WO2009121947A1 - Composition polymère acide et son procédé de fabrication - Google Patents

Composition polymère acide et son procédé de fabrication Download PDF

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Publication number
WO2009121947A1
WO2009121947A1 PCT/EP2009/053982 EP2009053982W WO2009121947A1 WO 2009121947 A1 WO2009121947 A1 WO 2009121947A1 EP 2009053982 W EP2009053982 W EP 2009053982W WO 2009121947 A1 WO2009121947 A1 WO 2009121947A1
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polymer composition
weight
water
solvent
polymer
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PCT/EP2009/053982
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German (de)
English (en)
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Frank Dietsche
Bolette Urtel
Christian Hubert Weidl
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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
    • C08K5/04—Oxygen-containing compounds
    • C08K5/06—Ethers; Acetals; Ketals; Ortho-esters

Definitions

  • the present invention relates to an acidic polymer composition, a process for the preparation of this polymer composition, and the use of specific alkyne alkoxylates as a corrosion inhibiting component for this polymer composition.
  • Acid polymers For decades, different acidic polymers, such as. As polyacrylic acids or polymethacrylic acids and methods for their preparation. Acid polymers find z. B. Use in the manufacture of building aids (such as glass fiber mats, concrete and cement additives), dispersants z. As for pigments or in formulations to prevent deposits, for example in water tanks, dishwashers and similar devices.
  • passivating agents such as, for example, phosphates, phosphonates or other heavy metal-containing auxiliaries
  • passivating agents such as, for example, phosphates, phosphonates or other heavy metal-containing auxiliaries
  • An alternative to avoiding transport and storage corrosion in acidic polyacrylic acids and other acidic polymers or copolymers is to carry out a (simultaneous) neutralization step directly in connection with the preparation and / or dilute the polymers so strongly that the aggressive corrosive properties reduce to a tolerated limit or disappear completely.
  • these options are often neither economically nor ecologically advantageous because high water and Salzfrachtanteile greatly reduce the polymeric drug content and can greatly degrade the overall properties of the products in their subsequent use.
  • An object of the present invention was to find heavy metal-free, preferably water-soluble (soluble more than 5 percent), non-toxic and phosphorus-free, optionally also nitrogen-free and non-pH-modifying and non-salt-forming components which inhibit corrosion and which can be used before, during and / or after the preparation of the polyacrylic acids or acidic polymers (in particular in the pH range of ⁇ 4) and ensure low removal rates and a low pitting tendency on all common types of steel (in particular stainless steel).
  • the pH of the compounds may be e.g. B. measured according to DIN 19268)
  • WO 2004/074372 presents various copolymers which comprise acrylic acid or methacrylic acid monomer units, these polymers also being able to comprise various auxiliaries.
  • EP-A 0 583 086 describes the preparation of polymers with customary starters and / or regulators, mention being also made of polyols (ethanolamines).
  • US Pat. No. 4,618,448 describes a process for the preparation of corrosion inhibitors in which a water-soluble polymer is used which may contain as monomer units, inter alia, unsaturated carboxylic acids or unsaturated sulfonic acids.
  • EP-A 0 239 770 describes corrosion-inhibiting substances which contain, for example, propargyl alcohol (3-propynol) as structural unit. From US 5,630,985 a method for water treatment to prevent deposits is further known in which a quantity of water, a polyol is added. Various water-soluble copolymers having acidic properties are further described in EP-A 1 719 784. These water-soluble copolymers consist essentially of olefinically unsaturated carboxylic acid monomers, olefinically unsaturated carboxylic acid ester monomers and olefinically unsaturated, nonionic monomers.
  • JP-A 11264085 describes polymers containing methacrylic acid monomers which can be used as corrosion inhibitors.
  • JP-A 2001 329386 describes copolymers based on acrylic acids which have a molecular weight of 2,000 to 15,000 and which can be used as a corrosion inhibitor.
  • JP-A 11 310 888 describes another anticorrosive agent which is based on a copolymer with methacrylic acid building blocks.
  • acidic polymers refers to those polymers which have a multiplicity of acidic carboxylate groups (see EP-A 0 583 086) and generally have a pH of from 0 to 4.
  • the pH can be, for example, 10 . be determined in a 10 percent aqueous solution (according to DIN 19268).
  • an acidic polymer composition is to be provided which is storage stable (preferably for a period of at least two Weeks, especially at least two months, can be stored without significant change in properties), has a high thermal capacity, can also be transported in concentrated form (preferably 30 to 70%), does not tend to discoloration due to metal salts and the surfaces of the vessels (eg made of steel or other metal alloys) does not attack.
  • the composition should also preferably have a low viscosity already at low temperatures (eg room temperature), which allows good processability. This should be done by using low molecular weight non-volatile corrosion inhibitors.
  • Containers of different metallic and non-metallic materials are suitable for transporting and storing the acidic polymers.
  • the corrosion protection should preferably not be achieved by temporary or permanent treatment of the metallic surface, for example by application of passivation layers or other protective layers (paints).
  • Another problem with providing the acidic polymer compositions is the increasing demand for improved biocompatibility, reduction of phosphorus-containing additives (inorganic phosphate, phosphonates and organically bound phosphorus), and improved tolerance of the individual components to each other, for example to prevent product spoilage , A reduction in nitrogen-containing additives is desired.
  • phosphorus-containing additives inorganic phosphate, phosphonates and organically bound phosphorus
  • Another object of the present invention is to provide a (stable) acidic polymer composition which can be provided easily and inexpensively and which does not have the above-mentioned disadvantages.
  • radicals R 1 are each independently H or methyl and the indices n and n 'are independently from 1 to 10, d) 0 to 20 wt .-%, in particular 0 to 10 wt .-%, of one or several additives and / or auxiliaries.
  • the polymer composition consists of the o. Components a) to d).
  • a further subject of the invention is also a polymer composition which contains:
  • radicals R 1 are each independently H or methyl and the indices n and n 'independently of one another are numbers from 1 to 10, d) 0 to 10 wt .-% of one or more additives and / or auxiliaries.
  • the invention also provides a polymer composition which contains water as solvent (L) and as polymer component (B) at least one polymeric or copolymeric compound composed of monomers from the group of acrylic acid, methacrylic acid and maleic anhydride (or maleic acid).
  • the invention also provides a polymer composition which contains water as solvent (L) and as polymer component (B) at least one polymeric or copolymeric compound selected from the group consisting of polyacrylic acids and polymethacrylic acids.
  • the invention also relates to a polymer composition containing 100 to 5,000 ppm of a Alkinalkoxylates as component A, wherein this contains 1 to 5 ethylene oxide or propylene oxide units, in particular 1 to 3 units.
  • the invention also provides a polymer composition which contains as solvent (L) water and additionally 0.1 to 5 wt .-% of at least one further polar solvent.
  • the invention also provides a polymer composition which comprises 30 to 70% by weight of polymer component (B), water as solvent (L) and 1 to 10% by weight of additives and / or auxiliaries from the group of water-soluble complexing agents, containing surface-active substances and pH regulators.
  • the polymer composition often contains from 30 to 70% by weight, in particular from 30 to 60% by weight, of polymer component (B), which is preferably a polyacrylic acid or a polymethacrylic acid.
  • the invention also provides a polymer composition
  • a polymer composition comprising 45 to 55% by weight of polyacrylic acid, 45 to 55% by weight of water and 0.1 to 5% by weight of one or more additives and / or auxiliaries from the group of surface-active agents Contains substances and / or pH regulators.
  • the invention also relates to a process for the preparation of a polymer composition in which an acidic polymer component (B) is prepared by polymerization in the presence of an alkinalxyl acrylate (A) of the general formula (I) or (II), and if appropriate with a solvent ( L) and / or additives and / or auxiliaries.
  • an acidic polymer component (B) is prepared by polymerization in the presence of an alkinalxyl acrylate (A) of the general formula (I) or (II), and if appropriate with a solvent ( L) and / or additives and / or auxiliaries.
  • the composition according to the invention contains at least one (water-soluble) alkoxylated alkynol (A) and optionally a solvent (L). It has been found that, surprisingly, the alkinal alkoxylates used as component (A) can be added before or during the polymerization.
  • alkyne alkoxylates are not destroyed or significantly consumed in the polymerization and acidic conditions.
  • composition according to the invention may also contain other components, such as further active ingredients and / or additives and / or auxiliaries.
  • the polymer compositions according to the invention contain at least one alkoxylated alkynol (A).
  • This component (A) which may preferably be added before or at, but optionally also after the polymerization, is explained in more detail below.
  • Alkyne alkoxylates have been known for years, for example from DE-A 2 241 155. They are used, inter alia, as an additive in the electrodeposition of nickel or cobalt.
  • US Pat. No. 3,004,925 already describes the use of ethoxylated butynediol derivatives and ethoxylated propynol derivatives as corrosion inhibitors in aqueous solutions.
  • the OH groups are each modified with - (CH 2 -CH 2 O) x - groups, where x has a value of 3 to 25.
  • the disclosed alkynols additionally have one or more alkyl, aryl, cycloalkyl and aralkyl groups.
  • the component (A) in the preparation used for the process according to the invention is preferably an amount of (based on the total composition) 1 to 7,000 ppm, in particular 10 to 6,000 ppm, often also 100 to 5,000 ppm, of at least one Alkinalkoxylates of the general formula (I) or (II),
  • indices n and n 'independently of one another are from 1 to 10.
  • n thus stand for average chain lengths, the average value not having to be a natural number but also being an arbitrary rational number. It is preferable that n and n 'and a number from 1 to 8, in particular from 1 to 3.
  • the radicals R 1 in (I) and (II) are each, independently of one another, preferably H or methyl.
  • the alkyleneoxy groups may be exclusively groups derived from ethylene oxide units (EO) or groups derived exclusively from propylene oxide (PO). However, they may also be groups having both ethylene oxide units and propylene oxide units. They are preferably polyoxyethylene units. It is also possible to use mixtures of (I) and (II) and / or mixtures of different compounds (I) or various compounds. fertilize (II) can be used. Preference is given to using compounds of the formula (I).
  • ppm (I) or (II) are preferably used, in particular 10 to 6,000 ppm and particularly preferably 100 to 5,000 ppm. All concentrations are based on the total polymer composition. It is also possible to first prepare and distribute a concentrate of the composition which can be chemically modified on site or diluted to the desired concentration.
  • the amount of (I) and / or (II) also depends on the type and amount of the polymer component (B) and the other components and on the temperature at which the polymer composition is to be processed. As a rule, the higher the temperature, the higher the concentration of component (A) should be.
  • the compounds used (A) are in a known manner z. B. by alkoxylation of butynediol or propynol (propargyl alcohol) available, as described for example in DE-A 22 41 155.
  • the composition of the invention may contain a solvent (L).
  • the component L is water or another solvent which is suitable for dissolving or dispersing, suspending or emulsifying the acidic polymer (component B).
  • a solvent is understood as meaning a liquid matrix in which the various constituents of the composition according to the invention are dispersed as finely as possible. Such a fine distribution can be, for example in the sense of a molecularly disperse distribution, a true solution of the ingredients in the solvent.
  • solvent also includes liquid matrices in which the ingredients are distributed in the sense of an emulsion or dispersion, i.e., do not form a molecular-disperse solution.
  • Suitable solvents (L) are, for example, water and water-miscible and water-immiscible solvents.
  • Suitable water-miscible solvents are, for example, primary or secondary mono- or polyalcohols, for example having 1 to about 6 C atoms, such as methanol, ethanol, propanol, isopropanol, n-butanol, isobutanol, pentanol, hexanol, cyclohexanol or glycerol.
  • Also suitable as water-miscible solvents are low molecular weight ketones such as acetone or methyl ethyl ketone or ether alcohols such as diethylene glycol or triethylene glycol.
  • solvents (L) which are immiscible or only to a small extent miscible with water.
  • solvents (L) include, for example, ethers, such as diethyl ether, dioxane or tetrahydrofuran, aromatic solvents, such as toluene or xylene, halogenated solvents, such as dichloromethane, chloroform or tetrachloromethane, and optionally substituted aliphatic solvents, including, for example, the higher homologs of the abovementioned alcohols and ketones and paraffin hydrocarbons ,
  • the abovementioned solvents (L) can be used individually or as a mixture of two or more of the solvents mentioned.
  • the solvent used is water, if appropriate in admixture with one or more of the abovementioned, preferably water-soluble, solvents.
  • Especially preferred are purely aqueous compositions which contain no other solvents.
  • the solvent may contain, for example, an emulsifier to form a substantially stable W / O emulsion (Water / Oil) or O. / W emulsion to allow.
  • an emulsifier to form a substantially stable W / O emulsion (Water / Oil) or O. / W emulsion to allow.
  • the composition contains from 20 to 60% by weight of water.
  • Polymer component B is an acidic polymer or copolymer, preferably composed of:
  • n is 0 to 10, preferably 0 to 5, particularly preferably 0 to 3;
  • R 1, R 2, R 3 independently of one another are hydrogen, C 1 - to C 8 -alkyl which may be branched or unbranched, C 3 - to C 6 cycloalkyl, C 2 - to C 18 -
  • Alkenyl which may be branched or unbranched, C 3 - to C 6 -cycloalkenyl, C 6 - to C 12 -aryl which may be substituted by alkyl or further aryl substituents, wherein said radicals R 1 , R 2 and / or R 3 may optionally be substituted by at least one carboxyl group, or a carboxyl group; preferably R 1 , R 2 and R 3 are hydrogen or C 1 - to C 18 -alkyl which is unbranched and is optionally substituted by at least one carboxyl group, or a carboxyl group; particularly preferably, one of the radicals R 1 or R 2 or R 3 is a carboxyl group and the remaining radicals are hydrogen or methyl; or R 1 , R 2 and R 3 are hydrogen or methyl; R 4 and R 5 are independently hydrogen, C 1 to C 18 alkyl, which may be branched or unbranched, C 3 to C 6 cycloalkyl, C 2 to C 18 alkeny
  • esters of compounds of the formula (I), particular preference is given to maleic acid, fumaric acid, itaconic acid, crotonic acid or their salts, (esters,) anhydrides;
  • the polymer component (B) may also contain other comonomers (B4).
  • Component (B1) is acrylic acid and / or methacrylic acid or a salt of (meth) acrylic acid. It is also possible to use mixtures of the stated components as component B1. Suitable salts of (meth) acrylic acid are, in particular, the alkali metal salts or alkaline earth metal salts, preferably lithium, sodium or potassium salts. umsalze. Very particular preference is given to using, as component B1, acrylic acid and / or methacrylic acid, in particular acrylic acid, in their free acid form.
  • n is 0 to 10, preferably 0 to 5, particularly preferably 0 to 3
  • R 1 , R 2 , R 3 are independently hydrogen, C 1 - to C 18 -alkyl, which may be branched or unbranched, C 3 - to C 6 -cycloalkyl, C 2 - to Cia-alkenyl, which may be branched or unbranched can, C 3 - to C 6 -cycloalkenyl, C 6 - to C 12 -aryl which may be substituted by alkyl or further aryl substituents, said radicals R 1 , R 2 and / or R 3 optionally having at least one carboxyl group or a carboxyl group; R 1 , R 2 and R 3 are preferably hydrogen or C 1 - to C 18 -alkyl which is unbranched and is optionally substituted by at least one carboxyl group, or a carboxyl group; particularly preferably, one of the radicals R 1 or R 2 or R 3 is a carboxyl group and the remaining radicals are hydrogen or methyl; or R 1 , R 2 and R
  • R 4 and R 5 are independently hydrogen, C 1 to C 18 alkyl, which may be branched or unbranched, C 3 to C 6 cycloalkyl, C 2 to C 18 alkenyl, which may be branched or unbranched can, C 3 - to C 6 - cycloalkenyl, C 6 - C 12 aryl can be up, the tuenten with alkyl or other substituted Arylsubsti-; R 4 and R 5 are preferably hydrogen or C 1 - to C 18 -alkyl which is unbranched, very particularly preferably hydrogen or methyl,
  • the component B2 is selected from at least one compound selected from the group consisting of crotonic acid, maleic acid, fumaric acid, itaconic acid, or salts, (optionally esters) and anhydrides of said acids. Particular preference is given to using maleic anhydride or maleic acid as component B2.
  • Suitable salts of the abovementioned acids are in particular the alkali metal and alkaline earth metal salts.
  • Optionally usable esters are the reaction products of said acids with C 1 - to C 20 -alcohols, preferably with C 1 - to C 16 -alcohols, particularly preferably with C 1 to C 10 -alcohols.
  • Preference is given to using maleic acid, salts or esters of maleic acid or maleic anhydride.
  • Preferred salts are already mentioned above. Very particular preference is given to using maleic anhydride as component (B2).
  • the acidic polymers (component B) may contain not only monomers (B1) and monomers (B2) but also other acid-stable, vinylidene monomers (B3). It is also possible that the polymers (component B) contain, in addition to monomers of component (B1), either monomers of component (B2) or (B3).
  • Suitable further components (B4) for the polymer component (B) are those comonomers which are polymerizable with the monomers mentioned under B1 and B2. Such monomers are preferably ethylenically unsaturated monomers. Suitable monomers having at least one ethylenically unsaturated group are, for example: olefins such as ethylene or propylene, vinylaromatic monomers such as styrene, divinylbenzene, 2-vinylnaphthalene and 9-vinyl-anthracene, substituted vinylaromatic monomers such as p-methylstyrene, .alpha.-methylstyrene, o-chlorostyrene, p-chlorostyrene, 2,4-dimethylstyrene, 4-vinylbiphenyl and vinyltoluene, esters of vinyl alcohol and monocarboxylic acids having 1 to 18 C atoms, such as vinyl acetate, vinyl propionat
  • R 'and R "independently of one another are H or C r to C 8 -alkyl and n is 0, 1, 2 or 3.
  • such polymer components B are used in the composition according to the invention which contain acid-stable, vinylidene comonomers (B3) in addition to monomers (B1).
  • the polymer component of the polymer composition is substantially free of monomers of group (B4).
  • component B may also be a copolymer composed of acrylic acid and maleic anhydride (or maleic acid).
  • the proportion of acrylic acid is preferably 50 to 99% by weight, more preferably 50 to 80% by weight, and the proportion of maleic anhydride (or maleic acid) is just 1 to 50% by weight, particularly preferably 15 to 40% by weight.
  • component B is a copolymer composed of
  • (Meth) acrylic acid and maleic anhydride For example, the copolymer is composed of 20 to 80% by weight of (meth) acrylic acid and 10 to 40% by weight of maleic anhydride.
  • the polymers used as component B can be prepared by various methods known to those skilled in the art.
  • the polymer compositions are preferably prepared by free radical copolymerization of the stated components B1 and / or B2 and / or B3 and / or B4.
  • the proportions of the components used are varied. bar.
  • the free radical copolymerization can be carried out, for example, in solution, emulsion, dispersion, suspension or substance.
  • Suitable polymerization processes for the preparation of the polymers used as component B are listed, for example, in DE-A 196 06 394.
  • the polymers B are particularly preferably prepared by free radical copolymerization in solution.
  • the solvent is preferably selected from the group consisting of water, alcohols, ethers and ketones, particularly preferably water alone. If anhydride copolymers are obtained, they are preferably hydrolyzed by addition of suitable amounts of water.
  • the polymerization conditions are known to the person skilled in the art.
  • the acidic polymers (component B) can be obtained in a further embodiment by polymer-analogous reactions. Suitable polymer-analogous reactions are known to the person skilled in the art.
  • the preparation of the carboxylate-containing copolymers by appropriate functionalization of copolymers prepared by copolymerization; by reaction of polyhydric alcohols with higher-valent carboxylic acids possible.
  • Homo- or copolymers are generally to be understood as meaning branched or preferably linear compounds which have at least 3 repeat units, preferably more than 10 repeat units.
  • the weight average molecular weight (Mw) of the homo- or copolymers used according to the invention is generally from 1000 to 5,000,000 g / mol, preferably from 1,000 to 500,000 g / mol, frequently from 1,000 to 100,000 g / mol, in particular from 1,000 to 50,000 g / mol.
  • the polymer may also have low cross-linking, so that no molecular weight can be stated, although the polymer can be dispersed, emulsified or suspended in technically customary solvents.
  • the molecular weight (Mw) can, for. B. be determined by gel permeation chromatography against a polystyrene standard.
  • the acidic polymers used as component B according to the invention are hydrophilic copolymers.
  • a polymer composition which contains
  • radicals R 1 are each independently H or methyl and the indices n and n 'independently of one another are numbers from 1 to 8, and d) 0.1 to 10 wt .-% of one or more additives and / or adjuvants ,
  • the subject matter is also a polymer composition which contains (L) water as solvent and contains as polymer component (B) at least one polymeric or copolymeric compound from the group of polyacrylic acids and polymethacrylic acids.
  • Preferred is a polymer composition containing as solvent (L) water and additionally 0.1 to 5 wt .-% of at least one further polar solvent.
  • the invention also relates to the use of a composition as described above for the preparation of building aids, dispersants or water treatment agents.
  • the invention also provides a polymer composition which contains water (or else water and contains no further solvent) as solvent (L) and as polymer component (B) at least one compound from the group of polyacrylic acids, polymethacrylic acids and copolymers of acrylic acid or methacrylic acid with monomers from the group of maleic anhydride (MSA), isobutene (IB), diisobutene (DIB), vinyl allyl ether, hydroxybuyl vinyl ether (HBVE) and polyethylene glycol acrylic acid polymers.
  • MSA maleic anhydride
  • IB isobutene
  • DIB diisobutene
  • HBVE hydroxybuyl vinyl ether
  • polyethylene glycol acrylic acid polymers instead of MSA, its open derivatives can also be used.
  • the polymer compositions may contain as solvent (L) water and further from 0.01 to 20 wt .-%, in particular 0.1 to 10 wt .-% of an additional component (additives and / or auxiliaries). You can also contain as solvent (L) water and at least one other polar solvent. For example, they may contain water as solvent (L) and a water-soluble complexing agent (K) as additional component.
  • the polymer composition according to the invention preferably contains water as solvent (L), the polymer composition generally being used as a concentrated polymer composition, ie. H. having a polymer content of at least 30% by weight, in particular at least 40% by weight, preferably at least 45% by weight.
  • L water as solvent
  • the solvent component (L) used for the polymer composition according to the invention is preferably a polar solvent, in particular water, in an amount of 0 to 70% by weight, preferably 20 to 60% by weight, in particular 30 to 50% by weight.
  • the water can also be used together with other solvents. The percentages here and below always refer to the amount of all components of the composition.
  • the polymer compositions often still contain one or more additives or auxiliaries, even if their addition is not necessary in every case.
  • the amount of such additives is often 0 to 20 wt .-%, preferably 0.01 to 10% by weight and particularly preferably 0.1 to 10 wt .-%.
  • Adjuvants are in particular a surface-active substance.
  • a surface-active substance Preferably, 0.01 to 10 wt .-% and particularly preferably 0.05 to 8 wt .-% of the surfactant used.
  • suitable surfactants include conventional anionic or nonionic surfactants. It can also be used several different surfactants. Among the surfactants, a suitable choice can be made depending on the desired application of the polymer composition. Nonionic and anionic surfactants are preferably used. The following examples are intended to explain the invention in more detail:
  • corrosion inhibitor (IV) propoxylated butynediol having 1 to 5 propylene oxide units, water content 0.8% by weight
  • the following test shows the extent to which the dissolution of iron from stainless steel surfaces and the pitting tendency of a solution which has been brought into contact with a steel surface for a long time is suppressed or completely prevented by the addition of a substance.
  • stainless steel 1.4541 (X ⁇ CrNiTi 18-10), stainless steel 1.4571 (X6CrNiMoTi17-12-2) and stainless steel 1.4539 (X1 NiCrMoCu32-28-7) of size 50 mm x 20 mm x 2 mm were used. Investigated were also center-welded corrosion samples (50 mm x 20 mm x 2 mm), which were installed in the liquid and in the vapor space. To evaluate a possible susceptibility to stress corrosion cracking, the samples of materials 1.4541 and 1.4571 were roughly ground on one side. b) The metal samples were cleaned for the tests as follows:
  • the panels were easily wiped with ethyl acetate.
  • the thus pretreated sheet is at a voltage of 10 volts in a degreasing bath of the following components
  • nonionic surfactant ethoxylated nonylphenol, approx. 10 EO units
  • the plate is removed and rinsed under running demineralised water for five seconds, blown off with air and used immediately for testing purposes.
  • the sheets will be used directly in the corrosion test without further storage, because otherwise the re-forming oxide layer falsifies the result of the corrosion test.
  • the test electrolyte used is a polymer composition (Ia) according to the invention. It is an unneutralized, 50% solution of a radically polymerized, aqueous Homopolyacryl Textre (M w 1,000-20,000 g / mol, Restacryl Text content ⁇ 2000 ppm, solids content 50%) of freshly distilled acrylic acid at pH 1-2.5 used; this polymer solution contains no phosphorus-containing additives; Sodium persulfate solution serves as a starter; the polymerization time is 14h; Solution (1a).
  • the test electrolyte used is furthermore a polymer composition (Ib) according to the invention: Unneutralized 30% solution of a free-radically polymerized aqueous polyacrylic-co-methacrylic acid (M w 1,000-50,000 g / mol, residual acrylic acid content ⁇ 2,000 ppm, solids content 30%) from 1 part fresh distilled acrylic or 3 parts of freshly distilled methacrylic acid at pH 2.1-3.5 used; this polymer solution contains no phosphorus-containing additives; Sodium persulfate solution as a starter; Polymerization time 20h; Solution (1b).
  • Unneutralized 30% solution of a free-radically polymerized aqueous polyacrylic-co-methacrylic acid M w 1,000-50,000 g / mol, residual acrylic acid content ⁇ 2,000 ppm, solids content 30%
  • this polymer solution contains no phosphorus-containing additives
  • Sodium persulfate solution as a starter
  • Polymerization time 20h Solution (1b).
  • the test electrolyte used is furthermore a polymer composition (Ic) according to the invention: Unneutralized 30% solution of a free-radically polymerized aqueous polyacrylic-co-maleic acid (M w 3,000-50,000 g / mol, residual acrylic acid content ⁇ 2,000 ppm, solids content 30%) from 1 part fresh distilled acrylic or 1 part of maleic anhydride used at pH 2.2-4; this polymer solution contains no phosphorus containing additives; Hydrogen peroxide solution as a starter; Polymerization time 22h; Solution (1c).
  • Unneutralized 30% solution of a free-radically polymerized aqueous polyacrylic-co-maleic acid M w 3,000-50,000 g / mol, residual acrylic acid content ⁇ 2,000 ppm, solids content 30%
  • this polymer solution contains no phosphorus containing additives
  • Hydrogen peroxide solution as a starter
  • Polymerization time 22h Solution (1c).
  • the corrosion inhibitor to be tested (component A) is dissolved in the original polymer solution in the form of a solution or as a pure liquid product in the amount indicated in Table 1. It was possible to determine by means of quantitative GC analysis (area% relative to a calibration substance) before, during (every 2 hours) and after the polymerization a corrosion inhibitor content of> 95% (at the initial charge), i. the corrosion inhibitors (I-IV) do not consume during the polymer synthesis.
  • the stainless steel sheet is used immediately after weighing. In each case a prepared sheet is hung in a filled with solution 1a, solution 1b and solution 1c 250 ml beaker with nitrogen inertization, so that it is completely covered by the solution and dormant.
  • the beaker is stored at 60 ° C. for a period of 28 days.
  • the plates are then removed from the solutions, rinsed with demineralized water and blown dry with air. Subsequently, the mass is determined in each case.
  • the efficiency (E) is determined by the mass loss ⁇ m p . ⁇ Relative to the loss of mass in a corresponding control experiment without inhibitor Am 0 .
  • component (A) can be added even before the polymerization.
  • the polymer composition according to the invention also satisfies the following requirements:

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Abstract

L'invention concerne une composition polymère, contenant les composants suivants : 10 à 70 % en poids d'un solvant (L), 30 à 70 % en poids d'un composant polymère acide (B), 1 à 7000 ppm d'un alcoxylate d'alcyne (A), qui correspond à la formule générale HC=C-CH2-O(-CH2-CHR1-O-)nH, dans laquelle le radical R1 représente H ou méthyle et n représente 1 à 10, ainsi qu'éventuellement des additifs supplémentaires. La composition selon l'invention est stable au stockage pendant des durées prolongées et peut être conservée dans des contenants de transport et de stockage usuels.
PCT/EP2009/053982 2008-04-04 2009-04-03 Composition polymère acide et son procédé de fabrication WO2009121947A1 (fr)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0294641A2 (fr) * 1987-06-06 1988-12-14 Bayer Ag Hydroxybenzamides polyaralcoylés, procédé de leur préparation et leur utilisation
WO2005033364A1 (fr) * 2003-09-30 2005-04-14 Basf Aktiengesellschaft Procedes pour decaper des surfaces metalliques au moyen d'alcynols alcoxyles
EP1719784A1 (fr) * 2005-05-06 2006-11-08 National Starch and Chemical Investment Holding Corporation copolymère compatible avec un alcool

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0294641A2 (fr) * 1987-06-06 1988-12-14 Bayer Ag Hydroxybenzamides polyaralcoylés, procédé de leur préparation et leur utilisation
WO2005033364A1 (fr) * 2003-09-30 2005-04-14 Basf Aktiengesellschaft Procedes pour decaper des surfaces metalliques au moyen d'alcynols alcoxyles
EP1719784A1 (fr) * 2005-05-06 2006-11-08 National Starch and Chemical Investment Holding Corporation copolymère compatible avec un alcool

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