WO2013060679A1 - Utilisation comme agent de trempe de métaux d'une composition comprenant un polymère contenant du vinyl-lactame, un solvant et au moins un biocide ne contenant pas d'halogène - Google Patents

Utilisation comme agent de trempe de métaux d'une composition comprenant un polymère contenant du vinyl-lactame, un solvant et au moins un biocide ne contenant pas d'halogène Download PDF

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Publication number
WO2013060679A1
WO2013060679A1 PCT/EP2012/070970 EP2012070970W WO2013060679A1 WO 2013060679 A1 WO2013060679 A1 WO 2013060679A1 EP 2012070970 W EP2012070970 W EP 2012070970W WO 2013060679 A1 WO2013060679 A1 WO 2013060679A1
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polymer
composition according
metal
composition
biocide
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PCT/EP2012/070970
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German (de)
English (en)
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Stephan Bauer
Frank Fischer
Erik Bohrer
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Basf Se
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0058—Biocides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/06—Ethers; Acetals; Ketals; Ortho-esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/45—Heterocyclic compounds having sulfur in the ring
    • C08K5/46—Heterocyclic compounds having sulfur in the ring with oxygen or nitrogen in the ring
    • C08K5/47—Thiazoles
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
    • C21D1/56—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering characterised by the quenching agents
    • C21D1/60—Aqueous agents

Definitions

  • the present invention relates to the use of compositions containing vinyl monomer-containing polymer, aqueous solvent and at least one halogen-free biocide, in particular as a metal coolant such as a metal quenching medium.
  • Aqueous polymer solutions such as solutions of vinyllactam polymers, such as polyvinylpyrrolidones, must be treated with suitable preservatives due to their guaranteed shelf life and storage conditions. The preservatives used must not adversely affect the applications of the polymer solution. The preservation of such polymer solutions is known to the person skilled in the art. Preserved solutions are important wherever aqueous polymer solutions are used, stored or transported. Important areas of application are cosmetic preparations, preparations in the field of detergents and cleaners, membranes, gas hydrate inhibitors, ceramics, photoresists, gels, lacquers, film coatings, displays, metalworking and metal fabrication.
  • these applications involve small amounts of polymer, sold as a solution in a particular application, based on the total amount of polymer produced. From the perspective of a producer, therefore, it is desirable to prepare and stabilize a polymer solution so that a variety of applications can be covered with a product.
  • the product a stabilized aqueous polymer solution
  • Preservatives must therefore meet the requirements of as many highly diversified application areas as possible in order to enable economic development, production and distribution of new polymer products.
  • Typical applications in the field of hair fixation are sprays, foams, mousses, gels and waxes. These applications and the preparations suitable therefor are well known to the person skilled in the art.
  • typical polymers used for this purpose for example the polyvinylpyrrolidones (vinylpyrrolidone homopolymers) and the vinylpyrrolidone copolymers, for example copolymers, vinylpyrrolidone and vinyl acetate or vinylpyrrolidone, vinylimidazole and methacrylamide.
  • the hardening of steels is a widely used method for influencing the quality of the steel, such as hardness and toughness. For this purpose, the steel is first heated to about 850 ° C.
  • the steel transforms from cubic face-centered austenite to the desired metastable tetragonal-distorted body-centered martensite crystal structure.
  • the conversion starts at around 400 ° C and is associated with a significant increase in the hardness of the steel.
  • the transformation from the austenite to the martensite structure leads to an increase in volume of up to 1%, which results in transformation stresses, in particular on the surface of the workpiece.
  • the quenching a volume contraction on. Both lead to thermal stresses in the workpiece.
  • These different voltages lead to cracks and unwanted dimensional and shape changes in large components, such as gear wreaths for wind turbines. For this reason, water can not be used as a quenching medium for these components.
  • hardening oils allow rapid quenching up to about 400 ° C, where the desired martensite formation begins. Due to the reduced thermal conductivity of the oil but then sets in a much slower cooling. The stresses in the steel structure can thereby be reduced, and the components have the desired hardness after deformation without deformation and cracks. Disadvantage of hardening oils are the strong soot and smoke during the quenching process and the associated fire hazard. In addition, the components must be degreased after quenching.
  • quenching media based on water-soluble polymers, which do not have the disadvantages of hardening oils or water. For example, an aqueous polymer solution containing 1% by weight of polyvinylpyrrolidone (PVP) has a similar quenching behavior as hardening oil.
  • PVP polyvinylpyrrolidone
  • aqueous PVP polymer solutions must be provided with sufficient preservation due to the high thermal load during the quenching process and the long service life of the quench baths of several years.
  • Metal coolants are, for example, metal quenching media as well as liquids used for cooling metal objects and / or machining tools in metalworking such as cutting, milling, drilling.
  • Polymeric nitrogen-containing preservatives such as Cosmocil CQ, which are used in industry as a preservative for aqueous PVP solutions, have a high affinity for example to the metal surface or to skin and hair. They therefore interfere with the good film properties of the usually high molecular weight PVP solutions when they are brought into contact with surfaces of keratinic structures, such as hair and skin, or of metals. For metals, this leads to a faster and thus undesirable cooling of the metal body, in particular in the temperature range of 400 ° C to room temperature relevant for the curing processes. Furthermore, these preservatives can coagulate and disturb the build-up of a uniform polymer film, as a result of which heat transfer with different levels of heat transfer and, thus, heat dissipation in the workpiece at different speeds.
  • Preservatives such as Cosmocil CQ® are toxicologically questionable.
  • preservatives with halogens in particular those with halide ions such as chloride, for example in Cosmocil CQ, can also lead to corrosion of the workpiece and the quench basin or to irritation of the skin and hair.
  • the halide ions can also impede the preparation of a stable preparation, for example as a result of undesired precipitation of gels or solids, disturbance of Gel structure with the result of about viscosity reduction, or other undesirable interactions with other ingredients.
  • biocides for the stabilization of, in particular, aqueous polymer solutions in the field of hair cosmetics.
  • IPCOM000202917D discloses a composition of three biocides and their use for the stabilization of PVP and the use of the thus stabilized polymers for use in cosmetic, in particular hair cosmetic preparations.
  • US Pat. No. 3,902,929 discloses metal quench baths containing from 1 to 13% by weight of polyvinylpyrrolidone having an average molecular weight between 5,000 and 400,000 g / mol as water-soluble polymers.
  • No. Re 34.1 19 describes a metal quench bath which contains as essential water-soluble polymer up to 25% by volume of a polyvinylpyrrolidone having an average molecular weight between 1270000 and 2240000 g / mol.
  • US-A 2009/65107 discloses metal quench baths, which as essential components inorganic nanoparticles having an average diameter of 0.2 to 10 ⁇ , in particular phyllosilicates, such as talc, mica, montmorillonite, hectorite or saponite and a water-soluble polymer such as polyalkylene glycol , Polyvinyl pyrrolidone, polyacrylamide or polyvinyl alcohol.
  • phyllosilicates such as talc, mica, montmorillonite, hectorite or saponite
  • a water-soluble polymer such as polyalkylene glycol , Polyvinyl pyrrolidone, polyacrylamide or polyvinyl alcohol.
  • the object of the invention was to find preservatives for compositions comprising vinyl monomer-containing polymer and aqueous solvent, in particular for use in metal quenching media, which have no negative effects on film formation, in particular on the quenching behavior of metal quenching media. They should be toxicologically safe. Furthermore, they should not cause damage, such as corrosion, of an article that comes in contact with the composition, and in particular should not contain halide ions such as chloride. Furthermore, sufficient preservation stability against bacteria and fungi was desired, both in handling the pure polymer solution, for example during storage and in the preparation, for example in metal quenching media.
  • compositions comprising vinyl monomer-containing polymer, aqueous solvent and at least one biocide, the biocide being halogen-free and soluble in the composition, has been found for preparations in the field of detergents and cleaners, membranes, gas hydrate inhibitors, ceramics, photoresists, gels, lacquers , Film coatings, displays, metalworking and metal fabrication.
  • Preferred use is the composition of the invention for preparations in the field of metal coolant, in particular as a metal quenching medium.
  • composition of the present invention film formation of the polymer on a surface which is contacted with the composition is not disturbed by the biocide upon evaporation of the solvent of the composition. Undesirable interactions with other ingredients of a preparation are avoided or at least minimized.
  • Biocides used according to the invention are the following substances as well as solutions and mixtures containing at least one of the named substances:
  • alkyl-substituted aliphatic or aromatic alcohols and their salts such as phenoxyethanol, benzyl alcohol, ethylhexylglycerol, octane-1,2-diol, 1,2-decanediol, 1 -5-pentanediol, 4-hydroxybenzoic acid methyl ester, propyl 4-hydroxybenzoate, sodium 4- (methoxycarbonyl) phenolate, sodium 4- (propyloxycarbonyl) phenolate,
  • nitrogen- and sulfur-containing heterocycles such as alkylisothiazolinones, such as 2-methylisothiazolinone, zinc bis [2-pyridinolate] -N, N'-dioxide.
  • potassium sorbate contains as active ingredient 10-25% potassium sorbate (CAS No. 24634-61 -5), 25-50% benzyl alcohol (CAS No. 100-51-6) and 25-50% 2-phenoxyethanol (CAS-No 122-99-6);
  • Phenonip® from Thor GmbH, contains as active ingredient 50-100% 2-phenoxyethanol (CAS No. 122-99-6).
  • Neolone® 950 from DOW Chemical
  • 2-phenoxyethanol contains as active ingredient 53-58% 2-phenoxyethanol (CAS Nos. 122-99-6 and 42-47%) 1,2-octanediol (CAS No 122-99-6); Particularly suitable are biocides comprising 2-phenoxyethanol, 3- (2-ethylhexyloxy) propane-1, 2-diol and / or 2-methyl-2H-isothiazol-3-one.
  • biocides in the context of this invention are those which are halogen-free and are soluble in the composition. Preference is also given to selecting those biocides which are clearly water-soluble, ie the preparations comprising polymer and biocide have a turbidity value determined as FTU value of less than 1. Another preferred property of the biocides is that they do not interfere with film formation of the polymer on the surface, such as on the workpiece to be quenched, upon evaporation of the solvent of the formulation, such as a metal quench medium, and thus, for example, uniform cooling of the workpiece, a relatively smooth Enable film on the object.
  • biocide Another desired property of the biocides is their regulatory approval for the intended use: this means that the biocide must be toxicologically approved for the particular application desired.
  • the biocide according to the invention therefore preferably has an approval for use in preparations for industrial applications. Thus, the greatest possible safety in the application is given. At the same time, the preparation containing polymer and biocide is thus given the broadest possible accessibility of application areas.
  • the preferred biocides have an approval according to the chemical safety program "REACH" of the European Union, as of the end of April 201 1. Furthermore, the preferred biocides have an approval according to Biocide Regulation 98/8 / EC of the European Parliament and Council of 16. February 1998.
  • biocide in the context of this invention comprises a single chemical substance having a biocidal effect or a mixture of several different individual substances and formulations of one or more individual substances.
  • the biocide is in the composition used in the invention in a concentration of the active ingredient, with several active ingredients of the sum of the individual active ingredients, from 1 ppm to 50,000 ppm, preferably 20 to 30,000 ppm, more preferably 50 to 10,000 ppm, most preferably 100 bis to 5000 ppm and especially 200 to 3000 ppm, based on the total mass of the composition.
  • Upper and lower limits can be individually combined with each other, about 1 to 10,000 ppm or 50 ppm to 5000 ppm.
  • the recommended range for the particular application to provide stabilization, in particular to microorganisms, depends on the Biocide and can be determined in a particular case by the expert easily by known test methods.
  • the biocide used in the invention is soluble in the composition.
  • Solubility data (based on 20 ° C) according to the DAB.
  • Preferred biocides are readily soluble in the composition of the invention.
  • biocides are very readily soluble in the composition according to the invention.
  • water-insoluble and “insoluble” mean that the polymer according to DAB is sparingly soluble, very sparingly soluble or practically insoluble.
  • a further preferred embodiment is the use of a composition according to the invention, wherein the addition of the biocide of the K value of the vinyl monomer-containing polymer by at most 2 units and - in a preparation containing up to 20 weight percent vinyl monomer-containing polymer - the viscosity at most 20%, the Haze color number by no more than 20, and the pH by no more than 0.5, and the ash content is not more than 0.02% by weight.
  • the K value is a measure of the molar mass and is determined by the solution viscosity of an aqueous solution having a defined polymer concentration (see Volker Bühler in "Polyvinylpyrrolidone Excipients for the Pharmaceutical Industry", 9th revised edition, BASF, pages 26 to 29) It is only determinable for polymers which have sufficient solubility in water.
  • the change in the K value is not greater than one unit, particularly preferably no change in the K value is observed within the scope of the measurement accuracy.
  • the viscosity of such a preparation is determined rheologically with a viscometer as apparent viscosity according to Brookfield according to DIN EN ISO 2555. Suitable measuring instruments are, for example, Brookfield viscometers, model DV-III +, with RV spindle sets. The samples are usually adjusted to 20 percent by weight solids content, in polymer solutions usually to polymer solids content. The solutions are thermostatted at 23 ° C for about one hour and then measured. After a minute rotation, the measured value is determined.
  • the viscosity of the preparation used according to the invention changes by the addition of the biocide by at most 20%, preferably at most 15%, more preferably at most 10% and most preferably at most 5% based on the viscosity of the same preparation without the addition of the biocide and changes, for example not at all.
  • the ash content is determined by the determination of the ash content known to those skilled in the art as "sulfate ash content.”
  • the ash content is preferably at most 0.01% by weight, more preferably at most 0.005% by weight and most preferably at most 0.001% by weight.
  • the indication of the ash content refers to the total mass of the preparation used in the invention.
  • the pH is determined according to known knowledge and applies to the preparation.
  • the pH value changes by at most 0.5 units, preferably by at most 0.4 units, particularly preferably at most 0.3 units, very particularly preferably at most 0.2 units and changes, for example, only by at most 0.1 units or even Not.
  • the Hazen color number is determined according to known knowledge.
  • the information on the viscosity of the preparation, K value change ash content and pH are based on a preparation containing at most 20 percent by weight of polymer (calculated as the solids content of polymer based on the total mass of the preparation).
  • Aqueous solvent and “solvent” are synonymous in the context of this invention and my water or a mixture of water and an organic solvent with at least 50 weight percent water, preferably at least 70 weight percent, more preferably at least 90 weight percent, most preferably at least 95 Weight percent water and consists in particular only of water.
  • water includes all qualities of water: technical grade water, water of naturally occurring quality, such as surface water, river water or groundwater, and purified water
  • Purified (“clean”) water may be obtained by purification methods such as single or multiple distillation, desalination, Diffusion, adsorption, by means of ion exchanger and activated carbon or other absorbers, be purified by a filtration process such as ultrafiltration or dialysis.
  • purified water is usually a or multiply distilled water and demineralized water referred to.
  • purified water is used.
  • organic solvent means a solvent which is composed of the atomic species carbon, hydrogen and, if appropriate, oxygen and / or nitrogen.
  • the solvent may be a single solvent or a mixture of several solvents Typical representatives of the organic solvents are approximately C1- to C8-alcohols such as methanol, ethanol, n-propanol, isopropanol, butanol and its isomers, amino alcohols such as mono-, di- and triethanolamine, glycol, glycerol and oligo- and polyethylene and -propylene glycols and their mono- and diethers with, for example, alcohols.
  • the organic solvents used are preferably amino alcohols such as mono-, di- and triethanolamine, glycol, glycerol and also oligo- and polyethylene- and -propylene glycols and their mono- and diethers with, for example, alcohols.
  • amino alcohols such as mono-, di- and triethanolamine, glycol, glycerol and also oligo- and polyethylene- and -propylene glycols and their mono- and diethers with, for example, alcohols.
  • oligo- and polyethylene- and -propylene glycols and their mono- and diethers with, for example, alcohols are still liquid or pourable at 25 ° C.
  • Vinyl monomer-containing polymer includes homopolymers, copolymers, graft homo- and graft copolymers.
  • Suitable vinyl monomers are vinylamides such as vinyllactams, acrylates, methacrylates, methacrylamide, acrylamides and amine-group-containing monomers, and monomers containing sulfonic acid groups.
  • Vinylamide polymers are preferably used. Suitable vinylamides are vinyllactams and vinylamides such as vinylformamide, vinylalkylamides such as vinylisopropylamide, vinylmethylamide and vinylbutylamide.
  • vinyllactam polymers are particularly preferred.
  • preferred vinyllactam polymers furthermore contain none, one or more monomers a) and none, one or more monomers b). That is, the polymers have been obtained by polymerization of said monomers and may still contain residual amounts of the monomers.
  • Vinyl lactam polymer may also be a vinyl lactam copolymer of two or more different vinyl lactams besides a vinyl lactam homopolymer.
  • Suitable vinyllactams are, for example, N-vinyl derivatives of the following lactams: 2-pyrrolidone, 2-piperidone, ⁇ -caprolactam and their alkyl derivatives, for example 3-methyl-2-pyrrolidone, 4-methyl-2-pyrrolidone, 5-methyl-2-pyrrolidone , 3-ethyl-2-pyrrolidone, 3-propyl-2-pyrrolidone, 3-butyl-2-pyrrolidone, 3,3-dimethyl-2-pyrrolidone, 3,5-dimethyl-2-pyrrolidone, 5,5-di - methyl-2-pyrrolidone, 3,3,5-trimethyl-2-pyrrolidone, 5-methyl-5-ethyl-2-pyrrolidone, 3,4,5-trimethyl-2-pyrrolidone, 3-methyl-2 piperidone, 4-methyl-2-piperidone, 5-methyl-2-piperidone, 6-methyl-2-piperidone, 6-ethyl-2-piperidone, 3,5
  • Preferred vinyllactams are N-vinylpyrrolidone, 3-methyl-N-vinylpyrrolidone, 4-methyl-N-vinylpyrrolidone, 5-methyl-N-vinylpyrrolidone, N-vinylpiperidone and N-vinylcaprolactam.
  • Particularly preferred vinyl lactams are N-vinyl pyrrolidone ("VP") and N-vinyl caprolactam (“VCap”). Very particular preference is given to N-vinylpyrrolidone.
  • VP N-vinyl pyrrolidone
  • VCap N-vinyl caprolactam
  • Preferred vinyllactam polymers are vinylpyrrolidone polymers such as polyvinylpyrrolidones and vinylpyrrolidone copolymers.
  • Preferred vinyl lactam copolymer containing only vinyl lactams contains N-vinyl pyrrolidone and N-vinyl caprolactam.
  • Suitable monomers a) are, for example, N-vinylamides such as N-vinylformamide and its N-vinylamine, N-vinyl-N-methylacetamide, N-isopropyl-methylacetamide available after the polymerization by hydrolysis; Amines such as N-vinyl or allyl-substituted heterocyclic compounds, preferably N-vinylpyridine, or N-allylpyridine, N-vinylimidazoles, which are also in the 2-, 4- or 5-position with C1-C4-alkyl, especially methyl or Phenyl radicals may be substituted, such as 1-vinylimidazole, 1-vinyl-2-methylvinylimidazole and their quaternized analogs such as 3-methyl-1-vinylimidazolium chloride, 3-methyl-1-vinylimidazoliummethylsulfat, N-C 1 to C 24 alkyl-substituted Diallylamines or their quatern
  • Preferred monomers a) are vinylamides such as vinylformamide and the vinylamine obtainable by hydrolysis after the polymerization, N-vinylimidazole, and vinylmethylamide.
  • Very particularly preferred monomers a) are vinylformamide and also the vinylamine obtainable by hydrolysis after the polymerization and also N-vinylimidazole.
  • Polymers of the invention may accordingly also be copolymers of at least one vinyl lactam and at least one monomer a), for example copolymers of N-vinylpyrrolidone and N-vinylimidazole, copolymers of N-vinylpyrrolidone and N-vinylformamide or copolymers of N-vinylpyrrolidone, N-vinylcaprolactam and N-vinylimidazole.
  • Preferred copolymers are copolymers of N-vinylpyrrolidone and N-vinylimidazole.
  • Suitable monomers b) are all monomers described in WO 2010/072640 from page 6, line 8 to page 8, line 17 as monomers b), which are expressly incorporated herein by reference.
  • monomers b) can also acrylamides of the general structure
  • R 1 to R 3 independently of one another represent hydrogen or a linear or branched, optionally substituted C 1 -C 10 -alkyl radical.
  • Preferred monomers b) are maleic acid, maleic anhydride, acrylamide, methacrylamide, 2-hydroxyethyl (meth) acrylamide, 2-hydroxyethyl-ethylacrylamide, isopropylmethacrylamide, N-tert-butylacrylamide, N-isopropylacrylamide, furthermore vinyl esters of aliphatic C 2 -C 18 -carboxylic acids, such as vinyl acetate, and the vinyl alcohol, vinyl propionate, vinyl butyrate, vinyl laurate, vinyl stearate, vinyl neononate "VEOVA 9" and vinyl neonate obtainable therefrom by hydrolysis after the polymerization.
  • decanoate "VEOVA 10” furthermore dimethylamino (m) ethyl (meth) acrylate and dimethylamino (m) ethyl (meth) acrylamide and their quaternized analogs and / or diallyldimethylammonium chloride
  • the term , (m) ethyl (meth) acrylate “and its variants containing only” (m) "or” (meth) "in the context of this invention comprises the substances" methyl acrylate ",” ethyl acrylate ", methyl methacrylate” and "ethyl methacrylate”.
  • Particularly preferred monomers b) are arylamide, methacrylamide, N-tert-butylacrylamide, N-isopropylacrylamide, vinyl acetate and the vinyl alcohol obtainable by hydrolysis after the polymerization, vinyl propionate, vinyl neonate VEOVA 9 and vinyl neodecanoate VEOVA 10, dimethylamino (m) ethyl ( meth) acrylate, dimethylamino (m) ethyl (meth) acrylamide.
  • methacrylamide, N-isopropylacrylamide and vinyl acetate are particularly preferred.
  • Polymers which are copolymers and contain monomers b) may contain one or more of the monomers b). Usually, however, not more than five different monomers b) are contained in a copolymer.
  • polymers according to the invention may also be copolymers of N-vinylpyrrolidone and vinyl acetate, copolymers of N-vinylpyrrolidone, vinylcaprolactam and vinyl acetate, copolymers of N-vinylcaprolactam and vinyl acetate or copolymers of N-vinylpyrrolidone and (meth) acrylamides.
  • Preferred copolymers comprising monomers b) consist of N-vinylpyrrolidone and vinyl acetate, (meth) acrylamide, N-tert-butyl (meth) acrylamide and / or N-isopropyl (meth) acrylamide.
  • Particularly preferred copolymers containing monomers b) consist of N-vinylpyrrolidone and vinyl acetate, acrylamide, N-tert-butylacrylamide and / or N-isopropylacrylamide.
  • the preferred polymers further include copolymers containing at least one vinyl lactam, at least one monomer a) and at least one monomer b).
  • Particularly preferred polymers include copolymers containing at least one vinyl lactam and at least one monomer b) but no monomer a).
  • the vinyl lactams, monomers a) and b) used for the polymerization may independently of one another be a single or mixtures of a plurality of vinyl lactams, a plurality of monomers a) and / or b), the respective common proportion of the vinyl lactams, monomers a) and b) in each case mentioned proportion of vinyllactam, monomer a) or monomer b) gives the polymer.
  • the total amounts of vinyl lactam, monomer a) and monomer b) always add up to 100 percent by weight based on the polymer.
  • the proportions by weight based on the total mass of the polymer for monomers a) and the monomers b) are usually independently up to 80 weight percent, preferably up to 70 weight percent, more preferably up to 50 weight percent, most preferably up to 40 weight percent and in particular up to 20 weight percent and, for example, are not present in the polymer at all.
  • the composition used contains one or more vinyllactam polymers.
  • the polymer is a vinylpyrrolidone polymer, such as a polyvinylpyrrolidone homopolymer or a vinylpyrrolidone copolymer.
  • the polymer is a polyvinylpyrrolidone.
  • Polyvinylpyrrolidones are, for example, polymers with K values of 10 to 200, preferably K 20 to K 150, for example 12, 15, 17, 25, 30, 60, 80, 85, 90, 95, 100, 15, 120, 130, 150, 180.
  • Vinylpyrrolidone copolymers are, for example, copolymers with N-vinylcaprolactam (VCap), vinyl acetate (VAc), N-vinylimidazole (VI), N-tert-butylacrylamide (TBAA) and / or N-isopropylacrylamide (IPAA) or mixtures thereof such as Copolymers of N-vinylpyrrolidone (VP) and vinyl acetate having a weight ratio VP / VAc of from 20:80 to 80:20, for example 30:70, 50:50, 60:40, 70:30, with K values of 10 to 150 , preferably from 15 to 80 and more preferably from 20 to 50.
  • VCap N-vinylcaprolactam
  • VAc vinyl acetate
  • VI N-vinylimidazole
  • TBAA N-tert-butylacrylamide
  • IPAA N-isopropylacrylamide
  • Particularly preferred copolymers of N-vinylpyrrolidone and vinyl acetate have a K value of from 25 to 60 and a VP to VAc weight ratio of from 55:45 to 70:30, such as 60 : 40, 50:50 and 65:35, copolymers of VP and VCap each having K values of from 15 to 150, preferably from 20 to 120 and in particular from 30 to 110 and weight ratios of the monomers VP to VI or VP to VCap from 95:05 to 20:80, preferably from 10:90 to 50:50, more preferably from 20:80 to 50:50 and for example also 30:70 m K values of from 10 to 200, preferably from 30 to 150 and particularly preferably from 60 to 120, and also copolymers of VP and TBAA or IPAA, each having K values of from 15 to 150, preferably from 20 to 100 and in particular from 30 to 90 and weight ratios of the monomers VP to TBAA or VP to IPAA of 99:01 to 30:70, preferably from
  • the vinyl monomer polymer used in the present invention has a Fikentscher K value of at least 60.
  • the vinyl monomer polymer used according to the invention has a K-value according to Fikentscher of from 10 to 200, particularly preferably from 20 to 180, very particularly preferably from 60 to 150 and in particular from 80 to 130.
  • the preparation of Vinyllactam polymers by radical polymerization is known per se. The polymerization thereby provides polymers which, depending on the monomer solubility and the physical structure (the arrangement of the polymer chains in the space) are water-soluble, dissolved in water. forming or insoluble in water. Included in the present invention are only water-soluble and gel-forming polymers. Preferred are only water-soluble polymers.
  • polyvinylpyrrolidones can be carried out, for example, as a solution or precipitation polymerization in a suitable solvent such as water, mixtures of water and organic solvents, for example ethanol-water or isopropanol-water mixtures or in purely organic solvents such as methanol, ethanol or isopropanol , These preparation methods are known to the person skilled in the art.
  • compositions used according to the invention contain as essential component in addition to the biocides at least one of the polymers according to the invention in a total amount, based on the total mass of the composition of at least 1 wt.%, Preferably at least 5 wt.%, Particularly preferably at least 10 wt.% As for example 15, 20, 25, 30, 35, 40, 45, 50 or even more than 50 wt.%.
  • compositions do not contain more than 70% by weight of polymer, preferably not more than 50% by weight, more preferably not more than 40% by weight and most preferably not more than 30% by weight, compositions containing high molecular weight Polymers (ie polymers having molecular weights above about 300,000 g / mol average weight average Mw) usually not more than 25, preferably not more than 20 and more preferably not more than 15 wt.% Polymer.
  • high molecular weight Polymers ie polymers having molecular weights above about 300,000 g / mol average weight average Mw
  • compositions according to the invention comprise, in addition to the biocides, at least one of the polymers according to the invention in a total amount of at least 0.1% by weight, preferably at least 0.2% by weight. , particularly preferably at least 0.5% by weight, for example 1 or 2% by weight, and up to 10% by weight, preferably up to 7% by weight, more preferably up to 5% by weight and very particularly preferably up to to 3% by weight.
  • compositions according to the invention may contain conventional additives known to the person skilled in the art, such as, in particular, foam inhibitors, for example silicone oils, fatty alcohol alkoxylates, alcohol alkoxylates, carboxylic acid esters or phosphoric acid esters and / or corrosion inhibitors, such as borax, sodium nitrite, amines, ammonium salts of organic acids, phosphoric acid esters, alcohol alkoxylates or 2-butyne-1, 4-diol, and other compounds such as ethanolamine, polyalkylene oxides, polyethylene glycols.
  • foam inhibitors for example silicone oils, fatty alcohol alkoxylates, alcohol alkoxylates, carboxylic acid esters or phosphoric acid esters and / or corrosion inhibitors, such as borax, sodium nitrite, amines, ammonium salts of organic acids, phosphoric acid esters, alcohol alkoxylates or 2-butyne-1, 4-diol, and other compounds such as ethanolamine, polyal
  • compositions according to the invention for use as a metal quenching medium therefore advantageously comprise at least 70 and at most 99.8% by weight of water, at least 0.1 and at most 10% by weight of polymer according to the invention, one or more of the inventive compositions.
  • a metal object to be cooled can be sprayed or sprinkled with the preparation according to the invention. It is also possible to direct a metal object to be quenched by a liquid film flowing down from the preparation according to the invention. Particularly advantageously, however, a metal object to be quenched is immersed in a preparation according to the invention and thereby cooled (“quenched"), whereby the heat energy is dissipated particularly efficiently.
  • composition used according to the invention as a metal quenching medium preferably has a cooling rate at 550 ° C. of at least 75 ° C./seconds at a polymer solids content of 1% by weight and at most 75 ° C./seconds at 350 ° C.
  • composition used according to the invention as a metal quenching medium particularly preferably has a cooling rate at 550 ° C of at least 80 ° C / second and at 350 ° C at most 50 ° C / second at a polymer solids content of 1 wt.%.
  • composition used according to the invention as a metal quenching medium at a polymer solids content of 1% by weight very particularly preferably has a cooling rate at 550 ° C. of at least 90 ° C./seconds and at 350 ° C. not more than 40 ° C./seconds.
  • the composition according to the invention finds particular use as a metal quenching medium for hardening metal. It has been found that the biocides used according to the invention allow the desired stabilization of the compositions used according to the invention. Negative influences on the properties of the polymer in aqueous polymer solution, in particular formation or deterioration of odor or color, increase or decrease in viscosity, K value and / or pH and increase in ash content can usually be almost complete or completely avoided (within the scope of the respective measuring accuracies of the measuring methods). Also, precipitates or corrosion of metallic objects that come into contact with the preparation were not observed.
  • stabilization of the composition according to the invention is achieved, for example during storage.
  • This stabilization is achieved during storage:
  • the stabilization is also achieved when using a preparation according to the invention as a metal quenching medium.
  • the composition which can be used as a metal quenching medium, for example, has properties such as the physicochemical properties of the composition as such as well as their properties during use, such as as a metal quenching medium during the quenching process - not or not significantly changed. In particular, there is no or no significant change in the cooling rates.
  • Polymer LUVITEC ® K 90, solution 20%: polyvinylpyrrolidone aqueous solution with a solids content of 20.0% and a K value of 97 of BASF SE, CAS-No. 9003-39-8
  • the quenching behavior of the quench media was measured by means of "Smart Quench” from the company IVF
  • the portable test system consists of a test rod which has a total length of 400 mm at the tip of the test rod is the test piece, which has a diameter of 12.5 mm, a length of 60 mm and a weight of 240 g
  • This test specimen consists of a nickel-based alloy "Inconel 600". Inside the specimen, a thermocouple is installed. Via a connected computer, the cooling curves of the quenching media can be measured and evaluated.
  • the test specimen meets the international standard ISO 9950 and the American standards ASTM D 6200-97 and ASTM D 6482-99.
  • test specimen was heated in an induction furnace to a temperature of 860 ° C and then immersed in the associated circulating device, containing 1, 5 liters of the corresponding quenching medium immersed.
  • the quench media had a temperature of 23 ° C before the start of the measurement.
  • the stirring speed of the circulator was set at 1000 rpm during the measurements.
  • the cooling measurements were automatically started at 850 ° C.
  • the total measurement time was 20 seconds each. Comparative Examples 1 to 4 and Examples 1 to 9:
  • aqueous LUVITEC ® K 90 solution 20 wt.% By weight with a solids content of 20.% was mixed with water to a solids content of 1.% (Short LUVITEC ® K 90, 1% solution) is diluted. The amounts of biocide given in Table 1 were added and stirred. 1.5 liters of this solution were introduced into the circulation device. The quench curves were measured as described.
  • % In each case means “weight percent of solid polymer based on the total mass of the preparation", ppm refers to the total mass of the preparation, calculated on the biocide used as commercially available)
  • Example 7 LUVITEC ® K 90, 1% solution with 50 ppm MicroCare MT
  • Example 8 LUVITEC ® K 90, 1% solution with 250 ppm MicroCare MT
  • Example 9 LUVITEC ® K 90, 1% solution with 500 ppm MicroCare MT
  • the viscosity was determined as Brookfield RVT, measured with spindle 7 at 100 rpm and 23 ° C., according to DIN EN ISO 2555
  • the Fikentscher K value was determined in 1% strength by weight solution in water.
  • the pH was measured as a 10% by weight solution in water, according to Ph. Eur. 2.2.3 at 20 ° C.
  • biocides show no influence on the physical-chemical parameters and thus the stability of the polymer solutions during storage. Also, the ash content remains below the relevant limit, despite in some cases significantly higher amounts of biocides.
  • Figures 1 to 8 show the cooling curves associated with the tests: Figure 1 and 1 a: Cooling curves of Comparative Examples 1 to 4

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Abstract

L'invention concerne l'utilisation d'une composition comprenant un polymère contenant un monomère vinyl-lactame, un solvant aqueux et au moins un biocide, le biocide étant sans halogène et soluble dans la composition, pour des préparations dans le domaine des détergents et produits de nettoyage, des membranes, des inhibiteurs d'hydrates de gaz, de la céramique, des résines photosensibles, des gels, des laques, des films de revêtement, des écrans, du traitement des métaux et de la fabrication de métaux, en particulier en tant qu'agent de trempe des métaux.
PCT/EP2012/070970 2011-10-27 2012-10-23 Utilisation comme agent de trempe de métaux d'une composition comprenant un polymère contenant du vinyl-lactame, un solvant et au moins un biocide ne contenant pas d'halogène WO2013060679A1 (fr)

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WO2014032989A1 (fr) * 2012-08-28 2014-03-06 Basf Se Mélanges de conservateurs et solutions polymères stabilisées au moyen de ceux-ci
CN106591548A (zh) * 2016-11-08 2017-04-26 广东工业大学 一种丙三醇水溶液淬火冷却介质及其制备方法
CN108179253A (zh) * 2017-12-20 2018-06-19 马鞍山金泉工业介质科技有限公司 一种低温冷速接近淬火油的淬火液及其制备方法和应用
US20230235212A1 (en) * 2018-10-31 2023-07-27 Arkema France Composition that can be used to delay the formation of gas hydrates

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Publication number Priority date Publication date Assignee Title
WO2014032989A1 (fr) * 2012-08-28 2014-03-06 Basf Se Mélanges de conservateurs et solutions polymères stabilisées au moyen de ceux-ci
CN106591548A (zh) * 2016-11-08 2017-04-26 广东工业大学 一种丙三醇水溶液淬火冷却介质及其制备方法
CN106591548B (zh) * 2016-11-08 2019-02-15 广东工业大学 一种丙三醇水溶液淬火冷却介质及其制备方法
CN108179253A (zh) * 2017-12-20 2018-06-19 马鞍山金泉工业介质科技有限公司 一种低温冷速接近淬火油的淬火液及其制备方法和应用
US20230235212A1 (en) * 2018-10-31 2023-07-27 Arkema France Composition that can be used to delay the formation of gas hydrates

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