (diluted 1:10 with water). You move the barrel for 2 hours.
  • Example B 6 Chrome-tanned car upholstery leather: The crimped wet white leathers of Example B 4 are agitated with 300% water (35 ° C) and 0.2% of a fatty alcohol ethoxylate at pH 7.6 for 20 minutes. After draining the liquor, 50% water, 3% of a naphthalenesulfonic acid / formaldehyde condensate (TANIGAN® RFS, product of LANXESS), 1.5% sodium formate and 3% of a lecithin-based fatliquoring agent (BAYKANOL® Licker SL, product of Lanxess) (diluted with water 1: 8) was added.
  • TANIGAN® RFS naphthalenesulfonic acid / formaldehyde condensate
  • BAYKANOL® Licker SL product of Lanxess
  • % Of water another 4% of a lecithin-based fatliquor (BAYKANOL® Licker SL, product of Lanxess) (diluted with water 1: 8) is added and drummed at 50 ° C for 1 hour. Then, by adding 2% formic acid (diluted with water 1: 5) in 2 portions fixed for 45 minutes (pH 4) and drained the liquor. It is washed with 200% water (50 ° C). In fresh liquor (100% water, 50 ° C) is mixed with 4% of a lecithin-based fatliquor
  • the folded wet-white leather from example B 5 are washed at 35 ° C. in 150% liquor with 0.3% formic acid (diluted 1:10 with water) for 20 min. (PH 4.3) and the liquor is drained off.
  • TANIGAN VR Dihydroxydiphenylsulfone / naphthalenesulfonic acid / formaldehyde condensate
  • RETINGAN® ZF Plus resin tanning agent
  • BAYKANOL® TF-2N product of Lanxess
  • the resulting cationic polymer solutions according to Examples Cl) and C2) are suitable for increasing the wet strength of paper.
  • Bleached pine / birch sulphate pulp (weight ratio 80:20) is ground to a freeness of 38 ° Schopper-Riegler at a stock consistency of 2.5% in Dutch. From the preserved
  • Pulp suspension is placed 100 g in a beaker and diluted to 1000 ml with water.
  • the amounts of the polycondensate solutions (% by weight of the application form, based on pulp) prepared according to Example C1) and Example C2) given in the following table are then added to the pulp and stirred for 3 minutes.
  • the contents of the beakers are placed on a sheet former (Rapid-Köthen apparatus), diluted with 8000 ml of water and forms paper sheets with a basis weight of about 80 g / m 2 (according to DIN 54358, part 1).
  • the paper sheets are dried for 8 minutes at 85 ° C and 60 mbar and heated in a drying oven for 10 minutes at 110 ° C.
  • test strips each 1.5 cm wide are cut out of each paper sheet and immersed in deionized water for 5 minutes. Then the wet strips of a tensile testing machine (DIN 53112, Part 2) are tested for their wet fracture load.
  • a tensile testing machine DIN 53112, Part 2

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)

Abstract

Composition contenant (a) au moins un composé contenant des groupes sulfonate de carbamoyle et (b) au moins un acide carboxylique contenant un émulsifiant à raison de moins de 0,001 pour cent en poids, par rapport à la composition, les composés contenant des groupes sulfonate de carbamoyle du constituant (a) étant un produit de réaction d'au moins un polyisocyanate organique et d'au moins un bisulfite et/ou un disulfite, caractérisée en ce que le polyisocyanate organique présente une masse moléculaire relative inférieure à 400 g/mol et contient des groupes NCO liés à des composés aliphatiques ou cycloaliphatiques.
EP12733655.0A 2011-06-29 2012-06-29 Composition à base de composés contenant des groupes sulfonate de carbamoyle Withdrawn EP2726522A1 (fr)

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EP12733655.0A EP2726522A1 (fr) 2011-06-29 2012-06-29 Composition à base de composés contenant des groupes sulfonate de carbamoyle

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
EP11171954A EP2540753A1 (fr) 2011-06-29 2011-06-29 Composition à base de composés contenant des groupes de carbamoylsulfonate
ITRM20110534 2011-10-06
EP12733655.0A EP2726522A1 (fr) 2011-06-29 2012-06-29 Composition à base de composés contenant des groupes sulfonate de carbamoyle
PCT/EP2012/062747 WO2013001077A1 (fr) 2011-06-29 2012-06-29 Composition à base de composés contenant des groupes sulfonate de carbamoyle

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Family Cites Families (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU499789B2 (en) 1973-04-16 1979-05-03 Commonwealth Scientific And Industrial Research Organisation (poly)carbamoyl sulphonate containing composition
DE2414470B2 (de) 1974-03-26 1977-01-13 Bayer Ag, 5090 Leverkusen Waessrige loesung eines bisulfitblockierten polyisocyanatvorpolymeren
DE2543093A1 (de) 1975-09-26 1977-04-07 Bayer Ag Verfahren zur herstellung von bisulfit-additionsprodukten von polyisocyanat-praepolymeren in wasser
JPS5427094A (en) 1977-08-03 1979-03-01 Teijin Ltd Production of suede like raised fabric
US4413997A (en) 1983-02-07 1983-11-08 The United States Of America As Represented By The Secretary Of Agriculture Dicarbamoylsulfonate tanning agent
DE4422569A1 (de) 1994-06-28 1996-01-04 Bayer Ag Bisulfit-blockierte Polyisocyanate als Gerbstoffe
DE19528782A1 (de) 1995-08-04 1997-02-06 Bayer Ag Verwendung von Polyasparaginsäureamiden als Lederhilfsmittel
DE19624821A1 (de) 1996-06-21 1998-01-02 Bayer Ag Verfahren zur Gerbung von Leder
WO1998038340A1 (fr) * 1997-02-26 1998-09-03 Bayer Aktiengesellschaft Cuir biodegradable
DE102004050284A1 (de) 2004-10-15 2006-04-27 Lanxess Deutschland Gmbh Isocyanat-basierende Gerbstoffe
DE102006056479A1 (de) 2006-11-28 2008-05-29 Henkel Kgaa Bisulfit-Addukte von Isocyanaten

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2013001077A1 *

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